CN106268705B - A kind of multifunctional air purifying film and preparation method thereof - Google Patents
A kind of multifunctional air purifying film and preparation method thereof Download PDFInfo
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- CN106268705B CN106268705B CN201610628443.4A CN201610628443A CN106268705B CN 106268705 B CN106268705 B CN 106268705B CN 201610628443 A CN201610628443 A CN 201610628443A CN 106268705 B CN106268705 B CN 106268705B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 62
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 47
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 210000004379 membrane Anatomy 0.000 claims abstract description 35
- 238000000746 purification Methods 0.000 claims abstract description 34
- 238000004887 air purification Methods 0.000 claims abstract description 26
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 25
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 15
- 239000011368 organic material Substances 0.000 claims abstract description 10
- 239000007921 spray Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 38
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 22
- 229930192474 thiophene Natural products 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 230000031709 bromination Effects 0.000 claims description 11
- 238000005893 bromination reaction Methods 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 230000000845 anti-microbial effect Effects 0.000 abstract description 5
- 239000005022 packaging material Substances 0.000 description 38
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 17
- 241000894006 Bacteria Species 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229920001109 fluorescent polymer Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- KFKRXESVMDBTNQ-UHFFFAOYSA-N 3-[18-(2-carboxylatoethyl)-8,13-bis(1-hydroxyethyl)-3,7,12,17-tetramethyl-22,23-dihydroporphyrin-21,24-diium-2-yl]propanoate Chemical compound N1C2=C(C)C(C(C)O)=C1C=C(N1)C(C)=C(C(O)C)C1=CC(C(C)=C1CCC(O)=O)=NC1=CC(C(CCC(O)=O)=C1C)=NC1=C2 KFKRXESVMDBTNQ-UHFFFAOYSA-N 0.000 description 5
- 238000003915 air pollution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 241001269238 Data Species 0.000 description 4
- 241001062009 Indigofera Species 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920000334 poly[3-(3'-N,N,N-triethylamino-1-propyloxy)-4-methylthiophene-2,5-diyl hydrochloride] polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- IBMWWEZVSIJDIW-UHFFFAOYSA-N C1=CC=CC=C1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound C1=CC=CC=C1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 IBMWWEZVSIJDIW-UHFFFAOYSA-N 0.000 description 3
- 241000700605 Viruses Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 230000000505 pernicious effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000004509 smoke generator Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- KCMZYCFSSYXEQR-UHFFFAOYSA-N CCCC[K] Chemical compound CCCC[K] KCMZYCFSSYXEQR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010052804 Drug tolerance Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 208000030303 breathing problems Diseases 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004035 chlorins Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 244000039328 opportunistic pathogen Species 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
- A61L9/18—Radiation
- A61L9/20—Ultraviolet radiation
- A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention is a kind of multifunctional air purifying film and preparation method thereof.The multifunctional air purifying film is one of following two：The first air purification film, including basement membrane, and it is sprayed on epilamellar Multifunctional layered；The Multifunctional layered is the mixture of nano graphene oxide and fluorescent conjugated polymer, and the basement membrane is non-woven fabrics；Alternatively, second of air purification film, spray fusing obtains after being mixed for high-molecular organic material, nano graphene oxide and fluorescent conjugated polymer, the use of the purification membrane aperture is 0.2~12 μm, and thickness is 500~5000 μm.The antimicrobial form that the present invention obtains eliminates PM2.5Air purification film, compared with traditional antibacterial, have the characteristics that efficiently, antibacterial, usage time length etc..
Description
Technical field
The invention belongs to antipollution air filtration purification applications field, it is related to a kind of multifunctional air purifying film and its preparation
A kind of method, and in particular to air purification film and its preparation side using nanoscale graphene and fluorescent conjugated polymer
Method.
Technical background
It is well known that the survival of life be unable to do without air, and air pollution can seriously damage us and breathe vitals lung,
Breathing problem is caused, people's health is seriously affected.Aggravate demand of the people for air purification with air pollution
It is more and more urgent.With pellet (PM10), fine particle (PM2.5) it is characterized the regional atmospheric environment problem of pollutant
It becomes increasingly conspicuous, damages body health of people, influence social harmony stabilization.As China's industrialization, urbanization deeply push away
Into energy consumption continues to increase, and prevention and control of air pollution pressure continues to increase.As the improvement of people's living standards, people
Become more concerned with the indoor environmental qualities problems such as living space, office space, the vehicles, Leisure Consumption place.
By investigating to Chinese air purification industry development and thinking to prospect analysis of market, due to air pollution, environment
Out of control, smoking population such as persistently rises at the factors, and in recent years, the incidence of lung cancer is continued for rising.Public's environmental pollution
Caused hidden danger shows unprecedented anxiety and concern, and Public Environmental Awareness constantly enhances.China's air purification at present
Device family ownership less than 1%, advance by leaps and bounds presentation the gesture of development by following air purifier market.
