CN111635536B - Graphene oxide loaded renewable antibacterial polypropylene material and preparation method thereof - Google Patents
Graphene oxide loaded renewable antibacterial polypropylene material and preparation method thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 69
- -1 polypropylene Polymers 0.000 title claims abstract description 58
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical compound C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 claims abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 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 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- GQECANUIPBFPLA-UHFFFAOYSA-N 2-(carboxymethylsulfanylcarbothioylsulfanyl)acetic acid Chemical compound OC(=O)CSC(=S)SCC(O)=O GQECANUIPBFPLA-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 238000013467 fragmentation Methods 0.000 abstract description 3
- 238000006062 fragmentation reaction Methods 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 abstract description 3
- 238000006276 transfer reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003384 small molecules Chemical group 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
- A41D13/1192—Protective face masks, e.g. for surgical use, or for use in foul atmospheres with antimicrobial agent
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/30—Antimicrobial, e.g. antibacterial
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- 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
- C08F8/42—Introducing metal atoms or metal-containing groups
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- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention discloses a graphene oxide loaded renewable antibacterial polypropylene material and a preparation method thereof; according to the graphene oxide loaded renewable antibacterial polypropylene material, 4-vinylbenzaldehyde is introduced to polypropylene with an antibacterial effect through a reversible addition-fragmentation chain transfer reaction, and then a product obtained through aldehyde-amine condensation reacts with graphene oxide to obtain a graphene oxide loaded renewable antibacterial polypropylene material; meanwhile, the tertiary amine element has good antibacterial performance.
Description
Technical Field
The invention belongs to a high polymer material, and particularly relates to a graphene oxide loaded renewable antibacterial polypropylene material and a preparation method thereof.
Background
The polypropylene has the advantages of rich raw materials, low production cost, light weight, high strength, good wear resistance and elasticity, good hot melt property, excellent ultrasonic welding property, low price and the like, and also has the advantages of relatively stable chemical property, acid and alkali resistance, organic chemical solvent resistance, moth-eating resistance, mildew and rot resistance and no toxicity, and the moisture absorption rate of the fiber material is zero, so that the polypropylene is suitable for environments under various conditions.
But polypropylene does not have the bacterinertness, and can not be regenerated, along with disposable non-woven fabrics polypropylene product quantity constantly increases, disposable non-woven fabrics polypropylene product rubbish pollution problem also is more and more serious, like CN107981441B discloses a medical high efficiency gauze mask that disinfects, the gauze mask is laminated structure, outside-in includes in proper order: the sterilization layer comprises a first non-woven fabric layer, a sterilization layer and a second non-woven fabric layer; the sterilizing layer consists of 90-95 parts by weight of polypropylene fibers and 5-10 parts by weight of erbium-doped nano zinc oxide, and the prepared medical high-efficiency sterilizing mask has good antibacterial performance. For example, CN103467843B discloses a PP antibacterial plastic, which is composed of the following components in parts by weight: 155 parts of PP (polypropylene), 5-10 parts of brucite, 10-20 parts of triphosphite, 10-15 parts of POE (polyolefin elastomer), 10-13 parts of ferrocene, 7-9 parts of phthalic anhydride, 10-15 parts of melamine cyanurate, 7-9 parts of silver-loaded zirconium phosphate, 10-15 parts of copper-loaded zirconium phosphate, 10 parts of potassium titanate whisker and 5-8 parts of organotin. The prepared PP antibacterial plastic has a good antibacterial function, and meanwhile, the PP antibacterial plastic has good compatibility with resin, and the plastic has long-term antibacterial property. But the obtained antibacterial polypropylene is not recyclable, so that the invention provides the graphene oxide loaded renewable antibacterial polypropylene material and the preparation method thereof, and the recycling of the antibacterial polypropylene is realized.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a graphene oxide loaded renewable antibacterial polypropylene material and a preparation method thereof, 4-vinylbenzaldehyde is introduced to polypropylene with antibacterial effect through reversible addition-fragmentation chain transfer reaction, and then a product obtained through aldehyde-amine condensation reacts with graphene oxide to obtain the graphene oxide loaded renewable antibacterial polypropylene material; meanwhile, the tertiary amine element has good antibacterial performance.
