CN106268705A - 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
- Publication number
- CN106268705A CN106268705A CN201610628443.4A CN201610628443A CN106268705A CN 106268705 A CN106268705 A CN 106268705A CN 201610628443 A CN201610628443 A CN 201610628443A CN 106268705 A CN106268705 A CN 106268705A
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- graphene oxide
- film
- fluorescent
- conjugated polymer
- polymer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000000243 solution Substances 0.000 claims description 35
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- 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)
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Abstract
The present invention is a kind of multifunctional air purifying film and preparation method thereof.Described multifunctional air purifying film is one of following two: the first air cleaning film, including basement membrane, and is sprayed on epilamellar Multifunctional layered；Described Multifunctional layered is the mixture of nano graphene oxide and fluorescent conjugated polymer, and described basement membrane is non-woven fabrics；Or, the second air cleaning film, obtain for spray fusing after the mixing of high-molecular organic material, nano graphene oxide and fluorescent conjugated polymer, using described purification membrane aperture is 0.2～12 μm, and thickness is 500～5000 μm.The eliminated PM of the antimicrobial form that the present invention obtains2.5Air cleaning film, with traditional antibacterial compared with, have efficient, antibacterial, use time length etc. feature.
Description
Technical field
The invention belongs to antipollution air filtration purification applications field, relate to a kind of multifunctional air purifying film and preparation thereof
Method, is specifically related to a kind of air cleaning film utilizing nanoscale Graphene and fluorescent conjugated polymer and preparation side thereof
Method.
Technical background
It is known that the survival of life be unable to do without air, and air pollution can seriously damage us and breathe vitals lung,
Cause respiratory tract disease, have a strong impact on the health of people.Along with air pollution aggravation people for air cleaning demand also
More and more urgent.With pellet (PM10), fine particle (PM2.5) it is characterized the regional atmospheric environment problem of pollutant
Become increasingly conspicuous, damage body health of people, affect social harmony stable.Along with China's industrialization, deeply the pushing away of urbanization
Entering, energy consumption continues to increase, and prevention and control of air pollution pressure continues to strengthen.Along with the raising of people's living standard, people
Become more concerned with the indoor environmental quality problems such as living space, office space, the vehicles, Leisure Consumption place.
By China's air cleaning industry development is investigated and is thought prospect analysis of market, due to air pollution, environment
The factors such as out of control, smoking population persistently rising, in recent years, the sickness rate of pulmonary carcinoma is continued for rising.Public's environmental pollution
The hidden danger brought shows unprecedented anxiety and concern, and Public Environmental Awareness constantly strengthens.China's air cleaning at present
Device family recoverable amount is less than 1%, and following air purifier market will present the gesture of development of advancing by leaps and bounds.
The most the most frequently used purification air technique is activated carbon adsorption.Activated carbon is a kind of porous carbon containing matter, it
Having highly developed hole structure, the loose structure of activated carbon is provided for substantial amounts of surface area, fully can connect with gas
Touch, impart, by capillarity, the absorption property that activated carbon is powerful so that it is be very easy to reach the purpose of adsorbing contaminant.When
The pore structure of activated carbon is slightly larger than the diameter of harmful gas molecule, it is possible to allow harmful gas molecule completely in the case of,
Owing to attracting each other between molecule, harmful impurity can be attracted in aperture, reach to purify the effect of air.This
Outward, utilizing the feature of activated carbon small-bore, in air, the Particulate Pollution thing of major diameter can be blocked on the side of activated carbon, from
And achieve the purpose of filtration, purification.Other air purifying process also include: light catalytic purifying, ozonization, Electrostatic Absorption, mistake
Filter etc..Current indoor air purification product can be divided into two classes, first kind product be utilize filters, adsorb, magnetize, electrostatic suction
Dirt, anion eliminate the purifiers such as flue dust.This purifier based on physical cleaning, shortcoming is cannot eliminate by different
The pollution that smell, pathogen, virus, microorganism etc. cause.Second filial generation product is to produce ozone anion as major function
Air purifier.Ozone has sterilization, sterilization, deodorant to taste and goes the functions such as paint pigment.
In the recent period, Beijing-tianjin-hebei Region mist, haze are multiple to take place frequently, and atmospheric pollution presents new feature, heavy metal ion, antibacterial, virus
Content in rising trend.Using traditional purification method cannot tackle such severe contamination problem, these technology are not only
Secondary pollution problem can be there is, and it is weak that the pathogenic bacterium in air are killed ability, it is impossible to reach the purpose being fully cleaned up.Cause
This, develop a kind of novel material for air purification and technology of preparing in the urgent need to.