Current most common purification air technique is activated carbon adsorption.Activated carbon is a kind of porous carbon containing matter, it
It is constructed with highly developed hole, the porous structure of activated carbon is provided for a large amount of surface area, can fully be connect with gas
It touches, the powerful absorption property of activated carbon is imparted by capillarity, it is made to be very easy to achieve the purpose that adsorbing contaminant.When
The pore structure of activated carbon is slightly larger than the diameter of pernicious gas molecule, can allow pernicious gas molecule completely into the case of,
Due to attracting each other between molecule, harmful impurity can be attracted in aperture, have the function that purify air.This
Outside, using activated carbon small-bore the characteristics of, the Particulate Pollution object of major diameter can be blocked on the side of activated carbon in air, from
And realize the purpose of filtration, purification.Other air purifying process further include：Light catalytic purifying, ozonization, Electrostatic Absorption, mistake
Filter etc..Current indoor air purification product can be divided into two classes, and first kind product is inhaled using filtering, absorption, magnetization, electrostatic
Dirt, anion eliminate the purifiers such as flue dust.This purifier based on physical cleaning, disadvantage are not eliminating by different
Pollution caused by smell, pathogen, virus, microorganism etc..Second generation product is to generate ozone anion as major function
Air purifier.Ozone has the function of disinfection, sterilization, deodorant to taste and removes paint pigment etc..
In the recent period, Beijing-tianjin-hebei Region mist, haze are multiple takes place frequently, and new feature, heavy metal ion, bacterium, virus is presented in atmosphere pollution
Content it is in rising trend.Such serious pollution problem can not be coped with using traditional purification method, these technologies are not only
Can there are problems that secondary pollution, and weak to the pathogenic bacteria killing ability in air, cannot achieve the purpose that be fully cleaned up.Cause
This, develop a kind of novel material for air purification and technology of preparing be there is an urgent need to.
Invention content
The purpose of the present invention is for be most badly in need of at present solve air pollution problems inherent, according to the new spy of current atmosphere pollution
Point, provide a kind of antimicrobial form eliminates PM2.5Air purification film.The purification membrane is total by nano graphene oxide and fluorescence
The addition of conjugated polymer component, collection eliminate PM2.5, antibacterial and monitoring etc. it is multi-functional in one, PM can be improved2.5Removal rate, and
With good bactericidal effect.
The technical scheme is that：
A kind of multifunctional air purifying film, the multifunctional air purifying film are one of following two：
The first air purification film, including basement membrane, and it is supported on epilamellar Multifunctional layered；Wherein, every square metre of base
Load has 0.8~10g Multifunctional layereds on film；The Multifunctional layered is the mixed of nano graphene oxide and fluorescent conjugated polymer
Object is closed, mass ratio is graphene oxide：Fluorescent conjugated polymer=5~20:1；The basement membrane is non-woven fabrics；
Alternatively, second of air purification film, is high-molecular organic material, nano graphene oxide and fluorescent conjugated polymer
Spray fusing after mixing and obtain, using the purification membrane aperture be 0.2~12 μm, thickness be 500~5000 μm；Wherein, mass ratio
For high-molecular organic material：Nano graphene oxide：Fluorescent conjugated polymer=50-300：3-6：1.
The material or high molecular material of the non-woven fabrics be polyvinyl chloride (PVC), polymethyl methacrylate (PMMA),
Polymethyl acrylate (PC), polystyrene (PS), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE),
Polypropylene (PP), polyethylene terephthalate (PET), poly- propionitrile (PAN), polyether sulfone (PES), gathers partially polyethylene (PE)
One kind in vinyl fluoride (PVDF).
The nano graphene oxide is the graphene oxide of a diameter of 10-2000nm；The nano graphene oxide is
The graphene oxide that the atom number of plies is 1-10 layers.
The fluorescent conjugated polymer includes：Pyridyl group porphyrin, phenyl porphyrin, methylenum careuleum, toluidine blue, haematoporphyrin, two
Hydrogen porphines, poly- [3- (2 '-N, N, N- triithylamine base -1 '-ethyoxyl) -4- methylthiophenes hydrochloride], poly- 3- (Isosorbide-5-Nitraes-dioxa -
6- brominations trimethylamine groups-hexyl) thiophene-co-3- (1,4,7- trioxas-octyl) thiophene.
The preparation method of the first multifunctional air purifying film, includes the following steps：
(1) mixed liquor is obtained after mixing nano graphene oxide solution and fluorescent polymer solution, then using coating
Method or infusion method are assembled on basement membrane；Wherein, a concentration of 0.1mg/mL~10mg/mL of nano graphene oxide aqueous solution, it is glimmering
A concentration of 0.1mg/mL~10mg/mL of the aqueous solution of photopolymer；Mass ratio is graphene oxide：Fluorescent conjugated polymer=
5~20:1；The basement membrane is non-woven fabrics；
The infusion method, includes the following steps：It will be immersed in mixed liquor on basement membrane, after impregnating 1-12 hours, then adopt
Take the mode of suction filtration by mixed liquor nano graphene oxide solution and fluorescent polymer be supported on basement membrane；Every square metre of base
Load has 0.8~10g nano graphene oxides solution and fluorescent polymer on film；
The cladding process, includes the following steps：By mixed liquor with membrane surface is coated onto, coating number is 1-20 times, is made
Adhere to 0.8~10g nano graphene oxides solution and fluorescent polymer on every square metre of basement membrane；
(2) in the organic basement membrane merging vacuum drying chamber obtained upper step, 20-60 DEG C, vacuum degree is under 100-1000Pa
Drying time is 1-24 hours.
