CN104998622B - It is a kind of to remove cationization skeleton polymer of bacterium in air and preparation method thereof - Google Patents
It is a kind of to remove cationization skeleton polymer of bacterium in air and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920001661 Chitosan Polymers 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000002118 epoxides Chemical group 0.000 claims abstract description 6
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims abstract description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 4
- -1 glycol glycidyl ethers Chemical class 0.000 claims abstract description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims abstract description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 4
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- 238000001179 sorption measurement Methods 0.000 claims abstract 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- 230000010148 water-pollination Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- 230000005595 deprotonation Effects 0.000 claims description 3
- 238000010537 deprotonation reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000004887 air purification Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 9
- 244000005700 microbiome Species 0.000 abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 4
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- 150000001450 anions Chemical class 0.000 abstract 1
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- 239000002245 particle Substances 0.000 abstract 1
- 229920000867 polyelectrolyte Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
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- 230000009286 beneficial effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
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- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
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- 238000009423 ventilation Methods 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000588881 Chromobacterium Species 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 241000186227 Corynebacterium diphtheriae Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 241000187479 Mycobacterium tuberculosis Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The present invention is on a kind of ionization skeleton polymer and its preparation method and the application in eliminating particle Substances Pollution.Utilize the existing distinctive three dimensional skeletal structure of melamine sponge, chitosan coat is coated on skeleton, reacted again by glycol glycidyl ethers and chitosan coat, it is crosslinked it and carries substantial amounts of epoxide group on surface, then epoxide group and sodium hydrogensulfite reaction generation azochlorosulfonate acid anion are utilized, PDDA is finally incorporated into material surface using electrostatic interaction, form polyelectrolyte hydration layer, skeleton surface is set to adsorb substantial amounts of small water droplet because of cationization, by bacterial adsorption to material surface or it can be transferred to when air circulation is in material duct in small water droplet, realize and purified by microorganism pollution air whereby.The advantage of this air cleaning mode is：Apparatus structure is simple, and material can be recycled for multiple times, and cost is low, and energy consumption is small, strong adaptability, all harmless to environment and people, without secondary pollution.
Description
Technical field
The present invention is to remove the cationization skeleton polymer and its preparation side of germ contamination in air on a kind of
Method.It can be polluted using the cationization skeleton polymer with convenient, fast, effective removal microbes in air.
Background technology
Air is not the existence place of microorganism well, because not only without required for microbial growth in air
The irradiation of nutriment and sufficient moisture, also daylight middle-ultraviolet lamp.But soil, water body, various rotten organic matters with
And the microorganism on humans and animals body, it can be carried in air, adrift be permitted really in air with the motion of air-flow
More invisible microorganism, they mainly have various coccuses, bacillus, production chromobacterium and have resistance to dry and ray
Fungal spore of power etc., it is also possible to have the pathogenic bacteria as mycobacterium tuberculosis, corynebacterium diphtheriae.Dust is the master of bacterium
Want carrier, thus in the air more than dust amount, microorganism is also more, typically in animal house, public place, hospital, dormitory, avenue
Deng air in, micro organism quantity is most.In recent years, urbanization life style promotes a large amount of aggregations and flowing, haze of population
Weather is further frequent, and the pollution of microbes in air substantially aggravates, and the health to the mankind produces serious threat, so increasingly drawing
Play the attention of people.
Bacterium is a kind of small form, semi-transparent clear and the tiny organism containing large quantity of moisture, controls the side of microorganism
Method has physical method and chemical method, and physical method includes：Heating power, radiation, filtering, osmotic pressure, drying and ultrasonic wave；Chemistry side
Method is exactly to kill microorganism using disinfectant.It must be noted that the means or method of eliminating bacteria are often same to people
Body is damaged, and institute's method described above mostly can only be for using, for the sky in human settlement under the special occasions of small range
Gas carries out sterilizing, a kind of safe method is lacked at present, ultraviolet is commonly used to efficiently sterilize human settlement, but
It is that ultraviolet is harmful in itself, while ultraviolet can produce ozone, will also result in the injury to human body.By contrast, mistake
Filtering method is that comparison is safe, but for the less bacterium of form, very little is also wanted in the aperture of filter medium, then air
Resistance will be very big, and the efficiency of filtering is exactly a problem, and in general filter method is relatively more suitable for thin in removing liquid
Bacterium pollutes.The present invention utilizes a kind of melamine resin of three dimensional skeletal structure, by being cationized to its surface, on the one hand makes
Material surface carries positive charge, and thus adsorbing negatively charged bacterium, (isoelectric point of bacterium is pH=2~5, in
Property environment in generally it is negatively charged)；On the other hand, the hydrophily of reinforcing material, it is found that its three-dimensional framework can be carried secretly countless
The small water droplet of segmentation, air is easy between small water droplet circulate with less resistance, and bacterium has good hydrophily,
It is easy to be transferred in water droplet, the polluter more usefully accumulated in framework material holds to be cleaned very much by water, so that
The material can be recycled for multiple times.The scheme of this air cleaning has many good qualities：Apparatus structure is simple, and use cost is low,
Energy consumption is small, strong adaptability, friendly to environment and people's all safety, without secondary pollution.
