CN108513987A - Amine polymer-modified activated carbon of a kind of halogen for indoor sterilization and preparation method thereof - Google Patents
Amine polymer-modified activated carbon of a kind of halogen for indoor sterilization and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of amine polymer-modified activated carbon of the halogen for indoor sterilization and preparation method thereof, the present invention is that glycolylurea sodium salt is made in raw material with 5,5 Dimethyl Hydan and sodium ethoxide, and substitution reaction occurs with 3 chloropropyl triethoxysilanes in DMF；Ultrasonic dissolution siloxanes glycolylurea, halogen acids, which is added, makes its homogeneous polymerization in activated carbon surface, and carrying out halogenation to modified activated carbon with hydracid sodium salt obtains polysiloxanes halogen amine antibacterial active carbon, and such modified activated carbon is sufficiently stable in air, will not volatilize；The present invention has higher antimicrobial efficiency and longer anti-microbial property compared with common polymer antibacterial agent；Not only the type of applicable bacterium is more, but also also has inactivation performance well to enveloped virus；Invention improves the halogenation efficiency of product using the improvement of new halogenating agent and process.
Description
Technical field
The present invention relates to sterilizing technical field, it is specifically related to a kind of modified activated carbon and preparation method thereof.
Background technology
With the continuous improvement of modern industrialization level, air pollution situation is more severe, and investigation shows Interior Space
Usually 2~3 times more serious than outdoor air pollution of gas pollution level, in some cases, even up to more than 100 times.And Interior Space
Gas biological pollution is to influence a key factor of indoor air quality.A Canadian investigation shows that indoor air quality is asked
It is as caused by microbial contamination that topic, which has 21%,.Currently, China《Indoor Air Quality standards》Indoor microbial contamination
It is classified as three big polluters of indoor environment jointly with chemical contamination, radioactive pollution.
Desk research investigation finds that the indoor microbial contamination factor for damaging human health mainly has：Mould, dust mite, army
Five kinds of group bacterium, the hair of animal, scurf and pellet.Wherein mould is that one kind can be in warm and wet environment
The microorganism bred rapidly is the main reason for causing anaphylactia.Mould can make one to generate Nausea and vomiting, abdominal pain
Etc. symptoms, it is serious to result even in respiratory tract and intestines problem, such as asthma, dysentery.Medical research shows that interlinkage embraces mould
Mould, which is embraced, with branch has been identified it is the anaphylactogen for inducing asthma.
Dust mite is one of most common indoor microorganism, is to cause one of arch-criminal of anaphylactia.The danger of dust mite
Evil stems primarily from its sensitization, wherein most typical sensitization is to induce asthma.Meanwhile acarid can also cause anaphylaxis
Rhinitis, allergic dermatitis, Chronic urticaria etc..
Legionella is the general designation of a kind of bacterium, it shares a type more than 30, and a serotype, main parasitic are set in hot-water heating more than 50
The inner surface of standby and aqueduct and various water carrying services.Legionella main harm is to cause legionaires' disease, the cardinal symptom of this disease
Show as fever, shiver with cold, myalgia, headache, cough, pectoralgia, expiratory dyspnea etc., more allow people worry be its be up to 15% to
20% case fatality rate.
Scurf, hair of pet etc. can be such that the content of allergen in air increases, to cause the allergy of people.
People's Particulate Pollution object can be inhaled to be primarily referred to as having adsorbed the particulate matter of bacterium, be suspended in room and easily occupied indoor personnel's suction
In human respiratory, make contactee's illness.
The type of indoor microbial contamination is various, and the body of resident is often influenced because of the comprehensive function of multiple pollutant
Health.Therefore inhibit or eliminate indoor harmful microorganism, especially various harmful bacteriums and virus, be that reduction indoor environment is dirty
A kind of effective means of dye.
Also occurs antibacterial product in the prior art, but these product operations personnel need to be equipped with when in use to protect and arrange
It applies, other staff cannot rest on the space sterilized, and remaining chemical substance may cause human body other danger in air
Evil；And the disinfectant residence time is short, is easy to be neutralized by air, long term effect unobvious.