The preparation method of second of multifunctional air purifying film, includes the following steps：
(1) organic polymer is melted at 120-160 DEG C；
(2) and then nano graphene oxide solution and fluorescent conjugated polymer solution is added, stirs evenly, wherein nanometer
A concentration of 0.1mg/mL~10mg/mL of graphene oxide water solution, a concentration of 0.1mg/mL of the aqueous solution of fluorescent polymer
~10mg/mL；Mass ratio is high-molecular organic material：Nano graphene oxide：Fluorescent conjugated polymer=50-300：3-6：1；
(3) spray fusing method is utilized to be film-made, it is 0.2~6 μm to obtain membrane aperture；The thickness of film is 500~5000 μm；
(4) by film made from upper step at 20-60 DEG C, vacuum degree is that drying is 1-10 hours under 100-500Pa, obtains second
Kind multifunctional air purifying film.
A kind of fluorescent conjugated polymer, the polymer are poly- 3- (Isosorbide-5-Nitrae-dioxa -6- brominations trimethylamine groups-hexyl) thiophene
Pheno-co-3- (Isosorbide-5-Nitrae, 7- trioxas-octyl) thiophene, structural formula are as follows：
Wherein, m1m2For the degree of polymerization, m1=1-10；m2=1-10.
The present invention substantive distinguishing features be：
Graphene oxide is the oxide of graphene, it is inside graphene and surrounding is connected to oxygen-containing group at random,
It is easy to further functionalization, can be combined with other molecules by a variety of non-covalent bonds such as hydrophobic effect, electrostatic interaction.
Graphene oxide derives from a wealth of sources, cheap, and intensity is high, and controllability is strong, meets the requirement of the big production of scale.
Fluorescent conjugated polymer is made up of many extinction units conjugation, thus catches light ability with extremely strong.
Nineteen ninety-five, Swager are put forward for the first time the concept of fluorescent conjugated polymer fluorescence signal enlarge-effect, when in detection architecture exist by
When body molecule, the energy of polymer capture can carry out delocalization along entire conjugated backbone, be ultimately transferred to acceptor molecule to put
Its big fluorescence signal (i.e. " molecular line effect "), this is particularly significant for improving imaging and diagnostic sensitivity.Small molecule is passed
Sense system, when Small-molecule probe and detected material effect, detected material is one-to-one with small molecule, if detected material
Concentration be less than Small-molecule probe concentration, only part sensor molecules generate response, so the sensing system based on small molecule
Sensitivity can not be comparable with fluorescent conjugated polymer.It can be at double using the fluorescence signal amplification characteristic of fluorescent conjugated polymer
Ground improves detection sensitivity, and new sensing modes are provided for the development of biosensor.Water soluble fluorescent conjugated polymer with
The surfaces such as bacterium, fungi and virus combine, and can generate singlet oxygen under white light illumination as light-sensitive material and reach sterilization
Effect in addition, fluorescent conjugated polymer for light power antimicrobial chemical therapy show toxic side effect it is small, to different types of disease
Opportunistic pathogen has many advantages, such as bactericidal effect, and compared with antibiotic, it is not easy to which in-ductive drug -tolerance is a kind of efficiently excellent antibacterial
Method.Purification membrane made by us uses the graphene oxide after ultrasonication, and graphene oxide layer is become smaller, then
Group loads onto fluorescent conjugated polymer, is added to high-molecular organic material basement membrane, overcomes some technological difficulties, greatly improves and inhales
Attached PM2.5It is realized while efficiency and kills harmful bacteria in purifying air event.
Beneficial effects of the present invention are：
The antimicrobial form that the present invention obtains eliminates PM2.5Air purification film, compared with traditional antibacterial, have efficiently,
The features such as antibacterial, usage time length etc..
(1) air-filtering membrane provided by the invention is to the PM in air2.5Removal rate height up to 95% or so, it is completely full
Sufficient PM2.5Protection requirements.
(2) air purification film provided by the invention has killing effect, antibiotic rate to bacterium, fungi, pathogen in air
Up to 90% or more.
(3) air purification film provided by the invention can monitor the PM for being adsorbed on purification film surface in real time2.5And all kinds of cause of diseases
Bacterium.
(4) service life of air purification film provided by the invention is long, and existing air-filtering membrane at most uses in the market
300 hours, air purification film service life provided by the invention was up to 1000 hours.
(5) air purification film provided by the invention uses electrostatic knot compared with existing air purification film currently on the market
It closes, Absorptive complex wave, not will produce reentrainment of dust pollution.
Description of the drawings
Fig. 1 is the shape appearance figure for the nano graphene oxide that the present invention utilizes.