The content of the invention
Primary technical problem to be solved by this invention is to provide one for the pollution problem of human settlement's microbes in air
Air cleaning new departure that is easy to operate, working well is planted, it relies on a kind of skeleton structure high polymer material of cationization, this
Kind of material is easy to adhere to small water droplet, air can be made quickly to circulate again, realizes fully crossing for water and air, the bacterium in air
Both it can be adsorbed, can also be transferred in water droplet by cationic surface, thus the purpose of purification air can be reached.It is deposited on material
Pollutant in material is easy to be cleaned with water, and high polymer material can be recycled for multiple times, and the scheme of this air cleaning has very
Many advantages：Apparatus structure is simple, and use cost is low, and energy consumption is small, strong adaptability, all friendly to environment and people, without secondary pollution,
It is highly suitable for applying in human settlement.
Another technical problem to be solved by this invention is to provide the syntheti c route of above-mentioned cationization skeleton polymer
With method, it is practical, easy to operate, it is easy to produce in batches.
Another technical problem to be solved by this invention is to provide a kind of above-mentioned cationization skeleton polymer in removing
The concrete application of microorganism is floated in air.
1st, the present invention solve technical scheme that primary technical problem used for：A kind of three-dimensional framework polymerization of cationization
Thing, its structure has the duct interconnected that about 100 μm are included between feature as shown in Figure 1, skeleton, and this duct is to sky
The logical resistance of air-flow is very low, is 5 μm or so at the size minimum of skeleton, is linked between skeleton by common ground, is constituted three-dimensional
Continuous network structure.
It is beneficial that above-mentioned three-dimensional framework polymer surfaces covering polycation electrolyte, can adsorb band negative
The bacterium of electric charge, while having very strong hydrophily, is very beneficial for carrying small water droplet secretly in duct, makes small water droplet in the space
In intensive arrangement, the air of itself and circulation is occurred interracial contact, the bacterium in air is transferred in water droplet, it is real
Existing purification of the air under secured fashion.
2., the present invention solve the technical scheme that is used of another technical problem for：A kind of above-mentioned high-molecular bone frame material
Ioning method, operate it is as shown in Figure 4 with reaction scheme.
Its characterization step is：First the chitosan of commodity is dissolved in dilute acetic acid aqueous solution (viscosity be more than 400mPa be made into 1
~2wt.% concentration, the concentration that is made into 2~3wt.% of the viscosity in 200~400mPa scopes) add a small amount of cationic surface
Activating agent (such as DTAC, content in the solution is 0.1~0.2wt.% scopes), then will be commercially available
Melamine sponge (melamine reacts the foamed material being made, commercialization with formaldehyde crosslinking) is soaked in the solution, after taking-up
Unnecessary solution is sopped up with vacuum, it is ensured that it does not have solution outflow under standing, then again in an oven at 60 DEG C dry 2~
3 hours, then soaked 20~30 minutes in the sodium carbonate liquor of pH=9~10, form insoluble after chitosan deprotonation
Film is covered in skeleton surface, and material is soaked in 10~15wt.% ethylene glycol diglycidylether again after being washed with clear water
In being reacted 1~2 hour under normal temperature in ethanol solution, then washed 1~2 time with 95% ethanol, then it is soaked in 10 at normal temperatures~
Handled 1~2 hour in the aqueous solution of 15wt.% sodium hydrogensulfite, skeleton is made by the reaction of epoxide group and inferior sulfate radical
Sulfonate radical anion group in material strips, then soaked with 1~2wt.% PDDA aqueous solution normal temperature
Bubble 2~3 hours, polycation electrolyte hydration layer is introduced using electrostatic interaction, by material be placed in clear water immersion 3~
4 hours, the unadsorbed polycation to wash away.