Or though product has bactericidal effect but effect is very limited, and storage life is short, is not suitable for being widely used.
Or need to carry out under the premise of having light, secondly its stability is insufficient, and cost is higher, and being not appropriate for large area makes
With.
Or it is only applicable to crops sterilization, can also degrade indoor formaldehyde to a certain extent, but to indoor bacteria disease
The killing effect of poison is not mentioned.
As it can be seen that explore and work out it is a kind of can play killing effect to indoor various bacterial fungus viruses etc., can grow
Nontoxic fungicide phase stabilization and persistently worked, reduces its influence to human body, improves its bactericidal effect, just seem
It is very necessary.Activated carbon is because having special microstructure, larger specific surface area and flourishing microcellular structure, while surface is contained
A large amount of chemical groups and the adsorbent for being used for multiple pollutant, and organic polymer antiseptic is with its low toxicity, sterilization in recent years
The features such as action temperature and stability are good receives more and more attention.
Invention content
To solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of halogen amine polymers for indoor sterilization
Modified activated carbon has the double effects for killing bacterium and virus, is a kind of solid phase macromolecule disinfection sanitizer of efficient stable.
The present invention will provide a kind of synthetic method of modified activated carbon simultaneously, and the low in raw material price of use is easy to get, and manufacturing process is simple,
It is easy to operate, it is easy to implement industrialized production.
In order to realize that the target, the present invention adopt the following technical scheme that：
A kind of amine polymer-modified activated carbon of halogen for indoor sterilization, structural formula are：
X includes：The ratio of Cl, Br and I, m and n are 1:1~1:9.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization, includes the following steps：
Step 1 is that glycolylurea sodium salt is made in raw material with 5,5- Dimethyl Hydan and sodium ethoxide；
Step 2, with 3- chloropropyl triethoxysilanes substitution reaction occurs for glycolylurea sodium salt in solvent dimethylformamide
Obtain siloxanes glycolylurea；
Step 3 sequentially adds activated carbon and hydrochloric acid after ultrasonic dissolution siloxanes glycolylurea, makes halogen acids homogeneous polymerization
In activated carbon surface；
Aqueous sodium hypochlorite solution is added in step 4, carries out halogenation to modified activated carbon with hydracid sodium salt, obtains poly- silicon
Oxygen alkane halogen amine antibacterial active carbon, structural formula are：
X includes：The ratio of Cl, Br and I, m and n are 1:1~1:9.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization above-mentioned, step 1, with 5,
5- Dimethyl Hydan and sodium ethoxide are that the detailed process that glycolylurea sodium salt is made in raw material is：
5,5- Dimethyl Hydan is dissolved in absolute ethyl alcohol, at room temperature stirring and dissolving by a, and sodium ethoxide, room temperature are added after dissolving
Lower reaction 20min stops reaction；
B is rotated at 40 DEG C, is put into 40 DEG C of vacuum drying chambers overnight after steaming ethyl alcohol, is obtained glycolylurea sodium salt.