Fig. 2 is air-filtering membrane described in embodiment 1 to PM2.5Removal effect photo, wherein Fig. 2 a are using net
Before change film PM in air is collected into using sampling film in Laboratory Module10Amount be 0.6mg photo；Fig. 2 b are using real before purification membrane
In hatch checking PM in air is collected into using sampling film2.5Amount be 4.5mg photo；Fig. 2 c are using in Laboratory Module after purification membrane
It is collected into PM in air using sampling film10Amount be 0.5mg photo；Fig. 2 d be using in Laboratory Module after purification membrane using sampling
Film is collected into PM in air2.5Amount be 3.4mg photo.
Fig. 3 is the air purification film anti-microbial property test result photo in embodiment 1, and wherein Fig. 3 a are cell plates culture
Use the photo of bacterium amount in Laboratory Module after purification membrane；Fig. 3 b are photograph of the cell plates culture using bacterium amount in Laboratory Module after non-woven fabrics
Piece.
Fig. 4 is that the air purification film detects PM in embodiment 12.5Design sketch, wherein Fig. 4 a are that purification membrane is not used in purple
The photo of fluorescent brightness under outer lamp；Fig. 4 b are the photo of used purification membrane fluorescent brightness in the UV lamp.
Specific implementation mode
The present invention will be described in further detail with reference to the following examples.The following examples be for explanation purposes, and
It is not intended to limit the scope of the present invention.Experimental method in following embodiments is conventional method unless otherwise specified.It is following
Experiment material used in embodiment is to be commercially available from routine biochemistry reagent shop unless otherwise specified.
Graphene oxide of the present invention is well known materials.Wherein, the preparation method of graphene oxide can be found in document
282-286 pages of volume 442 of Graphene-based composite materials, Nature, 2006 years.It is respectively provided with and weighs three times
Multiple experiment, results are averaged.Obtained nano graphene oxide is a diameter of 10-2000nm, the atom number of plies is 1-10 layers
Graphene oxide, it is 300-400nm that following embodiment, which uses, single layer.
Embodiment 1,
The first step prepares nano graphene oxide aqueous solution：
Graphene oxide is taken to dissolve, the ultrasonic disperse in ice bath, ultrasonic power 100W, ultrasound 60 minutes.Size can be obtained about
For the graphene oxide of 350nm, the atom number of plies is single layer.Dried for standby.
0.5g nano graphene oxides obtained above are taken, are dissolved into 1000mL ultra-pure waters, receiving for 0.5mg/mL is obtained
Rice graphene oxide water solution；
It is prepared by second step, conjugated polymer：
Monomer (1) 3- (1,4- dioxa -6- hydroxy-hexanes base) thiophene synthesis route：
45mL pyridines, diethylene glycol 15mL (16.75g, 157.8mmol), (5.6g, 49.9mmol), cuprous iodide is added
(1.4g, 7.34mmol) is added 3 bromo thiophene (5.16g, 31.6mmol) after being stirred to react 30min, rises to 100 DEG C, reaction
24h.Reaction solution is cooled to room temperature, dichloromethane dilution is added, filters, it is dry, obtain product pale yellowish oil liquid (4.16g,
Yield 70%).
The characterization of product：1H NMR(400MHz,CDCl3,ppm):):(400MHzdd,1H),6.79(dd,1H),6.28
(dd, 1H), 4.13 (t, 2H), 3.85 (t, 2H), 3.77 (t, 2H), 3.67 (t, 2H), 2.16 (s, 1H)；13CNMR(100MHz,
CDCl3,ppm):):,1H)；13C NMR(100MHz,CDCl3,ppm):2H), 3.67 (t, 2H) characterize datas show：It obtains
Monomer 3- (1,4- dioxa -6- hydroxy-hexanes base) thiophene.
Monomer (2) 3- (1,4- dioxa -6- p-methyl benzenesulfonic acid base-hexyl) thiophene synthesis route：
Monomer (1) (1.16g, 6.17mmol) is dissolved in dichloromethane, 0 DEG C is cooled in ice-water bath, pyridine 1mL is added.
TsCl (1.8g, 9.44mmol) is added, the reaction was continued for 24 hours.Use CH2Cl2Extraction, it is dry then with washing, it concentrates, purifying, most
Light yellow solid (1.62g, 76%) is obtained eventually.
The characterization of product：1H NMR(400MHz,CDCl3,ppm):):(400MHz,CDCl3,ppm):Hz,CDCl3,
Ppmdd, 1H), 6.75 (dd, 1H), 6.23 (dd, 1H), 4.19 (dd, 2H), 4.03 (dd, 2H), 3.76 (m, 4H), 2.42 (s,
3H).13C NMR(100MHz,CDCl3,ppm):):m,4H),2.42(s,3H).13C NMR(100MHz,CDCl3,),2H)
Dd, 2H) H) Calcd.C 52.63, H 5.26, Found C 53.02, H 5.96. characterize datas show：Monomer 3- is obtained
(1,4- dioxa -6- p-methyl benzenesulfonic acid base-hexyl)
The synthesis of monomer (3) 3- (the bromo- hexyls of 1,4- dioxas -6-) thiophene：
Monomer (2) (0.62g, 1.81mmol) is dissolved in 15mL acetone, addition LiBrH2O (0.68g,
6.48mmol), 8h is reacted.It is dry after extraction, it concentrates, purifying obtains pale yellow oily liquid (0.41g, 90%).