The invention aims to provide a graphene oxide loaded renewable antibacterial polypropylene material.
The invention also aims to provide a preparation method of the graphene oxide loaded renewable antibacterial polypropylene material.
The above purpose of the invention is realized by the following technical scheme:
the graphene oxide loaded renewable antibacterial polypropylene material has a structural formula shown as the following formula (I):
wherein n is 50-2000, and m is 10-5000.
The reaction process and the preparation method of the graphene oxide loaded renewable antibacterial polypropylene material are as follows:
1. and (3) preparing a small-molecule chain transfer agent.
Adding a certain amount of bis (carboxymethyl) trithiocarbonate, N, N-dimethyl isopropanolamine, benzene and p-toluenesulfonic acid into a three-necked flask for esterification, and heating and refluxing for 2.0h to obtain the micromolecule chain transfer agent. Wherein the molar ratio of the bis (carboxymethyl) trithiocarbonate to the N, N-dimethylisopropanolamine is 1: 1.5.
2. And (3) preparing a macromolecular precursor PP through esterification reaction.
Adding the micromolecule chain transfer agent obtained in the step (1) into a flask with a branch mouth, and dropwise adding SOCl2Obtaining an acyl chlorination product; and dissolving the acyl chloride product with toluene, adding acid-binding agent pyridine, and performing esterification reaction with the single-terminal hydroxyl polypropylene to obtain a macromolecular precursor PP, wherein the molar ratio of the bis (carboxymethyl) trithiocarbonate to the single-terminal hydroxyl polypropylene is 5: 1.
3. Preparing the block copolymer of antibacterial polypropylene and poly-4-vinyl benzaldehyde.
Adding a certain amount of the prepared macromolecular precursor PP, a monomer 4-vinylbenzaldehyde and an initiator azobisisobutyronitrile AIBN into a round-bottom flask, and dissolving by using an organic solvent dioxane; reacting for 6 hours at 70 ℃ to obtain the block copolymer of the antibacterial polypropylene and the poly 4-vinyl benzaldehyde. Wherein the molar ratio of the macromolecular precursor PP to the azobisisobutyronitrile and the 4-vinylbenzaldehyde is 1:4:500, and the molar concentration of the 4-vinylbenzaldehyde is 1 mol/L.
4. And (3) preparing the silane coupling agent modified antibacterial polypropylene.
Adding 3-Aminopropyltriethoxysilane (APTES) and glacial acetic acid into a round bottom flask, dissolving with toluene, and adding N2Protecting, and reacting for 16h at 100 ℃ to obtain the silane coupling agent modified antibacterial polypropylene。
5. And (3) preparing the graphene oxide loaded renewable antibacterial polypropylene.
Adding silane coupling agent modified antibacterial polypropylene and graphene oxide into a round bottom flask with a branch mouth, dissolving with ethanol, and adding N2And (4) protecting, and reacting for 16h at 80 ℃ to obtain the graphene oxide loaded renewable antibacterial polypropylene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the prepared graphene oxide loaded renewable antibacterial polypropylene material is prepared by introducing 4-vinylbenzaldehyde onto polypropylene with antibacterial effect through reversible addition-fragmentation chain transfer reaction, and then reacting a product obtained through aldehyde-amine condensation with graphene oxide to obtain the graphene oxide loaded renewable antibacterial polypropylene material; meanwhile, the tertiary amine element has good antibacterial performance.
Drawings
Fig. 1 is a nuclear magnetic hydrogen spectrum diagram of a graphene oxide-loaded renewable antibacterial polypropylene material.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
And (3) preparing a small-molecule chain transfer agent.
