CN102784623A - Preparation method of non-dissolving antibacterial polyquaternium modified active carbon - Google Patents
Preparation method of non-dissolving antibacterial polyquaternium modified active carbon Download PDFInfo
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- CN102784623A CN102784623A CN2012102516792A CN201210251679A CN102784623A CN 102784623 A CN102784623 A CN 102784623A CN 2012102516792 A CN2012102516792 A CN 2012102516792A CN 201210251679 A CN201210251679 A CN 201210251679A CN 102784623 A CN102784623 A CN 102784623A
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- active carbon
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- ammonium salt
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Abstract
Active carbon (AC) which has a super-large specific surface area and a super-strong adsorption capability is widely applied to routine treatment and deep treatment of water, especially the removal of organic pollutants from water, but the active carbon absorbing the organic pollutants becomes a hotbed for the growth and the breeding of microbes, so the microbes in the treatment water exceed standards. The preparation method enables non-dissolving antibacterial polyquaternium modified active carbon harmless to the environment to be prepared through adopting the AC as a carrier and through the onsite polymerization of a siloxane quaternary ammonium salt monomer compound on the surface of the AC. The surface of the polyquaternium modified active carbon has positive charges, so the polyquaternium modified active carbon has strong bacteriostatic and antibacterial efficacies, and can be widely applied to the purification and disinfection treatment of various water.
Description
Technical field
The present invention relates to a kind of quaternary ammonium salt-modified methods and applications of activated carbon surface.Be specifically related to a kind of quaternary ammonium salt siloxanyl monomers compound polymerized in-situ method and the application of quaternary ammonium salt-modified active carbon aspect water treatment of activated carbon surface.
Background technology
Active carbon (AC) has been widely used in the conventional treatment and advanced treating of water.Because the superpower adsorption capacity of active carbon self, make it to become one of effective method of the maturation of removing organic pollution in the water.U.S. water quality association (Water Quality Association) has approved that activated carbon filtration is a kind of effective means that can make some pollutant loads in the drinking water be lower than the national drinking water standard of Environmental Protection Agency (EPA) regulation.Yet active carbon in the cleaning equipment especially for the drinking water deep processing, also exists insurmountable problem, i.e. the self-pollution problem of activated carbon media in water treatment.It in a large amount of hazardous contaminant of absorption, can breed a large amount of bacteriums just as a super sponge in its micropore.In addition; Nitrated decomposition takes place in activated carbon surface in organic compounds containing nitrogen under action of microorganisms; Organic nitrogen progressively is decomposed into proteinic nitrogen, ammonia nitrogen, nitrite nitrogen etc., thereby makes active carbon filter in use for some time, and content of nitrite increases greatly in the water of its purification; So not only do not reach the purpose that purifies water, on the contrary can polluted water.Economy but also address this problem effectively and remain a challenging job until today how not only.
Some above-mentioned shortcomings possibly appear in use for some time in order to overcome active carbon; Feasible way is with the immobilized surface to active carbon of the material with sterilizing function, adopts the secondary pollution that microbial reproduction was brought in the active carbon purifying water process to eliminate.Chinese patent 101337704A discloses a kind of antimicrobial algae-killing active carbon and preparation method.This patented method spreads upon activated carbon surface with acrylonitrile-styrene resin, makes acrylonitrile-styrene resin combine copper ion to prepare antimicrobial algae-killing active carbon through chemical treatment.Japan Patent JP6287103 disclose a kind of through the Bio-sil on the active carbon outer surface fixedly silver prepare the method for antibacterial active carbon.Korean Patent KR20040110398 discloses a kind of method for preparing antibacterial active carbon through dopen Nano gold in active carbon.
Though more than the antibacterial active carbon of these methods preparation have good antibacterial performance, metal prices such as gold, silver, copper are relatively more expensive and rare.Therefore, develop the cheap antibacterial active carbon of a kind of anti-biotic material wide material sources and have very important realistic meaning.