The characterization of product：1H NMR(400MHz,CDCl3,ppm):):(400MHz,CDCl3,ppm):dd,1H),6.27
(dd, 1H), 4.13 (dd, 2H), 3.87 (m, 4H), 3.49 (t, 2H) .13C NMR (100MHz, CDCl3, ppm):)=157.4,
124.7,119.5,97.6,71.4,69.9,69.6,69.5.MS(EI):M/z=250,252 (M) .C8H11O2SBr:
Calcd.C 38.24, H 4.38, Found C 38.72, H 4.68. characterize datas show：Monomer 3- (1,4- dioxies are obtained
The miscellaneous bromo- hexyls of -6-) thiophene
The synthesis of monomer (4) 3- (1,4- dioxa -6- brominations trimethylamine groups-hexyl) thiophene：
Monomer (3) (1.23g, 4.9mmol) is dissolved in tetrahydrofuran, methanol solution, overnight, reaction stops for 40 DEG C of reactions
And after being cooled to room temperature, rotate, dissolving, 40mL n-hexanes are added and are settled out solid, centrifuges to obtain precipitation, it is solid that white is obtained after dry
Body (1.44g, 94.7%).
The characterization of product：1H NMR(400MHz,CDCl3,ppm):):(400MHzdd,1H),6.27(dd,1H),4.13
(dd,2H),4.12(dd,2H),4.03(t,4H),3.89(dd,2H),3.50(s,9H).13C NMR(100MHz,CDCl3,
ppm):):,3.50(s,9H).13C NMR(100MHz,CDCl3,ppm)::C NMR MS(ESI):M/z=
230.12.C11H20O2BrNO2S:Calcd.C 42.58,H 6.45,N 4.52Found C 41.72,H 6.66,N 4.49.
Characterize data shows：Monomer 3- (1,4- dioxa -6- brominations trimethylamine groups-hexyl) thiophene is obtained
The synthesis of monomer (5) 3- (1,4,7- trioxas-octyl) thiophene：
2,6- lutidines, diethylene glycol monomethyl ether (5.89g, 49.1mmol), uncle are sequentially added in two mouth flask
Butyl potassium alcoholate (3.58g, 32mmol) cuprous iodide (608mg, 0.36mmol), stirs evenly, and 3- bromine thiophenes are added after reacting 30min
The lutidines solution of pheno (5.16g, 31.6mmol), reaction is overnight.Reaction solution is cooled to room temperature, is filtered, is washed, is done
It is dry, it concentrates, chromatography, dry brown liquid (5.1g, 80%).
The characterization of product：1H NMR (400MHz, CDCl3, ppm):):(400MHdd,1H),6.78(dd,1H),6.26
(dd,1H),4.13(t,2H),3.85(t,2H),3.71(dd,2H),3.58(dd,2H),3.39(s,3H).13C NMR
(100MHz, CDCl3, ppm):=157.6,124.6,119.6,97.5,72.0,70.7,69.7,69.5,59.1.MS (EI):
M/z=202 (M) .C9H14O3S:Calcd.C 53.46, H 6.93, Found C 53.27, H 7.29. characterize datas show：
Monomer 3- (1,4,7- trioxas-octyl) thiophene is obtained
Poly- 3- (1,4- dioxa -6- brominations trimethylamine groups-hexyl) thiophene-co-3- (1,4,7- trioxas-octyl)
The synthesis of thiophene (PT)：
10mL chloroforms are sequentially added in reaction bulb, monomer (4) is then added dropwise in anhydrous ferric trichloride (325mg, 2mmol)
(155mg, 0.5mmol) and monomer (5) (101mg, 0.5mmol) reacts at room temperature 2 days.It is sudden that methanol is added into reaction mixture
It goes out reaction, centrifugation, methanol/chloroform (1:1) it washs, tetrabutylammonium chloride is then added, generate black precipitate.Precipitation is filtered,
Filter cake again with methanol dissolves, and hydrazine hydrate, solution is added to be spin-dried for, and washs, and utilizes the bag filter dialysis 2 that molecular cut off is 3500Da
It；Solvent is removed, solid is dried to obtain.
The characterization of product：1H NMR(400MHz,CDCl3,ppm):):(400MHz,CDbr),4.50-4.18(br),
3.81-3.02(br),2.68-2.61(br),1.87(br).Characterize data shows：Poly- 3- (1,4- dioxa -6- bromines are obtained
Change trimethylamine groups-hexyl) thiophene-co-3- (1,4,7- trioxas-octyl) thiophene (PT)
The fluorescent conjugated polymer, poly- 3- (Isosorbide-5-Nitrae-dioxa -6- brominations trimethylamine groups-hexyl) thiophene-co-3-
(1,4,7- trioxas-octyl) thiophene (PT) structural formula is as shown below：
Wherein, m1m2For polymer, m1Value range：1-10；m2Value range is 1-10.
Third walks, and configures the aqueous solution of fluorescent conjugated polymer：
Fluorescent conjugated polymer：Poly- 3- (1,4- dioxa -6- brominations trimethylamine groups-hexyl) thiophene-co-3- (1,4,
7- trioxas-octyl) thiophene (PT) solution preparation：It takes 0.01g PT to be added in 10mL ultra-pure waters, obtains 1mg/mL storages
Liquid.