The preparation method of the amine polymer-modified activated carbon of a kind of halogen for indoor sterilization above-mentioned, 5,5- in step 1
Dimethyl Hydan：3- chloropropyl triethoxysilanes：The mole dosage ratio of sodium ethoxide is 1:1:1~1:1:9.One kind above-mentioned
The preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization, step 2 are extra large in solvent dimethylformamide
Because sodium salt and 3- chloropropyl triethoxysilanes substitution reaction occur obtain the detailed process of siloxanes glycolylurea be：
A dissolves obtained glycolylurea sodium salt with solvent dimethylformamide, stirring, after being warming up to 40 DEG C；
3- chloropropyl triethoxysilanes are added dropwise in b, are continuously heating to 90 DEG C, sustained response 8-10h；
C is cooled to room temperature after reaction, is filtered, and is rotated at 90 DEG C of filtrate, is extracted solvent dimethylformamide out, is obtained
Siloxanes glycolylurea.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization above-mentioned, step 3 pass through
After ultrasonic dissolution siloxanes glycolylurea, activated carbon and hydrochloric acid are sequentially added, makes halogen acids homogeneous polymerization in the specific of activated carbon surface
Process is：A, the 3- that step 2 is obtained (5,5- Dimethyl Hydan) propyl-triethoxysilicane deionized water ultrasonic dissolution,
Activated carbon is added,
30min is shaken at room temperature, and activated carbon is made to be come into full contact with siloxanes glycolylurea；
Halogen acid solution is then added in b, and mixture is placed in 50 DEG C of isothermal vibration sinks, shakes 6h；
C, after the completion of reaction, in the modified activated carbon for being loaded with polysiloxanes glycolylurea is cleaned with deionized water being in solution
Property, it is placed in 120 DEG C of air dry ovens.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization above-mentioned, step 3 pass through
After ultrasonic dissolution siloxanes glycolylurea, activated carbon and hydrochloric acid are sequentially added, makes halogen acids homogeneous polymerization in the specific of activated carbon surface
Process is：
A, the 3- that step 2 is obtained (5,5- Dimethyl Hydan) propyl-triethoxysilicane deionized water ultrasonic dissolution,
Activated carbon is added, shakes 30min at room temperature, activated carbon is made to be come into full contact with siloxanes glycolylurea；The siloxanes glycolylurea and work
Property charcoal quality usage ratio be 1：20~1：30；
Halogen acid solution is then added in b, and mixture is placed in 50 DEG C of isothermal vibration sinks, shakes 6h；The halogen acids
Solution concentration is 0.1~1.0mol/L；
C, after the completion of reaction, in the modified activated carbon for being loaded with polysiloxanes glycolylurea is cleaned with deionized water being in solution
Property, it is placed in 120 DEG C of air dry ovens.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization above-mentioned, step 4 are added
Aqueous sodium hypochlorite solution carries out halogenation to modified activated carbon with hydracid sodium salt, obtains polysiloxanes halogen amine antibacterial active carbon
Detailed process be：
Modified activated carbon is impregnated in deionized water under the conditions of ice-water bath, hydracid sodium-salt aqueous solution is added dropwise dropwise by a；
The mass fraction of the hydracid sodium salt is 10%~90%；
Halogen acids is added dropwise in b, after reacting 4h, filtration washing, until the aqueous solution of detergent active charcoal no longer contains oxidation state halogen
Element；
C after the completion of washing, the activated carbon after halogenation is placed in 45 DEG C of vacuum drying chambers and is dried in vacuo 2h.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization above-mentioned, halogen acids include：
Hydrochloric acid, hydrobromic acid or hydroiodic acid.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization above-mentioned, step 4 are added
Aqueous sodium hypochlorite solution carries out halogenation to modified activated carbon with hydracid sodium salt, obtains polysiloxanes halogen amine antibacterial active carbon
Detailed process be：
Modified activated carbon is impregnated in deionized water under the conditions of ice-water bath, hydracid sodium-salt aqueous solution is added dropwise dropwise by a；
Halogen acids is added dropwise in b, keeps the range of the pH of solution 6.0~9.0, after reacting 4h, filtration washing, until washing
The aqueous solution of activated carbon no longer contains oxidation state halogen element；
C after the completion of washing, the activated carbon after halogenation is placed in 45 DEG C of vacuum drying chambers and is dried in vacuo 2h.
The invention has the beneficial effects that：
The modified activated carbon of the present invention is sufficiently stable in air, will not volatilize；
The present invention uses halogen amine polymer antiseptic, has higher antimicrobial efficiency compared with common polymer antibacterial agent
With longer anti-microbial property；
Antiseptic provided by the present invention is not only to gram-positive bacteria such as staphylococcus aureus etc. and Gram-negative
Bacterium such as Escherichia coli etc. have extraordinary bactericidal effect, while also having inactivation well to enveloped virus such as common cold virus etc.
Performance；
The low in raw material price that the present invention uses is easy to get, and manufacturing process is simple, easy to operate, is easy to implement industrial metaplasia
Production；
Since the present invention uses halogen acids as raw material, product adds the control of halogen reaction condition harsher, halogenation is caused to be imitated
Rate is unstable；The halogenation that the present invention can improve product by using the improvement of process in new halogenating agent and step 4 is imitated
Rate.