Above-mentioned ethylene glycol diglycidylether plays two effects：One is the amino reaction with chitosan surface, is drawn
The epoxide group of suspension；Two are reacted with the amino inside chitosan, chitosan is crosslinked reaction, are conducive to the clad
Stabilisation.The existing very strong hydrophily of chitosan, has preferable mechanical strength, so can guarantee that coating will not take off easily again
Fall.
3., the present invention solve the technical scheme that is used of another technical problem for：Above-mentioned cationization skeleton polymer
Application process in germ contamination in removing air, it is characterised in that first make skeleton polymer fully absorb water, be subsequently placed in one
In individual ventilation unit, under the thrust of moving air, the part water in three-dimensional framework is extruded, and forms the logical of air flow
Road (as shown in Figure 2), reach balance after small water droplet with regard to dense distribution in the material.Obviously, the hydrophily of material is stronger, then water droplet
It is distributed more intensive, undressed melamine sponge only retains seldom water droplet.In air flow process, before and after measurement purification
Bacterium number in air is with regard to that can evaluate its effect to air cleaning.
It is beneficial that above-mentioned processing method is simple to operate, material may be reused, and operating cost is reasonable, due to
Work principle of filter is not based on, so no matter the bacterium of which kind of size can remove, air drag is small, effect is preferable, does not result in
Secondary pollution.
The advantage of the invention is that：Existing ultraviolet sterilization is avoided the drawbacks of secure context, by by air
Bacterium is directly adsorbed onto in material or is transferred directly in aqueous phase, can be simplified air cleaning problem, be conducive to people and ring
Border is got along amiably and peacefully.In addition, using wet method air cleaning can also simultaneously to air with humidification, in water deficient can and
When moisturizing, be particularly suitable for the use of northern area.
Brief description of the drawings
Fig. 1 is the stereochemical structure of cationization three-dimensional framework material；
Fig. 2 is the basic model of wet method air cleaning；
Fig. 3 is the bacterium colony on culture medium before and after purification；
Fig. 4 is the operation reaction scheme of framework material.
Embodiment
The present invention is described in further detail with reference to embodiments.
It is prepared by material：First the chitosan of commodity is dissolved in dilute acetic acid aqueous solution (viscosity be more than 400mPa be made into 1~
2wt.% concentration；The concentration that is made into 2~3wt.% of the viscosity in 200~400mPa scopes) add a small amount of cationic surface work
Property agent (such as DTAC, content in the solution is 0.1~0.2wt.% scopes), then melamine sponge is soaked
Bubble in the solution, sops up unnecessary solution, it is ensured that it does not have solution outflow under standing, then again in baking oven with vacuum after taking-up
Soaked 20~30 minutes in drying 2~3 hours at 60 DEG C, then in the sodium carbonate liquor of pH=9~10, chitosan deprotonation
After form insoluble film and be covered in skeleton surface, material is soaked in 10~15wt.% ethylene glycol again after being washed with clear water
React 1~2 hour, then washed 1~2 time with 95% ethanol under normal temperature in the ethanol solution of diglycidyl ether, then in normal temperature
Under soaked 1~2 hour in the aqueous solution of 10~15wt.% sodium hydrogensulfite, pass through the anti-of epoxide group and inferior sulfate radical
It should make sulfonate radical anion group on framework material band, then with the 1~2wt.% PDDA aqueous solution
Soaked 2~3 hours under normal temperature, polycation electrolyte hydration layer is introduced using electrostatic interaction, material is placed in clear water
Middle immersion 3~4 hours, the unadsorbed polycation to wash away, PDDA is commercialization medicine, weight
Average molecular weight is 5.2 × 104, polydispersity is 1.8.
Water retention is tested：Three-dimensional framework material can absorb substantial amounts of water, but in the presence of air flow thrust, greatly
Partial water will be discharged (as shown in Figure 2), and always the water of some still retains, affine with skeleton in airflow thrust
Under the collective effect of power, system can keep a kind of poised state automatically, and experiment proves that in the presence of same airflow thrust it is protected
Hydrophily of the water rate with material in itself is relevant.So-called water retention refers to the weight of water and the percentage of material own wt in experiment
Than table 1 lists experimental result, and water retention declines with the increase of air mass flow, under the promotion of same air mass flow, water conservation
Rate can increase because of the hydrophilic raising of material skeleton, since the present invention is to use wet method air purifying process, so water conservation
Rate is a critically important inspection target, and high water retention is naturally favourable to air cleaning, this be also framework material is carried out from
The basic reason of sonization.