4th step, the preparation of multifunctional air purifying film：
(1) by prefabricated non-woven fabrics according to requiring to be cut into right dimensions and shapes.The non-woven fabrics polypropylene
Material, size are 25cm × 25cm, and aperture is 2000 μm；
(2) the nano graphene oxide aqueous solution of a concentration of 0.5mg/mL of 100mL is prepared；
(3) fluorescent conjugated polymer in dilution third step is to 0.1mg/mL；Take 100mL；
(4) mixed liquor is obtained after mixing nano graphene oxide solution obtained above and fluorescent polymer solution, so
It will be immersed in mixed liquor on high-molecular organic material basement membrane afterwards, after impregnating 1 hour, then take the mode repeatedly filtered that will mix
Nano graphene oxide solution and fluorescent polymer in liquid are all supported on basement membrane (mark is that filtrate is clarified)；It often puts down at this time
Load has 0.960g nano graphene oxides solution and fluorescent polymer on square rice basement membrane；
(5) in the basement membrane merging vacuum drying chamber obtained upper step, 30 DEG C, 200Pa, drying time：12 hours, obtain this
The used purification membrane of invention.
It verifies purification membrane and adsorbs PM2.5Ability (this embodiment is with reference to People's Republic of China (PRC) environment protectment protection HJ
656-2013 and HJ 618-2013)：
(a) particle PM is adopted by used on air sampler in Laboratory Module2.5And PM10Sampling film, take four, respectively
Mark A, B and A ', B ' according to People's Republic of China's environment protectment protection HJ 656-2013 processing,
(b) test process：According to the national standard GB-T14295-2008 identical Laboratory Modules 1 established and Laboratory Module 2.
In Laboratory Module 1, after generating smog using aerosol producer, opens sampler and collected in laboratory respectively using sampling film A, B
PM2.5And PM10Particle, collect 2h after, obtain initial p M in Laboratory Module2.5And PM10Concentration value.In Laboratory Module 2, cigarette is used
After fog generator generates smog, purifier of the unlatching equipped with air purification film 3 hours.After purification, it is then turned on sampler
PM in laboratory is collected using sampling film A ', B '2.5And PM10Particle, obtain PM in the rear deck of Laboratory Module internal filter filtering2.5
And PM10Concentration value.
Result of calculation PM2.5And PM10Concentration, unit be μ g/m3。
With reference to the accompanying drawings 2, it can obtain the indoor PM before opening air filter2.5And PM10Concentration and used air mistake
PM in filter rear chamber2.5And PM10Concentration, you can obtain self-control purification membrane and reduce room air PM2.5And PM10The ability of concentration.
As a result it can show, use PM in Laboratory Module after purification membrane2.5And PM10Amount reduce.It demonstrates and purifies sky using purification membrane of the present invention
The ability of gas.
Verifying purification membrane antibacterial ability, (this embodiment is with reference to People's Republic of China (PRC) environment protectment protection GB 21551.3-
2010)：
(a) picking E.coli single bacteriums fall in 5mL LB culture mediums (in 50 in (B551.3-20) 37 culture 12h；
(b) PBS (PBS concrete compositions are used：Sodium chloride 4g, potassium chloride 0.1g, disodium hydrogen phosphate 0.71g, potassium dihydrogen phosphate
0.135g is dissolved in 500mL ultra-pure waters, ionic strength 137mM PH=7.4) wash bacterium 3 times, then wash bacterium with PBS suspensions；
(c) suspended bacteria 10 is adjusted7Cfu/mL；
(d) bacterium solution in being walked on 10 μ L is taken, 990 μ L PBS is added, drips to the non-woven fabrics and Ben Fa of 1cm × 1cm respectively
In bright purification membrane；
(e) purification membrane of non-woven fabrics in upper step and the present invention is respectively put into and is put into holes among 12 orifice plates, side hole adds
Enter 3mL ultra-pure waters.It is put into 37 DEG C of culture 3h in incubator；
(f) it washes bacterium with 1mL PBS respectively in three times, collects, suspended again using 1mL PBS；
(g) bacterium solution, each concentration take 50 μ L coated plates in step on gradient dilution, are put into 37 DEG C of culture 12h in incubator；
(h) tablet observation is taken out to count.
With reference to the accompanying drawings 3 as a result, it was observed that, the dot on tablet a, point represents a bacterium, uses Laboratory Module after purification membrane
Interior bacterium amount declines 90% or so.Demonstrate the ability of purification membrane antibacterial of the present invention.
Detect purification membrane service life：
(a) cigarette smoke generator is opened in the closed Laboratory Module established according to national standard GB-T14295-2008 to be allowed to not
PM is given birth in stopping pregnancy2.5；
(b) it is carried out at the same time filtering using the air purification film of non-woven fabrics and the present invention；
(c) it removed filter membrane every 12 hours to weigh, is put back to again after having weighed and continue to filter, when filter membrane weight no longer becomes
When change, duration is exactly the service life of graphene oxide filter membrane；
When experiment proceeds to 300 hours, non-woven fabrics no longer increases weight, and non-woven fabrics service life is 300 hours.The present invention's
Purification membrane no longer increases weight when proceeding to 1000 hours, and purification membrane service life of the present invention is 1000 hours.