Description of the drawings
Fig. 1 is the flow chart of this preparation method；
Fig. 2 is the surface chlorine element point that the activated carbon obtained with the preparation method for lacking step 4 is taken with transmission electron microscope instrument
Butut；
Fig. 3 is the surface chlorine element distribution map that the modified activated carbon that this is obtained with preparation method is taken with transmission electron microscope instrument.
Specific implementation mode
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
A kind of amine polymer-modified activated carbon of halogen for indoor sterilization, including such as lower structure：
X includes：The ratio of Cl, Br and I, m and n are 1:1~1:9.
A kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization, includes the following steps：
Step 1 is that the detailed process that glycolylurea sodium salt is made in raw material is with 5,5- Dimethyl Hydan and sodium ethoxide：
5,5- Dimethyl Hydan is dissolved in absolute ethyl alcohol, at room temperature stirring and dissolving by a, and sodium ethoxide, room temperature are added after dissolving
Lower reaction 20min stops reaction；
B is rotated at 40 DEG C, is put into 40 DEG C of vacuum drying chambers overnight after steaming ethyl alcohol, is obtained glycolylurea sodium salt.
Step 1 is all reduced and is produced into using cheap starting material using conventional laboratory condition and drug
This, and each step suffers from higher yield, and the post-processing for often walking reaction is also fairly simple, and not generating largely has poison gas
The impurity of body and some pollution environment, is especially advantageous for industrialized production.
Step 2, with 3- chloropropyl triethoxysilanes substitution reaction occurs for glycolylurea sodium salt in solvent dimethylformamide
The detailed process for obtaining siloxanes glycolylurea is：
A dissolves obtained glycolylurea sodium salt with solvent dimethylformamide, stirring, after being warming up to 40 DEG C；
3- chloropropyl triethoxysilanes are added dropwise in b, are continuously heating to 90 DEG C, sustained response 8-10h；
C is cooled to room temperature after reaction, is filtered, and is rotated at 90 DEG C of filtrate, is extracted solvent dimethylformamide out, is obtained
Siloxanes glycolylurea.
Step 2, as substituting agent, is had the characteristics that at low cost, easy-operating using 3- chloropropyl triethoxysilanes；Reaction
With substrate one step substitution reaction can occur for 3- chloropropyl triethoxysilanes at a suitable temperature in the process, and for final
Product predecessor has higher yield；Also avoid involved in conventional sterilization agent synthetic method open simultaneously using the method
The cumbersome chemical step such as ring, oximate, hydrolysis, improves the combined coefficient of product.
Step 3 sequentially adds activated carbon and hydrochloric acid after ultrasonic dissolution siloxanes glycolylurea, makes halogen acids homogeneous polymerization
It is in the detailed process of activated carbon surface：
A, the 3- that step 2 is obtained (5,5- Dimethyl Hydan) propyl-triethoxysilicane deionized water ultrasonic dissolution,
Activated carbon is added, shakes 30min at room temperature, activated carbon is made to be come into full contact with siloxanes glycolylurea；As a kind of preferred siloxanes
The quality usage ratio of glycolylurea and activated carbon is 1：20~1：30；
Halogen acid solution is then added in b, and mixture is placed in 50 DEG C of isothermal vibration sinks, shakes 6h；As a kind of excellent
Choosing, a concentration of 0.1~1.0mol/L of halogen acid solution；
C, after the completion of reaction, in the modified activated carbon for being loaded with polysiloxanes glycolylurea is cleaned with deionized water being in solution
Property, it is placed in 120 DEG C of air dry ovens.
Step 3 has fully considered that activated carbon has multi-pore channel, high-specific surface area, unformed using activated carbon as carrier
The features such as processing, realizes to the higher load factor of presoma and utilization rate, has stronger operability and economy.It utilizes
Hydrochloric acid carries out just one-step chlorination synthesis as chlorine source to product, avoids and uses high toxicity chlorinated organics institute in conventional synthesis process
Caused by secondary pollution problem.