Summary of the invention
The objective of the invention is to overcome some shortcomings that existing antibacterial active carbon material and technology thereof exist, provide that a kind of anti-biotic material wide material sources are cheap, the preparation simple antibacterial active carbon material of route and technology thereof.
Technical scheme of the present invention does, quaternary ammonium salt is one type of non-oxidative bactericide that has positive charge, and its biocidal efficacies is stable permanent.If through unique polymerized in-situ method; Make quaternary ammonium salt siloxanyl monomers compound equably polymerization in the surface of active carbon; Make full use of the anti-microbial property of quaternary ammonium salt and the high-specific surface area and strong absorption property of active carbon, just might prepare the good non-dissolution type polyquaternium modified activated carbon material of anti-microbial property.At present, the report that does not also have this respect.For this reason, it is carrier that the present invention adopts active carbon, prepares the antibiotic polyquaternium modified activated carbon of non-dissolution type of environmental sound through quaternary ammonium salt siloxanyl monomers compound at its surperficial polymerized in-situ, and the polymerized in-situ reaction equation is following:
The antibiotic polyquaternium modified activated carbon of non-dissolution type of the present invention can prepare at the polymerized in-situ of activated carbon surface through alkylhalide group siloxanes and the synthetic quaternary ammonium salt siloxanyl monomers compound of reactive tertiary amine, quaternary ammonium salt siloxanyl monomers compound, and detailed process comprises the steps:
(1) quaternary ammonium salt siloxanyl monomers compound is synthetic
Alkylhalide group siloxanes and the tertiary amine mol ratio by 1:1～5:1 is joined in the organic solvent, under nitrogen or inert gas shielding, 40 ℃～150 ℃ reactions 4 to 72 hours down; The mol ratio of alkylhalide group siloxanes and tertiary amine is preferably 1:1～2:1; Reaction temperature is preferably 80 ℃～120 ℃; Reaction time is preferably 24～48 hours.Reaction finishes the back decompression distillation and removes unreacted alkylhalide group siloxanes and tertiary amine and solvent, obtains quaternary ammonium salt siloxanyl monomers compound.
The structure of alkylhalide group siloxanes is suc as formula (I):
R wherein
1, R
2And R
3Be C
1～C
8Alkyl or hydroxyl, R
1, R
2And R
3Be preferably C
1～C
3Alkyl or hydroxyl; X is halogen Cl, Br, I; N is 1～12 integer, and n is preferably 1～4 integer.
The structure of tertiary amine is suc as formula (II):
R wherein
4, R
5And R
6Be C
1～C
24Alkyl or olefin group, C
1～C
24Haloalkyl or alkenyl halide group, C
1～C
24Hydroxy alkyl, R
4And R
5, R
5And R
6Or R
4And R
6Also can unite and be C
3～C
7Cycloalkyl or cycloolefin group, R
1, R
2And R
3Be preferably C
1～C
18Alkyl.
Organic solvent comprises C
1～C
6Alcohol, acetone, dioxane, oxolane, N, two or more mixture in N dimethyl formamide (DMF) or the above-mentioned solvent, organic solvent is preferably C
1～C
3Pure and mild dimethyl formamide.
(2) the quaternary ammonium salt siloxanyl monomers is at the polymerized in-situ of activated carbon surface
Active carbon and the quaternary ammonium salt siloxanyl monomers compound weight ratio with 10:1～10000:1 is joined in the hydrochloric acid solution that molar concentration is 0.001～10mol/L; 0 ℃～100 ℃ polymerized in-situ reactions 1 to 72 hour; The weight ratio of active carbon and quaternary ammonium salt siloxanyl monomers compound is preferably 10:1～200:1, more preferably 20:1～100:1; The molar concentration of hydrochloric acid solution is preferably 0.05～1.00mol/L; Polymeric reaction temperature is preferably 15 ℃～50 ℃; Reaction time is preferably 4～24 hours.Filtration washing obtained the antibiotic polyquaternium modified activated carbon of non-dissolution type after the polymerized in-situ reaction was accomplished, 80～100 ℃ of oven dry down.
Has good antibacterial effect through the antibiotic polyquaternium modified activated carbon of the non-dissolution type of method for preparing.