Detect PM2.5Method.
In the Laboratory Module established according to national standard GB-T14295-2008, smog is persistently generated using cigarette smoke generator
Afterwards, it is purified 1 hour using purification membrane.After purification, air purification film is removed, with the naked eye directly observes sample in the UV lamp
Color, compared with original purification membrane is in the color under lamp, fluorescent quenching.
Embodiment 2-8
With embodiment 1, difference is for other steps and test method, fluorescent conjugated polymer used in step 3 by
The aqueous solution of third step configuration fluorescent conjugated polymer, which replaces with, in embodiment 1 configures in order following fluorescent conjugated polymer：
(a) preparation of pyridylporphyrin TPP solution：It takes 0.0068g pyridylporphyrins TPP to be added in 20mL ultra-pure waters, obtains
0.25mM stores liquid.
(b) preparation of benzene porphyrin TP solution：It takes 0.0076g phenyl porphyrins TP to be added in 20mL ultra-pure waters, obtains
0.25mM stores liquid.
(c) preparation of sub- indigo plant M-B solution：It takes the sub- indigo plant M-B of 0.0016g that the ultrapure water dissolutions of 20mL are added and obtains 0.25mM storages
Liquid.
(d) preparation of toluene blue T-BO solution：It takes 0.001g toluidine blues TBO that the ultrapure water dissolutions of 20mL are added and obtains 0.25mM
Store liquid.
(e) preparation of haematoporphyrin H-P solution：It takes 0.0033g haematoporphyrin HP that the ultrapure water dissolutions of 20mL are added and obtains 0.25mM storages
Liquid storage.
(f) preparation of chlorin P-C solution：It takes 0.003g chlorins PC that the ultrapure water dissolutions of 20mL are added and obtains 0.25mM
Store liquid.
(g) fluorescent conjugated polymer：Poly- [3- (2 '-N, N, N- triithylamine base -1 '-ethyoxyl) -4- methylthiophene hydrochloric acid
Salt] (PMNT) solution preparation：It takes 0.004g PMNT to be added in 5mL ultra-pure waters, obtains 0.125mM storage liquid.
Each middle fluorescent conjugated polymer embodiment result：
| Fluorescent polymer title | Reduce PM2.5Ability | Antibacterial ability | Service life (h) |
| PT | 98% | 90% | 1000 |
| Pyridylporphyrin TPP | 97% | 85% | 1000 |
| Benzene porphyrin TP | 99% | 87% | 1000 |
| Sub- indigo plant M-B | 97% | 87% | 1000 |
| Toluene blue T-BO | 99% | 86% | 1000 |
| Haematoporphyrin H-P | 97% | 89% | 1000 |
| Chlorin P-C | 97% | 90% | 1000 |
| PMNT | 99% | 89% | 1000 |
Embodiment 9
The first step makes purification membrane：
Organic polymer polypropylene is melted at 140 DEG C；
Then nano graphene oxide solution and fluorescent conjugated polymer (poly- 3- (1,4- dioxa -6- bromination front threes is added
Amido-hexyl) thiophene-co-3- (Isosorbide-5-Nitrae, 7- trioxas-octyl) thiophene (PT)) solution, it stirs evenly, wherein nano oxygen
A concentration of 0.5mg/mL of graphite aqueous solution, 600mL, a concentration of 1.0mg/mL of the aqueous solution of fluorescent polymer,
100mL；Mass ratio is high-molecular organic material：Nano graphene oxide：Fluorescent conjugated polymer=200：3：1；
Said mixture is film-made using spray fusing method, it is 1 μm to obtain membrane aperture；2000 μm of the thickness of film；Wherein：Spray fusing is set
It is standby：Wuxi Ai Jiemeisi Machinery Co., Ltd.s (spinneret width 30cm, die head draw ratio 1:10, orifice diameter 0.3mm, hole
Deep 3mm.Process conditions：Air pressure：0.15-0.3MPa；Receive distance 5-9cm；Measure revolution speed：45-60Hz, preferably work
Skill：Air pressure：0.25MPa；Receive distance：6cm；Measure revolution speed：50Hz (can obtain 0.45 μm of optimum aperture)
By film made from upper step at 40 DEG C, vacuum degree is that drying is 3 hours under 200Pa, obtains second of multi-functional air
Purification membrane.
Second of multifunctional air purifying film test method is obtained with embodiment 1, experimental result is approximate with embodiment 1.
Embodiment 10-16
With embodiment 9, difference is the fluorescent conjugated polymer that uses by embodiment 9 for other steps and test method
In fluorescent conjugated polymer (poly- 3- (1,4- dioxa -6- brominations trimethylamine groups-hexyl) thiophene-co-3- (1,4,7- tri-
Oxa--octyl) thiophene (PT)) aqueous solution replace with successively the aqueous solution of pyridylporphyrin TPP, benzene porphyrin TP aqueous solution,
The sub- indigo plant aqueous solution of M-B, the aqueous solution of toluene blue T-BO, the aqueous solution of haematoporphyrin H-P, chlorin P-C aqueous solution, gather
The aqueous solution of [3- (2 '-N, N, N- triithylamine base -1 '-ethyoxyl) -4- methylthiophenes hydrochloride] (PMNT).