Summary of the invention
It is an object of the invention to for being badly in need of at present most the air pollution problems inherent that solves, new special according to current atmospheric pollution
Point, it is provided that the eliminated PM of a kind of antimicrobial form2.5Air cleaning film.This purification membrane is total to by nano graphene oxide and fluorescence
The addition of conjugated polymer component, collection eliminates PM2.5, antibacterial and monitoring etc. multi-functional in one, PM can be improved2.5Clearance, and
There is good bactericidal effect.
The technical scheme is that
A kind of multifunctional air purifying film, described multifunctional air purifying film is one of following two:
The first air cleaning film, including basement membrane, and is supported on epilamellar Multifunctional layered；Wherein, every square of mesityl
0.8～10g Multifunctional layered it is loaded with on film；Described Multifunctional layered is the mixed of nano graphene oxide and fluorescent conjugated polymer
Compound, mass ratio is graphene oxide: fluorescent conjugated polymer=5～20:1；Described basement membrane is non-woven fabrics；
Or, the second air cleaning film, for high-molecular organic material, nano graphene oxide and fluorescent conjugated polymer
Spray fusing after mixing and obtain, using described purification membrane aperture is 0.2～12 μm, and thickness is 500～5000 μm；Wherein, mass ratio
For high-molecular organic material: nano graphene oxide: fluorescent conjugated polymer=50-300:3-6:1.
The material of described non-woven fabrics or macromolecular material be polrvinyl chloride (PVC), polymethyl methacrylate (PMMA),
Polymethyl acrylate (PC), polystyrene (PS), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE),
Polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), poly-propionitrile (PAN), polyether sulfone (PES), poly-partially
One in fluorothene (PVDF).
Described nano graphene oxide is the graphene oxide of a diameter of 10-2000nm；Described nano graphene oxide is
The atom number of plies is the graphene oxide of 1-10 layer.
Described fluorescent conjugated polymer includes: pyridine radicals porphyrin, phenyl porphyrin, methylene blue, toluidine blue, hemoporphyrin, two
Hydrogen porphin, poly-[3-(2 '-N, N, N-triithylamine base-1 '-ethyoxyl)-4-methylthiophene hydrochlorate], poly-3-(Isosorbide-5-Nitrae-dioxa-
6-bromination trimethylamine groups-hexyl) thiophene-co-3-(1,4,7-trioxa-octyl) thiophene.
The preparation method of the first described multifunctional air purifying film, comprises the steps:
(1) obtain mixed liquor after nano graphene oxide solution and fluorescent polymer solution being mixed, then use coating
Method or infusion method are assembled on basement membrane；Wherein, the concentration of nano graphene oxide aqueous solution is 0.1mg/mL～10mg/mL, glimmering
The concentration of the aqueous solution of photopolymer is 0.1mg/mL～10mg/mL；Mass ratio is graphene oxide: fluorescent conjugated polymer=
5～20:1；Described basement membrane is non-woven fabrics；
Described infusion method, comprises the steps: to be immersed on basement membrane in mixed liquor, after soaking 1-12 hour, then adopts
Nano graphene oxide solution in mixed liquor and fluorescent polymer are supported on basement membrane by the mode taking sucking filtration；Every square of mesityl
0.8～10g nano graphene oxide solution and fluorescent polymer it is loaded with on film；
Described cladding process, comprises the steps: mixed liquor with being coated onto membrane surface, and coating number of times is 1-20 time, makes
0.8～10g nano graphene oxide solution and fluorescent polymer is adhered on every square metre of basement membrane；
(2) inserting in vacuum drying oven by organic basement membrane that upper step obtains, 20-60 DEG C, vacuum is under 100-1000Pa
Drying time is 1-24 hour.
The preparation method of described the second multifunctional air purifying film, comprises the steps:
(1) organic polymer is melted at 120-160 DEG C；
(2) it is subsequently adding nano graphene oxide solution and fluorescent conjugated polymer solution, stirs, wherein, nanometer
The concentration of graphene oxide water solution is 0.1mg/mL～10mg/mL, and the concentration of the aqueous solution of fluorescent polymer is 0.1mg/mL
～10mg/mL；Mass ratio is high-molecular organic material: nano graphene oxide: fluorescent conjugated polymer=50-300:3-6:1；
(3) utilizing spray fusing method masking, obtaining membrane aperture is 0.2～6 μm；The thickness of film is 500～5000 μm；
(4) film upper step prepared is at 20-60 DEG C, and vacuum is to be dried as 1-10 hour under 100-500Pa, obtains second
Plant multifunctional air purifying film.