Aqueous sodium hypochlorite solution is added in step 4, carries out halogenation to modified activated carbon with hydracid sodium salt, obtains poly- silicon
The detailed process of oxygen alkane halogen amine antibacterial active carbon is：
Modified activated carbon is impregnated in deionized water under the conditions of ice-water bath, hydracid sodium-salt aqueous solution is added dropwise dropwise by a；
The mass fraction of the hydracid sodium salt is 10%~90%；
Halogen acids is added dropwise in b, after reacting 4h, filtration washing, until the aqueous solution of detergent active charcoal no longer contains oxidation state halogen
Element；It should be noted that：When halogen acids is added dropwise, need the pH ranges for keeping solution between 6.0~9.0, such range
It can promote the substitution reaction of halogen element and substrate；
C after the completion of washing, the activated carbon after halogenation is placed in 45 DEG C of vacuum drying chambers and is dried in vacuo 2h；Obtain structure
Formula is：
X includes：The ratio of Cl, Br and I, m and n are 1:1~1:9.
Step 4 carries out depth chlorination synthesis as chlorine source using hydrochloric acid to product, avoids in conventional synthesis process and uses
Secondary pollution problem caused by high toxicity chlorinated organics；The product obtained does not have chlorinated organics, efficiently low, right
Human body is harmless.
Product can be improved in order to verify the present invention by using the improvement of process in new halogenating agent and step 4
Halogenation efficiency；Do following experiment：
By above Step 1: the product of two, three synthesis, is sample 1；
By above Step 1: the product of two, three, four synthesis, is sample 2；
Respectively surface chlorine element distribution map is obtained with transmission electron microscope instrument；As a kind of embodiment, transmission electron microscope instrument is Japan
The Tecnai G2 F20 S-TWIN transmission electron microscope instrument of FEI Co., the transmission electron microscope instrument accelerate electricity equipped with EDX and HAADF, field
Pressure is 400kV；
The experimental result of sample 1 is as shown in Fig. 2, the experimental result of sample 2 is as shown in Figure 3；Pass through scanning electron microscope-energy color
It dissipates after x-ray spectrometer (SEM-EDX) carries out surface content of Cl element analysis to the modified activated carbon of polysiloxanes glycolylurea and finds,
Product surface chlorinity, i.e. halogenation efficiency are effectively increased by step 4 process.
As a kind of embodiment, halogen acids includes：Hydrochloric acid, hydrobromic acid or hydroiodic acid.Hydracid sodium salt includes：Sodium hypochlorite,
Sodium bromate, sodium iodate.
It should be noted that 5,5- Dimethyl Hydan：3- chloropropyl triethoxysilanes：The mole dosage ratio of sodium ethoxide
It is 1:1:1~1:1:9.
Embodiment 1
(1) 5, the 5- Dimethyl Hydan of 6.40g is dissolved in 100.0mL absolute ethyl alcohols, at room temperature stirring and dissolving, after dissolving
3.40g sodium ethoxides are added, react 20min at room temperature, stop reaction；It is rotated at 40 DEG C, steams that be put into 40 DEG C of vacuum after ethyl alcohol dry
In dry case overnight, glycolylurea sodium salt is obtained；
(2) obtained glycolylurea sodium salt is dissolved with DMF, is stirred.After being warming up to 40 DEG C, the 3- chlorine third of 12.04g is added dropwise
Ethyl triethoxy silicane alkane is continuously heating to 90 DEG C, sustained response 8-10h；
(3) after reaction, it is cooled to room temperature, filters, rotated at 90 DEG C of filtrate, extract DMF out.
(4) 0.146g is taken to use 3- (5,5- Dimethyl Hydan) propyl-triethoxysilicane obtained by the reaction
39.50mL deionized waters ultrasonic dissolution is added 4.00g activated carbons, shakes 30min at room temperature, make activity in 250mL beakers
Charcoal comes into full contact with siloxanes glycolylurea；
(5) 0.5mL 4.00mol/L hydrochloric acid solutions are then added, mixture is placed in 50 DEG C of isothermal vibration sinks, shake
Swing 6h；
(6) after the completion of reacting, in the modified activated carbon for being loaded with polysiloxanes glycolylurea cleaned with deionized water being in solution
Property, it is placed in 120 DEG C of air dry ovens；
(7) under the conditions of ice-water bath, 4.00g modified activated carbons is immersed in 30.00mL deionized waters, are added dropwise dropwise
10% aqueous sodium hypochlorite solution；
(8) 0.10mol/L hydrochloric acid is added dropwise keeps the pH of solution to remain at 7.0 or so, after reacting 4h, filtration washing,
Until the aqueous solution of detergent active charcoal no longer contains oxidation state chlorine, after the completion of washing, the activated carbon after chlorination is placed in 45 DEG C very
2h is dried in vacuo in empty drying box to get polysiloxanes halogen amine antibacterial activity carbon material.