Test result is approximate with embodiment 9.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. a kind of multifunctional air purifying film, it is characterized in that the multifunctional air purifying film is one of following two：
The first multifunctional air purifying film, including basement membrane, and it is supported on epilamellar Multifunctional layered；Wherein, every square metre
Load has 0.8 ~ 10g Multifunctional layereds on basement membrane；The Multifunctional layered is nano graphene oxide and fluorescent conjugated polymer
Mixture, mass ratio are nano graphene oxide：Fluorescent conjugated polymer=5 ~ 20:1；The basement membrane is non-woven fabrics；
Alternatively, second of multifunctional air purifying film, is high-molecular organic material, nano graphene oxide and fluorescence conjugated polymerization
Object mixing after spray fusing and obtain, the purification membrane aperture be 0.2 ~ 12 μm, thickness be 500 ~ 5000 μm；Wherein, mass ratio is to have
Machine high molecular material：Nano graphene oxide：Fluorescent conjugated polymer=50-300：3-6：1；
The fluorescent conjugated polymer is：Poly- [3-（2 '-N, N, N- triithylamine base -1 '-ethyoxyl）- 4- methylthiophenes hydrochloride]
Or poly- 3-（1,4- dioxa -6- brominations trimethylamine groups-hexyl）Thiophene-co -3-（1,4,7- trioxas-octyl）Thiophene
Pheno.
2. multifunctional air purifying film as described in claim 1, it is characterized in that the material of the non-woven fabrics or organic high score
Sub- material be polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, polystyrene, ethylene-vinyl acetate copolymer,
One kind in ethylene-octene copolymer, polypropylene, polyethylene, polyethylene terephthalate, polyether sulfone, Kynoar.
3. multifunctional air purifying film as described in claim 1, it is characterized in that the nano graphene oxide is a diameter of 10-
The graphene oxide of 2000nm；The nano graphene oxide is the graphene oxide that the atom number of plies is 1-10 layers.
4. the preparation method of multifunctional air purifying film as described in claim 1, it is characterized in that the first multi-functional air is net
The preparation method for changing film includes the following steps：
（1）Mixed liquor is obtained after nano graphene oxide solution and fluorescent conjugated polymer solution are mixed, then using coating
Method or infusion method are assembled on basement membrane；Wherein, the mg/mL of a concentration of 0.1mg/mL ~ 10 of nano graphene oxide solution, fluorescence
A concentration of mg/mL of 0.1 mg/mL ~ 10 of the solution of conjugated polymer；Mass ratio is nano graphene oxide：It is fluorescence conjugated poly-
Close object=5 ~ 20:1；
The basement membrane is non-woven fabrics；
The infusion method, includes the following steps：Basement membrane is immersed in mixed liquor, after impregnating 1-12 hours, then takes suction filtration
Mode by mixed liquor nano graphene oxide solution and fluorescent conjugated polymer be supported on basement membrane；Every square metre of basement membrane
Upper load has 0.8 ~ 10g nano graphene oxides solution and fluorescent conjugated polymer；
The cladding process, includes the following steps：Mixed liquor is coated to membrane surface, coating number is 1-20 times, makes often to put down
Adhere to 0.8 ~ 10g nano graphene oxides solution and fluorescent conjugated polymer on square rice basement membrane；
（2）In the basement membrane merging vacuum drying chamber that upper step is obtained, 20-60 DEG C, vacuum degree is dry under 100-1000Pa, the time
It is 1-24 hours.
5. the preparation method of multifunctional air purifying film as described in claim 1, it is characterized in that second of multi-functional air is net
The preparation method for changing film includes the following steps：
（1）High-molecular organic material is melted at 120-160 DEG C；
（2）Then nano graphene oxide solution and fluorescent conjugated polymer solution is added, stirs evenly, wherein nano oxidized
The mg/mL of a concentration of 0.1mg/mL ~ 10 of graphene solution, a concentration of 0.1 mg/mL ~ 10 of the solution of fluorescent conjugated polymer
mg/mL；Mass ratio is high-molecular organic material：Nano graphene oxide：Fluorescent conjugated polymer=50-300：3-6：1；
（3）It is film-made using spray fusing method, it is 0.2 ~ 6 μm to obtain membrane aperture；The thickness of film is 500 ~ 5000 μm；
（4）By film made from upper step at 20-60 DEG C, vacuum degree is 1-10 hours dry under 100-500Pa, obtains work(more than second
It can air purification film.
6. a kind of fluorescent conjugated polymer, it is characterized in that the polymer is poly- 3-（1,4- dioxa -6- brominations trimethylamine groups-oneself
Alkyl）Thiophene-co -3-（1,4,7- trioxas-octyl）Thiophene, structural formula are as follows：
Wherein, m1=1-10；m2=1-10。
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