A kind of fluorescent conjugated polymer, this polymer is poly-3-(Isosorbide-5-Nitrae-dioxa-6-bromination trimethylamine groups-hexyl) thiophene
Fen-co-3-(Isosorbide-5-Nitrae, 7-trioxa-octyl) thiophene, its structural formula is as follows:
Wherein, m1m2For the degree of polymerization, m1=1-10；m2=1-10.
The substantive distinguishing features of the present invention is:
Graphene oxide is the oxide of Graphene, and it is to be connected to oxy radical at random in Graphene inside and surrounding,
It is prone to further functionalization, can be combined with other molecule by the multiple non-covalent bond such as hydrophobic interaction, electrostatic interaction.
Graphene oxide wide material sources, cheap, intensity is high, and controllability is strong, meets the requirement of the big production of scale.
Fluorescent conjugated polymer is made up of by being conjugated many extinction unit, thus has and extremely strong catch light ability.
Nineteen ninety-five, Swager proposes the concept of fluorescent conjugated polymer fluorescence signal enlarge-effect first, is subject to when existing in detection system
During body molecule, the energy of polymer capture can carry out delocalization along whole conjugated backbone, is ultimately transferred to acceptor molecule thus puts
Big its fluorescence signal (i.e. " molecular line effect "), this is particularly significant for improving imaging and diagnostic sensitivity.Little molecule is passed
Sense system, when Small-molecule probe and detected material effect, detected material and little molecule are one to one, if detected material
Concentration produce response less than the concentration of Small-molecule probe, only part sensor molecules, so sensing system based on little molecule
Sensitivity cannot be comparable with fluorescent conjugated polymer.The fluorescence signal amplification characteristic utilizing fluorescent conjugated polymer can be at double
Ground improves detection sensitivity, and the development for biosensor provides new sensing modes.Water soluble fluorescent conjugated polymer with
The surfaces such as antibacterial, fungus and virus combine, it is possible to produce singlet oxygen as light-sensitive material under white light illumination and reach sterilization
To show toxic and side effects little, to different types of disease additionally, fluorescent conjugated polymer is for light power antimicrobial chemical therapy for effect
Former bacterium has the advantages such as bactericidal effect, and compared with antibiotic, it is not easy to in-ductive drug-tolerance, is a kind of the most excellent antibacterial
Method.Our made purification membrane uses the graphene oxide after ultrasonication, is diminished by graphene oxide lamella, then
Fluorescent conjugated polymer in assembling, adds high-molecular organic material basement membrane to, overcomes some technological difficulties, improves suction greatly
Attached PM2.5Achieve while efficiency and kill harmful bacteria in purifying air event.
The invention have the benefit that
The eliminated PM of the antimicrobial form that the present invention obtains2.5Air cleaning film, with traditional antibacterial compared with, have efficiently,
Antibacterial, use time length etc. feature.
(1) air-filtering membrane that the present invention provides is to the PM in air2.5Clearance high up to about 95%, the fullest
Foot PM2.5Protection requirements.
(2) the air cleaning film that the present invention provides has killing action, antibiotic rate to antibacterial, fungus, pathogen in air
Up to more than 90%.
(3) the air cleaning film that the present invention provides can monitor the absorption PM on purification membrane surface in real time2.5And all kinds of cause of disease
Bacterium.
(4) service life of the air cleaning film that the present invention provides is long, and on market, existing air-filtering membrane at most uses
300 hours, the present invention provides air cleaning film service life was up to 1000 hours.
(5) the air cleaning film that the present invention provides is compared with the most existing air cleaning film, uses electrostatic knot
Close, Absorptive complex wave, reentrainment of dust will not be produced and pollute.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of the nano graphene oxide that the present invention utilizes.
Fig. 2 is that the air-filtering membrane described in embodiment 1 is to PM2.5The photo of removal effect, wherein, Fig. 2 a is clean for using
Sampling film is used to collect PM in air before changing film in Laboratory Module10The photo that amount is 0.6mg；Fig. 2 b is for real before using purification membrane
Sampling film is used to collect PM in air in hatch checking2.5The photo that amount is 4.5mg；Fig. 2 c is in Laboratory Module after use purification membrane
Sampling film is used to collect PM in air10The photo that amount is 0.5mg；Fig. 2 d is for using sampling in Laboratory Module after using purification membrane
Film collects PM in air2.5The photo that amount is 3.4mg.