Placing a 100mL three-necked flask provided with a water separator, a thermometer and a reflux condenser on a stirrer, adding bis (carboxymethyl) trithiocarbonate (1.12g,5.0mmol), N, N-dimethyl isopropanolamine (0.67g,6.5mmol), (0.026g,0.15mmol) p-toluenesulfonic acid and 50mL toluene, heating and refluxing at 130 ℃ for 2.0h, cooling the reaction solution to below 30 ℃, pouring the reaction solution into a separating funnel, and sequentially using saturated NaHCO3Solution, saturated NaCl solution, saturated CaCl2Washing the solution, and adding anhydrous MgSO4Dried overAnd (4) performing fractional distillation, and collecting corresponding fractions to obtain 1.38g of the small-molecular chain transfer agent with the yield of 84.2%.
Example 2
Preparation of macromolecular precursor PP by esterification reaction
A50 mL flask was charged with bis (carboxymethyl) trithiocarbonate (1.12g,5.0mmol) and 20mL anhydrous tetrahydrofuran THF, and after the reaction temperature rose to 70 deg.C, SOCl was slowly added dropwise2(3.6ml,5.0mmol), reaction was carried out for 1.5h after completion of dropwise addition, and after completion of the reaction, SOCl was removed by distillation under reduced pressure2And THF to obtain bis (carboxymethyl) trithiocarbonate acyl chloride product, and dissolving with proper amount of toluene.
Into a 50ml Schlenk flask were added single-terminal hydroxypolypropylene (0.84g,1.0mmol), N2Under protection, adding 40ml of anhydrous toluene by using a disposable syringe, slowly heating to 70 ℃, injecting 1ml of pyridine after the single-end hydroxyl polypropylene is completely dissolved, stirring for 30min, dropwise adding the bis (carboxymethyl) trithiocarbonate acyl chloride product, heating to 80 ℃, continuing to react for 1.5h, cooling the product to room temperature, continuously dissolving/precipitating twice by using toluene/methanol, and drying at the temperature of 45 ℃ in vacuum to constant weight to obtain 0.80g of polypropylene macromolecule transfer agent, wherein the yield is 75.6%.
Example 3
Preparing the block copolymer of antibacterial polypropylene and poly-4-vinyl benzaldehyde.
Macromolecular precursor PP (0.0232g,0.01mmol), monomer 4-vinylbenzaldehyde (0.6608g,5mmol) and initiator azobisisobutyronitrile AIBN (0.066g,0.4mmol) are added into a 10mL Schlenk bottle, nitrogen is pumped for three times, 5mL dioxane is added, and a flask containing the mixture is put into an oil bath kettle at 75 ℃ for reaction for 4 hours. After the reaction time is reached, the reaction is terminated, precipitating for 3 times by using a precipitator methanol/water, removing residual monomers and impurities, and drying at the temperature of 45 ℃ in vacuum until the weight is constant, so that 0.063g of the antibacterial polypropylene and poly 4-vinylbenzaldehyde segmented copolymer is obtained, and the yield is 71.3%.
Example 4
And (3) preparing graphene oxide.
In a 500mL round bottom flask, 3g of layered graphite was added followed by slow addition of 150mL of concentrated sulfurAcid (98%) was stirred in an ice bath until homogeneous. Under the condition of ensuring that the temperature of the system in the beaker is less than 10 ℃, 11.3g of KMnO is slowly added into the beaker4The dropwise addition was completed in about 1 hour. The beaker was placed on stirring at room temperature for a further 18 h. Then 500mL of deionized water was slowly added to the system until no more bubbles were formed. 10mL of a 30 wt% aqueous hydrogen peroxide solution was added to the reaction flask. And (3) carrying out vacuum filtration on the suspension, washing the suspension for 3 times by using 5% dilute hydrochloric acid, re-dispersing the obtained solid product by using deionized water, centrifuging the obtained primary purified product, and washing the product for several times until the pH value is neutral. And freeze-drying the centrifuged dispersion liquid in a freeze-drying machine to obtain 2.5g of graphite oxide, wherein the yield is 83.3%.