Embodiment 2
Weigh 3.20g 5 respectively, 5- Dimethyl Hydan, 1.70g sodium ethoxides, 7.525g 3- chloropropyl triethoxysilanes,
Other operating procedures are according to embodiment 1.
Embodiment 3
Weigh 4.00g 5 respectively, 5- Dimethyl Hydan, 2.125g sodium ethoxides, 9.03g 3- chloropropyl triethoxysilanes,
Other operating procedures are according to embodiment 1.
Embodiment 4
Halogen is changed to bromine from chlorine element, that is, hydrochloric acid is changed to hydrobromic acid；Sodium hypochlorite is changed to sodium bromate；Other
Ingredient and operating procedure are according to embodiment 1.
Embodiment 5
Weigh 3.20g 5 respectively, 5- Dimethyl Hydan, 1.70g sodium ethoxides, 7.525g 3- chloropropyl triethoxysilanes,
Other operating procedures are according to embodiment 4.
Embodiment 6
Weigh 4.00g 5 respectively, 5- Dimethyl Hydan, 2.125g sodium ethoxides, 9.03g 3- chloropropyl triethoxysilanes,
Other operating procedures are according to embodiment 4.
The 6 polysiloxanes halogen amine antibacterial activity carbon samples obtained using embodiment 1-6, do anti-microbial property evaluation experimental；
Anti-microbial property evaluation test method is as described below：
Anti-microbial property test：
After bacterial solution is by centrifugation, a layer bacterial solids are removed, required bacterium is diluted to PBS buffer solutions
Concentration (10-7CFU/mL), take PBS bacterial solutions 75.00mL in 7 250mL conical flasks, be separately added into the unmodified work of 0.75g
Polysiloxanes halogen amine antibacterial activity carbon material prepared by property charcoal (as a comparison) and embodiment 1 to embodiment 6, is placed in 37 DEG C of perseverances
It is shaken with the rotating speed of 200r/min in warm shaking water bath, takes 0.50mL bacterium solutions to be measured after 1h in conical flask, take out tested bacteria
After liquid, (the 0.05N of 9.00mL phosphate buffers and 0.50mL in 9.50mL phosphate-sodium thiosulfate mixed solution is added
Hypo solution), hypo solution is added to restore free oxidation state that may be present in bacterium solution to be measured
Halogen element then carries out a series of dilutions, and the quantity of surviving bacteria is determined using plate count, to calculate the reduction of bacterium
Amount, to assess the antibiotic effect of polysiloxanes halogen amine modified activated carbon (or unmodified activated carbon), bacteriostasis rate calculation formula is：
Table 1 is the polysiloxanes halogen amine modified activated carbon prepared by embodiment 1 to embodiment 6 respectively to Staphylococcus aureus
The bactericidal property evaluation result of bacterium and Escherichia coli.
The bactericidal effect of 1 polysiloxanes halogen amine modified activated carbon of table
Obtained polysiloxanes halogen amine modified active Carbon Materials have good broad spectrum antibacterial as can be seen from Table 1
Energy.
Antiviral property is tested：
Existed by the polysiloxanes halogen amine modified activated carbon obtained by virus plaque measuring embodiment 1 and embodiment 4
To the inactivation ratio of common cold virus (A/PR8/8/34) under various concentration, used test cell is dog kidney cells (MDCK).Test knot
Fruit refers to table 2.
Inactivation performance of the 2 polysiloxanes halogen amine modified activated carbon of table to virus
As can be seen from Table 2 obtained polysiloxanes halogen amine modified active Carbon Materials to the inactivation performance of common cold virus with
It the increasing of dosage and greatly improves, 3g modified activated carbons are the virus mortality rate that can reach 95% or more, it is seen that the present invention has
There is very high practical value.