Fig. 3 is this air cleaning film anti-microbial property test result photo in embodiment 1, and wherein Fig. 3 a is that cell plates is cultivated
The photo of bacterium amount in Laboratory Module after use purification membrane；Fig. 3 b is that cell plates is cultivated and used after non-woven fabrics the photograph of bacterium amount in Laboratory Module
Sheet.
Fig. 4 is this air cleaning film detection PM in embodiment 12.5Design sketch, wherein, Fig. 4 a is not for use purification membrane at purple
The photo of fluorescent brightness under outer lamp；Fig. 4 b be use after purification membrane under uviol lamp fluorescent brightness photo.
Detailed description of the invention
The present invention be will be described in further detail with reference to the following examples.The following examples are for explanation purposes, and
It is not intended to limit the scope of the present invention.Experimental technique in following embodiment is conventional method if no special instructions.Following
Experiment material used in embodiment, is if no special instructions and is commercially available from routine biochemistry reagent shop.
The graphene oxide that the present invention relates to is well known materials.Wherein, the preparation method of graphene oxide can be found in document
Graphene-based composite materials, Nature, 2006 year volume 442 282-286 page.It is respectively provided with three weights
Multiple experiment, results averaged.The nano graphene oxide obtained is a diameter of 10-2000nm, the atom number of plies is 1-10 layer
Graphene oxide, following example use for 300-400nm, monolayer.
Embodiment 1,
The first step, prepares nano graphene oxide aqueous solution:
Take graphene oxide to dissolve, ultrasonic disperse in ice bath, ultrasonic power 100W, ultrasonic 60 minutes.Size can be obtained about
For the graphene oxide of 350nm, the atom number of plies is monolayer.Dried for standby.
Take 0.5g nano graphene oxide obtained above, be dissolved in 1000mL ultra-pure water, obtain receiving of 0.5mg/mL
Rice graphene oxide water solution；
Second step, prepared by conjugated polymer:
Monomer (1) 3-(1,4-dioxa-6-hydroxy-hexane base) thiophene synthesis route:
Add 45mL pyridine, diethylene glycol 15mL (16.75g, 157.8mmol), (5.6g, 49.9mmol), Hydro-Giene (Water Science).
(1.4g, 7.34mmol), adds 3 bromo thiophene (5.16g, 31.6mmol) after stirring reaction 30min, rises to 100 DEG C, reaction
24h.Reactant liquor is cooled to room temperature, adds dchloromethane, filter, be dried, obtain product pale yellowish oil liquid (4.16g,
Productivity 70%).
The sign 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)；, 3.67 (t, 2Hs) 13C NMR (100MHz, CDCl3, ppm): 2H). characterize data and show: obtain
Monomer 3-(1,4-dioxa-6-hydroxy-hexane 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, ice-water bath is cooled to 0 DEG C and adds pyridine 1mL.
Add TsCl (1.8g, 9.44mmol), continue reaction 24h.Use CH2Cl2Extraction, then with washing, is dried, concentrates, purification,
Obtain light yellow solid (1.62g, 76%) eventually.
The sign 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 data and show: obtained monomer 3-
(1,4-dioxa-6-p-methyl benzenesulfonic acid base-hexyl)
The synthesis of monomer (3) 3-(the bromo-hexyl of 1,4-dioxa-6-) thiophene:
Monomer (2) (0.62g, 1.81mmol) is dissolved in 15mL acetone, addition LiBr H2O (0.68g,
6.48mmol), reaction 8h.After extraction, it is dried, concentrates, purification, obtain pale yellow oily liquid body (0.41g, 90%).
The sign 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 data and show: obtained monomer 3-(1,4-dioxy
The bromo-hexyl of miscellaneous-6-) thiophene
The synthesis of monomer (4) 3-(1,4-dioxa-6-bromination trimethylamine groups-hexyl) thiophene:
Being dissolved in oxolane by monomer (3) (1.23g, 4.9mmol), methanol solution, overnight, reaction stops in 40 DEG C of reactions
And after being cooled to room temperature, rotation is steamed, and dissolves, add 40mL normal hexane and be settled out solid, be centrifuged to obtain precipitation, obtain white after drying solid
Body (1.44g, 94.7%).
The sign 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.