Example 5
And (3) preparing the silane coupling agent modified antibacterial polypropylene.
A100 mL round bottom flask was charged with the antimicrobial polypropylene block copolymer with poly 4-vinylbenzaldehyde (3.65g,1.0mmol), 3-Aminopropyltriethoxysilane (APTES) (0.443g,2mmol), and 8mL glacial acetic acid, N2And (3) protecting, adding 40mL of toluene, reacting at 100 ℃ for 16h, repeatedly washing the product with ethanol and dichloromethane, and drying at 45 ℃ in vacuum until the weight is constant to obtain 2.84g of silane coupling agent modified antibacterial polypropylene with the yield of 69.3%.
Example 6
And (3) preparing the graphene oxide loaded renewable antibacterial polypropylene material.
In a 100mL round bottom flask, 5g of silane coupling agent modified antibacterial polypropylene, 0.3g of graphene oxide and 40mL of ethanol, N2And (3) protecting, reacting for 16h at 80 ℃, repeatedly washing a product by using ethanol and dichloromethane after the reaction is finished, and drying at 45 ℃ in vacuum until the weight is constant to obtain 4.4g of the graphene oxide loaded renewable antibacterial polypropylene material, wherein the yield is 83.0%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. The graphene oxide-loaded renewable antibacterial polypropylene material is characterized by having a structure shown in formula (I):
wherein n is 50-2000, and m is 10-5000.
2. The preparation method of the graphene oxide-loaded renewable antibacterial polypropylene material according to claim 1, characterized by comprising the following steps:
(1) adding a certain amount of bis (carboxymethyl) trithiocarbonate, N, N-dimethyl isopropanolamine, benzene and p-toluenesulfonic acid into a three-necked flask to perform esterification reaction, and heating and refluxing for 2.0h to obtain a micromolecular chain transfer agent; wherein the molar ratio of the bis (carboxymethyl) trithiocarbonate to the N, N-dimethylisopropanolamine is 1: 1.5;
(2) adding the micromolecule chain transfer agent obtained in the step (1) into a flask with a branch mouth, and dropwise adding SOCl2Obtaining an acyl chlorination product; dissolving an acyl chloride product by using toluene, adding an acid-binding agent pyridine, and performing esterification reaction with single-terminal hydroxyl polypropylene to obtain a macromolecular precursor PP; wherein the molar ratio of the bis (carboxymethyl) trithiocarbonate to the single-terminal hydroxyl polypropylene is 5: 1;
(3) adding a certain amount of the prepared macromolecular precursor PP, a monomer 4-vinylbenzaldehyde and an initiator azobisisobutyronitrile AIBN into a round-bottom flask, and dissolving by using an organic solvent dioxane; reacting for 6 hours at 70 ℃ to obtain an antibacterial polypropylene and poly 4-vinylbenzaldehyde segmented copolymer; wherein the molar ratio of the macromolecular precursor PP to the azobisisobutyronitrile to the 4-vinylbenzaldehyde is 1:4:500, and the molar concentration of the 4-vinylbenzaldehyde is 1 mol/L;
(4) adding 3-aminopropyl triethoxysilane (APTES) and glacial acetic acid into round bottom flask, and dissolving with tolueneSolution of N2Protecting, and reacting for 16h at 100 ℃ to obtain silane coupling agent modified antibacterial polypropylene;
(5) adding silane coupling agent modified antibacterial polypropylene and graphene oxide into a round bottom flask with a branch mouth, dissolving with ethanol, and adding N2And (4) protecting, and reacting for 16h at 80 ℃ to obtain the graphene oxide loaded renewable antibacterial polypropylene.
3. The graphene oxide-loaded renewable antibacterial polypropylene material according to claim 1, wherein the graphene oxide-loaded renewable antibacterial polypropylene material can be used for preparing a mask.
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