The modified activated carbon of the present invention is sufficiently stable in air, will not volatilize.The present invention is anti-using halogen amine polymer
Microbial inoculum has higher antimicrobial efficiency and longer anti-microbial property compared with common polymer antibacterial agent.It is provided by the present invention
Antiseptic not only has very gram-positive bacteria such as staphylococcus aureus etc. and Gram-negative bacteria such as Escherichia coli etc.
Good bactericidal effect, while also there is inactivation performance well to enveloped virus such as common cold virus etc..The raw material that the present invention uses
Cheap to be easy to get, manufacturing process is simple, easy to operate, is easy to implement industrialized production.Since the present invention is made using halogen acids
For raw material, product adds the control of halogen reaction condition harsher, causes halogenation efficiency unstable；The present invention can by process modification with
And develop new the methods of halogenating agent and the halogenation efficiency of product is further increased, there is certain researching value.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the invention is not limited in any way the embodiment, all to be obtained by the way of equivalent substitution or equivalent transformation
Technical solution is all fallen in protection scope of the present invention.
Claims (10)
1. a kind of amine polymer-modified activated carbon of halogen for indoor sterilization, which is characterized in that structural formula is：
X includes：The ratio of Cl, Br and I, m and n are 1:1~1:9.
2. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization, which is characterized in that including as follows
Step：
Step 1 is that glycolylurea sodium salt is made in raw material with 5,5- Dimethyl Hydan and sodium ethoxide；
Step 2, glycolylurea sodium salt is obtained with the generation substitution reaction of 3- chloropropyl triethoxysilanes in solvent dimethylformamide
Siloxanes glycolylurea；
Step 3 sequentially adds activated carbon and halogen acids after ultrasonic dissolution siloxanes glycolylurea, and halogen acids homogeneous polymerization is made to exist
Activated carbon surface；
Hydracid sodium-salt aqueous solution is added in step 4, carries out halogenation to modified activated carbon with hydracid sodium salt, obtains polysiloxanes
Halogen amine antibacterial active carbon, structural formula are：
X includes：The ratio of Cl, Br and I, m and n are 1:1~1:9.
3. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 2,
It is characterized in that, step 1, is that the detailed process that glycolylurea sodium salt is made in raw material is with 5,5- Dimethyl Hydan and sodium ethoxide：
5,5- Dimethyl Hydan is dissolved in absolute ethyl alcohol, at room temperature stirring and dissolving by a, sodium ethoxide is added after dissolving, at room temperature instead
20min is answered, reaction is stopped；
B is rotated at 40 DEG C, is put into 40 DEG C of vacuum drying chambers overnight after steaming ethyl alcohol, is obtained glycolylurea sodium salt.
4. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 2,
It is characterized in that, 5,5- Dimethyl Hydan in step 1：3- chloropropyl triethoxysilanes：The mole dosage ratio of sodium ethoxide is
1:1:1~1:1:9.
5. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 2,
It is characterized in that, step 2, glycolylurea sodium salt replaces with 3- chloropropyl triethoxysilanes in solvent dimethylformamide
The detailed process that siloxanes glycolylurea is obtained by the reaction is：
A dissolves obtained glycolylurea sodium salt with solvent dimethylformamide, stirring, after being warming up to 40 DEG C；
3- chloropropyl triethoxysilanes are added dropwise in b, are continuously heating to 90 DEG C, sustained response 8-10h；
C is cooled to room temperature after reaction, is filtered, and is rotated at 90 DEG C of filtrate, is extracted solvent dimethylformamide out, is obtained silica
Alkane glycolylurea.
6. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 2,
It is characterized in that, step 3 sequentially adds activated carbon and halogen acids after ultrasonic dissolution siloxanes glycolylurea, keep halogen acids equal
The even detailed process for being aggregated in activated carbon surface is：
A, the 3- that step 2 is obtained (5,5- Dimethyl Hydan) propyl-triethoxysilicane deionized water ultrasonic dissolution is added
Activated carbon shakes 30min at room temperature, and activated carbon is made to be come into full contact with siloxanes glycolylurea；
Halogen acid solution is then added in b, and mixture is placed in 50 DEG C of isothermal vibration sinks, shakes 6h；
C after the completion of reaction, the modified activated carbon for being loaded with polysiloxanes glycolylurea is cleaned with deionized water to solution and is in neutrality, is set
In 120 DEG C of air dry ovens.
7. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 2,
It is characterized in that, step 3 sequentially adds activated carbon and halogen acids after ultrasonic dissolution siloxanes glycolylurea, keep halogen acids equal
The even detailed process for being aggregated in activated carbon surface is：
A, the 3- that step 2 is obtained (5,5- Dimethyl Hydan) propyl-triethoxysilicane deionized water ultrasonic dissolution is added
Activated carbon shakes 30min at room temperature, and activated carbon is made to be come into full contact with siloxanes glycolylurea；The siloxanes glycolylurea and activated carbon
Quality usage ratio be 1：20~1：30；
Halogen acid solution is then added in b, and mixture is placed in 50 DEG C of isothermal vibration sinks, shakes 6h；The halogen acid solution
A concentration of 0.1~1.0mol/L；
C after the completion of reaction, the modified activated carbon for being loaded with polysiloxanes glycolylurea is cleaned with deionized water to solution and is in neutrality, is set
In 120 DEG C of air dry ovens.
8. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 2,
It is characterized in that, step 4, is added hydracid sodium-salt aqueous solution, halogenation is carried out to modified activated carbon with hydracid sodium salt, is obtained
Polysiloxanes halogen amine antibacterial active carbon, detailed process be：
Modified activated carbon is impregnated in deionized water under the conditions of ice-water bath, hydracid sodium-salt aqueous solution is added dropwise dropwise by a；It is described
The mass fraction of hydracid sodium salt is 10%~90%；
Halogen acids is added dropwise in b, after reacting 4h, filtration washing, until the aqueous solution of detergent active charcoal no longer contains oxidation state halogen member
Element；
C after the completion of washing, the activated carbon after halogenation is placed in 45 DEG C of vacuum drying chambers and is dried in vacuo 2h.
9. a kind of its preparation side of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 7 or 8
Method, which is characterized in that the halogen acids includes：Hydrochloric acid, hydrobromic acid or hydroiodic acid.
10. a kind of preparation method of the amine polymer-modified activated carbon of halogen for indoor sterilization according to claim 8,
It is characterized in that, step 4, is added hydracid sodium-salt aqueous solution, halogenation is carried out to modified activated carbon with hydracid sodium salt, is obtained
The detailed process of polysiloxanes halogen amine antibacterial active carbon is：
Modified activated carbon is impregnated in deionized water under the conditions of ice-water bath, hydracid sodium-salt aqueous solution is added dropwise dropwise by a；
Halogen acids is added dropwise in b, keeps the range of the pH of solution 6.0~9.0, after reacting 4h, filtration washing, until detergent active
The aqueous solution of charcoal no longer contains oxidation state halogen element；
C after the completion of washing, the activated carbon after halogenation is placed in 45 DEG C of vacuum drying chambers and is dried in vacuo 2h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114934356A (en) * | 2022-06-07 | 2022-08-23 | 赵辛欣 | Degradable nanofiber mask filter element with reproducible antibacterial performance and preparation method thereof |
| CN116622051A (en) * | 2023-07-25 | 2023-08-22 | 苏州久翔纺织整理有限公司 | Preparation method and application of antibacterial aqueous polyurethane emulsion |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114934356A (en) * | 2022-06-07 | 2022-08-23 | 赵辛欣 | Degradable nanofiber mask filter element with reproducible antibacterial performance and preparation method thereof |
| CN114934356B (en) * | 2022-06-07 | 2023-12-01 | 赵辛欣 | Degradable nanofiber mask filter core with renewable antibacterial property and preparation method thereof |
| CN116622051A (en) * | 2023-07-25 | 2023-08-22 | 苏州久翔纺织整理有限公司 | Preparation method and application of antibacterial aqueous polyurethane emulsion |
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