Sign data show: obtained monomer 3-(1,4-dioxa-6-bromination trimethylamine groups-hexyl) thiophene
The synthesis of monomer (5) 3-(1,4,7-trioxa-octyl) thiophene:
2,6-lutidines, diethylene glycol monomethyl ether (5.89g, 49.1mmol), uncle it is sequentially added in two mouthfuls of flasks
Butyl potassium alcoholate (3.58g, 32mmol) Hydro-Giene (Water Science). (608mg, 0.36mmol), stirs, and adds 3-bromine thiophene after reaction 30min
The lutidines solution of fen (5.16g, 31.6mmol), reaction is overnight.Reactant liquor is cooled to room temperature, filters, washing, dry
Dry, concentrate, chromatography, be dried to obtain brown liquid (5.1g, 80%).
The sign 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. sign data show:
Obtain monomer 3-(1,4,7-trioxa-octyl) thiophene
Poly-3-(1,4-dioxa-6-bromination trimethylamine groups-hexyl) thiophene-co-3-(1,4,7-trioxa-octyl)
The synthesis of thiophene (PT):
In reaction bulb, it is sequentially added into 10mL chloroform, anhydrous ferric trichloride (325mg, 2mmol), then drips monomer (4)
(155mg, 0.5mmol) and monomer (5) (101mg, 0.5mmol), room temperature reaction 2 days.Methanol is added sudden in reaction mixture
Going out reaction, centrifugal, methanol/chloroform (1:1) washs, and is subsequently adding tetrabutylammonium chloride, generates black precipitate.Precipitation is filtered,
Filter cake again with methanol is dissolved, and adds hydrazine hydrate, and solution is spin-dried for, washing, utilizes the bag filter dialysis 2 that molecular cut off is 3500Da
My god；Remove solvent, be dried to obtain solid.
The sign 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).Sign data show: obtained poly-3-(1,4-dioxa-6-bromine
Change trimethylamine groups-hexyl) thiophene-co-3-(1,4,7-trioxa-octyl) thiophene (PT)
Described fluorescent conjugated polymer, poly-3-(Isosorbide-5-Nitrae-dioxa-6-bromination trimethylamine groups-hexyl) thiophene-co-3-
(1,4,7-trioxa-octyl) thiophene (PT) structural formula is as shown below:
Wherein, m1m2For polymer, m1Span: 1-10；m2Span is 1-10.
3rd step, the aqueous solution of configuration fluorescent conjugated polymer:
Fluorescent conjugated polymer: poly-3-(1,4-dioxa-6-bromination trimethylamine groups-hexyl) thiophene-co-3-(1,4,
7-trioxa-octyl) preparation of thiophene (PT) solution: take 0.01g PT and add in 10mL ultra-pure water, obtain 1mg/mL storage
Liquid.
4th step, the preparation of multifunctional air purifying film:
(1) prefabricated non-woven fabrics is cut into right dimensions and shapes as requested.Described non-woven fabrics polypropylene
Material, size is 25cm × 25cm, and aperture is 2000 μm；
(2) the nano graphene oxide aqueous solution that 100mL concentration is 0.5mg/mL is prepared；
(3) fluorescent conjugated polymer in dilution the 3rd step is to 0.1mg/mL；Take 100mL；
(4) mixed liquor is obtained, so after nano graphene oxide solution obtained above and fluorescent polymer solution being mixed
After will be immersed in mixed liquor on high-molecular organic material basement membrane, after soaking 1 hour, then take repeatedly sucking filtration mode will mixing
Nano graphene oxide solution and fluorescent polymer in liquid is all supported on basement membrane (being masked as filtrate clarification)；The most often put down
0.960g nano graphene oxide solution and fluorescent polymer it is loaded with on Fang meter Ji film；
(5) basement membrane that upper step obtains is inserted in vacuum drying oven, 30 DEG C, 200Pa, drying time: 12 hours, obtain this
Invent used purification membrane.
Checking purification membrane absorption PM2.5Ability (this embodiment is with reference to People's Republic of China's environment protectment protection HJ
656-2013 and HJ 618-2013):
A () is adopted granule PM by use on air sampler in Laboratory Module2.5And PM10Sampling film, take four, respectively
Labelling A, B and A ', B ' according to People's Republic of China's environment protectment protection HJ 656-2013 process,
(b) test process: the identical Laboratory Module 1 set up according to GB GB-T14295-2008 and Laboratory Module 2.?