The moisture-holding capacity of the material under the promotion of different air mass flows of table 1*
*Ventilation time is fixed as 1 minute
Purify test mode：An air circulation device is built in one 2 cubic metres of closing space, will with pressure fan
Air passes through skeleton polymer material by pipeline, and air mass flow is calculated with the sectional area of material.Measure single with the method for standard
The number of bacterium in the air of position volume, specific method is：Preprepared aseptic culture medium is used in purification process, every
A period of time is exposed 2~2.5 minutes in atmosphere, the bacterium in detection space is fallen on culture medium, and then closing is placed on
Cultivated 36 hours in constant incubator, calculate culture dish colony quantity, thus calculate of bacterium in every cubic metre in air
Number, the situation of culture dish colony is as shown in figure 3, culture dish colony is changed significantly before and after purification.In experimentation
Further look at influence of the material air flow to clean-up effect.
Test result：Table 2 lists the measurement result under the different air mass flows of different time, therefore deduces that following three
Individual conclusion：1st, bacterium number is reduced with the extension of clarification time, and it is present to illustrate wet method air purification effect；2nd, cation
General melamine sponge will be significantly better than by changing the clean-up effect of material, and this aspect is relevant with the moisture-holding capacity of material, and moisture-holding capacity is got over
The high clean-up effect to bacterium is better, and on the other hand also relevant with the surface characteristic of cationization, cationized surface is more favourable
In absorption bacterium；3rd, air velocity is bigger, and the speed of air circulation is faster, and it is faster that the density of bacterium is reduced, and illustrates that it tires out
Long-pending clean-up effect is more notable.
Clean-up effect * under the different time of table 2 difference air mass flow
* the thickness of experiment material is 6cm, and draught area is 64cm2。
Claims (4)
1. one kind cationization skeleton polymer material, it is characterised in that be 5 μm at the size minimum of skeleton, pass through between skeleton
Common ground is connected, and constitutes the duct interconnected for including 100 μm between continuous three-dimensional net structure, skeleton；
Described cationization skeleton polymer material is the skeleton based on melamine sponge, and poly dimethyl diene is contained on its surface
Propyl ammonium chloride is the polycation of composition, and its strong hydrophily contributes to absorption of the framework material to water droplet.
2. cationization skeleton polymer material according to claim 1, it is characterised in that described cationization skeleton
Polymeric material by bacterial adsorption to material surface or can be transferred in small water droplet in air circulation when wherein, realized whereby
Fast, efficient microbes in air purification.
3. the preparation method of the cationization skeleton polymer material described in a kind of claim 1, it is characterised in that step is successively
For：
(1) melamine sponge is immersed in chitosan solution, sops up unnecessary solution after taking-up with vacuum, it is ensured that it is under standing
There is no solution outflow, then in an oven in drying 2~3 hours at 60 DEG C, then the immersion in the sodium carbonate liquor of pH=9~10
20~30 minutes, insoluble film is formed after chitosan deprotonation and is covered in skeleton surface；
(2) ethanol solution of 10~15wt.% ethylene glycol diglycidylether is soaked in after above-mentioned material is washed with clear water again
React 1~2 hour, then washed 1~2 time with 95% ethanol under middle normal temperature；
(3) at normal temperatures in the aqueous solution of 10~15wt.% sodium hydrogensulfite soak 1~2 hour, by epoxide group with
The reaction of inferior sulfate radical makes sulfonate radical anion group on framework material band；
(4) soaked 2~3 hours with 1~2wt.% PDDA aqueous solution normal temperature, utilize electrostatic phase
Interaction is hydrated layer to introduce polycation electrolyte, and resulting materials are soaked 3~4 hours in clear water, not inhaled to wash away
Attached polycation.
4. the preparation method of cationization skeleton polymer material according to claim 3, it is characterised in that chitosan is molten
The viscosity of the concentration of liquid with itself is relevant：Viscosity is more than the 400mPa concentration for being made into 1~2wt.%, viscosity 200~
The concentration for being made into 2~3wt.% of 400mPa scopes.
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| CN105771924B (en) * | 2014-09-16 | 2018-02-27 | 宁波大学 | A kind of skeleton polymer for capsicum red pigment extraction and preparation method thereof |
| CN111214695A (en) * | 2020-01-10 | 2020-06-02 | 中美医药科技河北有限公司 | Novel 3D structure biological high molecular material prepared by covalent reaction and synthetic method thereof |
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| CN101327424B (en) * | 2008-04-29 | 2010-06-02 | 上海博物馆 | Formaldehyde adsorbing agent containing chitosan |
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