In Laboratory Module 1, after using aerosol generator to produce smog, open sampler and use sampling film A, B to collect respectively in laboratory
PM2.5And PM10Granule, collect after 2h, obtain initial p M in Laboratory Module2.5And PM10Concentration value.In Laboratory Module 2, use cigarette
Fog generator produces after smog, opens the purifier 3 hours equipped with air cleaning film.After purification, it is then turned on sampler
Sampling film A ', B ' is used to collect PM in laboratory2.5And PM10Granule, obtain PM in the rear deck of Laboratory Module internal filter filtration2.5
And PM10Concentration value.
Result of calculation PM2.5And PM10Concentration, unit is μ g/m3。
With reference to the accompanying drawings 2, the indoor PM opened before air filter can be drawn2.5And PM10Concentration and make to be finished air mistake
PM in filter rear chamber2.5And PM10Concentration, i.e. can obtain make by oneself purification membrane reduce room air PM2.5And PM10The ability of concentration.
Result can show, PM in Laboratory Module after use purification membrane2.5And PM10Amount reduce.Demonstrate use purification membrane of the present invention and purify sky
The ability of gas.
(this embodiment is with reference to People's Republic of China (PRC) environment protectment protection GB 21551.3-for checking purification membrane antibacterial ability
2010):
The mono-bacterium colony of (a) picking E.coli in 5mL LB culture medium (in 50 in (B551.3-20) 37 cultivate 12h；
B () uses PBS (PBS particular make-up: sodium chloride 4g, potassium chloride 0.1g, disodium hydrogen phosphate 0.71g, potassium dihydrogen phosphate
0.135g, is dissolved in 500mL ultra-pure water, ionic strength 137mM PH=7.4) wash bacterium 3 times, then wash bacterium with PBS suspension；
C () adjusts suspended bacteria 107Cfu/mL；
D () takes the bacterium solution on 10 μ L in step, add 990 μ L PBS, drip to non-woven fabrics and the Ben Fa of 1cm × 1cm respectively
In bright purification membrane；
E the purification membrane of non-woven fabrics and the present invention in upper step is respectively put into and puts into holes in the middle of 12 orifice plates by (), hole, side adds
Enter 3mL ultra-pure water.Put into 37 DEG C of cultivation 3h in incubator；
F () washes bacterium with 1mL PBS the most respectively, collect, and uses 1mL PBS again to suspend；
G bacterium solution in step on () gradient dilution, each concentration takes 50 μ L coated plates, puts into 37 DEG C of cultivation 12h in incubator；
H () is taken out flat board and is observed counting.
With reference to the accompanying drawings 3 as a result, it was observed that, the point on flat board, a point represents a bacterium, uses Laboratory Module after purification membrane
Interior bacterium amount declines about 90%.Demonstrate the ability that purification membrane of the present invention is antibacterial.
Detection purification membrane service life:
A () is opened cigarette smoke generator in the airtight Laboratory Module set up according to GB GB-T14295-2008 and is allowed to not
The raw PM of pregnancy ceased2.5；
B () uses the air cleaning film of non-woven fabrics and the present invention to filter simultaneously；
C () was taken off filter membrane every 12 hours and is weighed, put back to continuation again and filter, when filter membrane weight no longer becomes after having weighed
During change, duration is exactly the service life of graphene oxide filter membrane；
When experiment proceeds to 300, little non-woven fabrics no longer increases weight constantly, and non-woven fabrics service life is 300 hours.The present invention's
Purification membrane is until proceeding to 1000 and little no longer increasing weight constantly, and purification membrane of the present invention service life is 1000 hours.
Detection PM2.5Method.
In the Laboratory Module set up according to GB GB-T14295-2008, cigarette smoke generator is used persistently to produce smog
After, use purification membrane to purify 1 hour.After purification, take off air cleaning film, under uviol lamp, the most directly observe sample
Color, compared with original purification membrane color under lamp, fluorescent quenching.
Embodiment 2-8
Other step and method of testing with embodiment 1, difference be, fluorescent conjugated polymer used in step 3 by
In embodiment 1, the aqueous solution of the 3rd step configuration fluorescent conjugated polymer replaces with and configures following fluorescent conjugated polymer successively:
The preparation of (a) pyridylporphyrin TPP solution: take 0.0068g pyridylporphyrin TPP and add in 20mL ultra-pure water, obtain
0.25mM stock solution.
The preparation of (b) benzene porphyrin TP solution: take 0.0076g phenyl porphyrin TP and join in 20mL ultra-pure water, obtain
0.25mM stock solution.
The preparation of (c) sub-blue M-B solution: take 0.0016g Asia indigo plant M-B and add 20mL ultra-pure water and dissolve and to obtain 0.25mM storage
Liquid.
The preparation of (d) C.I. 49410. T-BO solution: take 0.001g toluidine blue TBO addition 20mL ultra-pure water and dissolve to obtain 0.25mM
Stock solution.
The preparation of (e) hemoporphyrin H-P solution: take 0.0033g hemoporphyrin HP add 20mL ultra-pure water dissolve to obtain 0.25mM storage
Liquid storage.
The preparation of (f) chlorin P-C solution: take 0.003g chlorin PC addition 20mL ultra-pure water and dissolve to obtain 0.25mM
Stock solution.
(g) fluorescent conjugated polymer: poly-[3-(2 '-N, N, N-triithylamine base-1 '-ethyoxyl)-4-methylthiophene hydrochloric acid
Salt] preparation of (PMNT) solution: take 0.004g PMNT and add in 5mL ultra-pure water, obtain 0.125mM stock solution.
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-blue M-B | 97% | 87% | 1000 |
| C.I. 49410. T-BO | 99% | 86% | 1000 |
| Hemoporphyrin H-P | 97% | 89% | 1000 |
| Chlorin P-C | 97% | 90% | 1000 |
| PMNT | 99% | 89% | 1000 |
Embodiment 9
The first step, making purification membrane:
Organic polymer polypropylene is melted at 140 DEG C；
It is subsequently adding nano graphene oxide solution and fluorescent conjugated polymer (poly-3-(1,4-dioxa-6-bromination front three
Amido-hexyl) thiophene-co-3-(Isosorbide-5-Nitrae, 7-trioxa-octyl) thiophene (PT)) solution, stir, wherein, nano oxygen
The concentration of functionalized graphene aqueous solution is 0.5mg/mL, 600mL, and the concentration of the aqueous solution of fluorescent polymer is 1.0mg/mL,
100mL；Mass ratio is high-molecular organic material: nano graphene oxide: fluorescent conjugated polymer=200:3:1；
Said mixture utilizes spray fusing method masking, and obtaining membrane aperture is 1 μm；Thickness 2000 μm of film；Wherein: spray fusing sets
Standby: Wuxi Ai Jiemeisi Machinery Co., Ltd. (spinneret width 30cm, die head draw ratio 1:10, orifice diameter 0.3mm, hole
Deep 3mm.Process conditions: air pressure: 0.15-0.3MPa；Receiving range 5-9cm；Dosing pump rotating speed: 45-60Hz, preferably work
Skill: air pressure: 0.25MPa；Receiving range: 6cm；Dosing pump rotating speed: 50Hz (can obtain optimum aperture 0.45 μm)
The film upper step prepared is at 40 DEG C, and vacuum is that to be dried under 200Pa be 3 hours, obtains the second multi-functional air
Purification membrane.
Obtain the second multifunctional air purifying film method of testing to approximate with embodiment 1 with embodiment 1, experimental result.
Embodiment 10-16
Other step and method of testing are that the fluorescent conjugated polymer of use is by embodiment 9 with embodiment 9, difference
In fluorescent conjugated polymer (poly-3-(1,4-dioxa-6-bromination 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, the aqueous solution of benzene porphyrin TP,
The sub-blue aqueous solution of M-B, the aqueous solution of C.I. 49410. T-BO, the aqueous solution of hemoporphyrin H-P, the aqueous solution of chlorin P-C, poly-
The aqueous solution of [3-(2 '-N, N, N-triithylamine base-1 '-ethyoxyl)-4-methylthiophene hydrochlorate] (PMNT).
Test result approximates with embodiment 9.
Unaccomplished matter of the present invention is known technology.
Claims (7)
1. a multifunctional air purifying film, is characterized by that this multifunctional air purifying film is one of following two:
The first air cleaning film, including basement membrane, and is supported on epilamellar Multifunctional layered；Wherein, on every square metre of basement membrane
It is loaded with 0.8～10g Multifunctional layered；Described Multifunctional layered is the mixing of nano graphene oxide and fluorescent conjugated polymer
Thing, mass ratio is graphene oxide: fluorescent conjugated polymer=5～20:1；Described basement membrane is non-woven fabrics；
Or, the second air cleaning film, mix for high-molecular organic material, nano graphene oxide and fluorescent conjugated polymer
Rear spray fusing and obtain, using described purification membrane aperture is 0.2～12 μm, and thickness is 500～5000 μm；Wherein, mass ratio is for having
Machine macromolecular material: nano graphene oxide: fluorescent conjugated polymer=50-300:3-6:1.
2. multifunctional air purifying film as claimed in claim 1, is characterized by material or the macromolecule material of described non-woven fabrics
Material for polrvinyl chloride (PVC), polymethyl methacrylate (PMMA), polymethyl acrylate (PC), polystyrene (PS), ethylene-
Acetate ethylene copolymer (EVA), ethylene-octene copolymer (POE), polypropylene (PP), polyethylene (PE), poly terephthalic acid second
One in diol ester (PET), poly-propionitrile (PAN), polyether sulfone (PES), Kynoar (PVDF).
3. multifunctional air purifying film as claimed in claim 1, is characterized by that described nano graphene oxide is a diameter of 10-
The graphene oxide of 2000nm；Described nano graphene oxide be the atom number of plies be the graphene oxide of 1-10 layer.
4. multifunctional air purifying film as claimed in claim 1, is characterized by that described fluorescent conjugated polymer includes: pyridine radicals
Porphyrin, phenyl porphyrin, methylene blue, toluidine blue, hemoporphyrin (HP), chlorin, poly-[3-(2 '-N, N, N-triithylamine base-1 '-
Ethyoxyl)-4-methylthiophene hydrochlorate], poly-3-(1,4-dioxa-6-bromination trimethylamine groups-hexyl) thiophene-co-3-(1,
4,7-trioxa-octyl) thiophene.
5. the preparation method of the first multifunctional air purifying film as claimed in claim 1, is characterized by comprise the steps:
(1) obtain mixed liquor after nano graphene oxide solution and fluorescent polymer solution being mixed, then use cladding process or
Infusion method is assembled on basement membrane；Wherein, the concentration of nano graphene oxide aqueous solution is 0.1mg/mL～10mg/mL, and fluorescence gathers
The concentration of the aqueous solution of compound is 0.1mg/mL～10mg/mL；Mass ratio is graphene oxide: fluorescent conjugated polymer=5～
20:1；
Described basement membrane is non-woven fabrics；
Described infusion method, comprises the steps: to be immersed on basement membrane in mixed liquor, after soaking 1-12 hour, then takes to take out
Nano graphene oxide solution in mixed liquor and fluorescent polymer are supported on basement membrane by the mode of filter；On every square metre of basement membrane
It is loaded with 0.8～10g nano graphene oxide solution and fluorescent polymer；
Described cladding process, comprises the steps: mixed liquor with being coated onto organic membrane surface, and coating number of times is 1-20 time, makes
0.8～10g nano graphene oxide solution and fluorescent polymer is adhered on every square metre of basement membrane；
(2) inserting in vacuum drying oven by organic basement membrane that upper step obtains, 20-60 DEG C, vacuum is to be dried under 100-1000Pa
Time is 1-24 hour.
6. the preparation method of the second multifunctional air purifying film as claimed in claim 1, is characterized by comprise the steps:
(1) organic polymer is melted at 120-160 DEG C；
(2) it is subsequently adding nano graphene oxide solution and fluorescent conjugated polymer solution, stirs, wherein, nano oxidized
The concentration of graphene aqueous solution is 0.1mg/mL～10mg/mL, the concentration of the aqueous solution of fluorescent polymer be 0.1mg/mL～
10mg/mL；Mass ratio is high-molecular organic material: nano graphene oxide: fluorescent conjugated polymer=50-300:3-6:1；
(3) utilizing spray fusing method masking, obtaining membrane aperture is 0.2～6 μm；The thickness of film is 500～5000 μm；
(4) film upper step prepared is at 20-60 DEG C, and vacuum is to be dried as 1-10 hour under 100-500Pa, obtains the second many
Function air cleaning film.
7. a fluorescent conjugated polymer, is characterized by that this polymer is poly-3-(Isosorbide-5-Nitrae-dioxa-6-bromination trimethylamine groups-own
Alkyl) thiophene-co-3-(Isosorbide-5-Nitrae, 7-trioxa-octyl) thiophene, its structural formula is as follows:
Wherein, m1=1-10；m2=1-10.
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| CN109851233A (en) * | 2019-03-27 | 2019-06-07 | 孙玉白 | One kind containing photosensitive internally coated extraordinary quartz ampoule and the preparation method and application thereof |
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