The present invention's beneficial effect compared with prior art is that the antibiotic polyquaternium modified activated carbon of non-dissolution type has good antibacterial effect, its preparation technology's environmental protection, and raw material is cheap and easy to get.Through the polymerized in-situ of quaternary ammonium salt siloxanyl monomers compound, in the process of purifying water body, can suppress harmful microbe breeding and growth simultaneously thereby make prepared antibacterial active carbon possess at activated carbon surface.
The specific embodiment
Through embodiment the present invention is described further below, but embodiment does not limit protection scope of the present invention.
Embodiment 1
This instance is the preparation of 3-(trimethoxy silane base) third class hexadecyldimethyl benzyl ammonium ammonium chloride, and reaction equation is following:
Take by weighing 3-chloropropyl-trimethoxy silane 12.03g (0.06mol); Hexadecyldimethyl benzyl ammonium tertiary amine 8.15g (0.03mol) adds 21.93g (0.3mol) N, in the dinethylformamide (DMF); Charge into nitrogen protection; At 110 ℃ of following stirring reaction 28-30h, reactant is removed solvent and excess reactant through rotary evaporation, and to obtain content be 96% 3-(trimethoxy silane base) third class hexadecyldimethyl benzyl ammonium ammonium chloride, and crude product obtains pure product through the acetone purification; Elementary analysis test value: C/%61.45 (61.56), N/%2.98 (2.99) H/%11.63 (11.62) (in the bracket is theoretical value); M/z 432.30; IR (KBr cm
-1): 3430.86,2921.05,2851.13,1195.30,1076.42.
Can use methyl alcohol, ethanol, propyl alcohol to replace DMF, perhaps use methyl alcohol and DMF mixed solution, reaction result is identical.
Embodiment 2
This instance is the polymerized in-situ reaction on active carbon of 3-(trimethoxy silane base) third class hexadecyldimethyl benzyl ammonium ammonium chloride.
Take by weighing the 0.2g quaternary ammonium salt and add in the 250ml band plug ground conical flask, add the 38ml deionized water, behind the ultrasonic dissolution; Add the 4g active carbon, at room temperature shake 30min after, add 2ml 4mol/L hydrochloric acid solution; The adjustment concentration of hydrochloric acid solution is that 0.2mol/L places 50 ℃ of isothermal vibration tanks to react 6h, and reaction is clarified with washed with de-ionized water to solution after accomplishing; Place 80 ℃ of dry 2h of air dry oven, make modified activated carbon.Every gram activated carbon supported 1.07 * 10
-4The mol quaternary ammonium salt.
Embodiment 3
This instance is the polymerized in-situ reaction on active carbon of 3-(trimethoxy silane base) third class hexadecyldimethyl benzyl ammonium ammonium chloride.
Experiment takes by weighing the 0.1g quaternary ammonium salt and adds in the 250ml band plug ground conical flask, adds the 47.5ml deionized water, behind the ultrasonic dissolution; Add the 5g active carbon, at room temperature shake 30min after, add 2.5ml 4mol/L hydrochloric acid solution; The adjustment solution concentration is that 0.2mol/L places 50 ℃ of isothermal vibration tanks to react 6h, and reaction is clarified with washed with de-ionized water to solution after accomplishing; Place 80 ℃ of dry 2h of air dry oven, make modified activated carbon.Every gram activated carbon supported 4.29 * 10
-5The mol quaternary ammonium salt.
Embodiment 4
This instance is the polymerized in-situ reaction on active carbon of 3-(trimethoxy silane base) third class hexadecyldimethyl benzyl ammonium ammonium chloride.
Experiment takes by weighing the 0.1g quaternary ammonium salt and adds in the 250ml band plug ground conical flask, adds the 95ml deionized water, behind the ultrasonic dissolution; Add the 10g active carbon, at room temperature shake 30min after, add 5ml 4mol/L hydrochloric acid solution; The adjustment solution concentration is that 0.2mol/L places 50 ℃ of isothermal vibration tanks to react 6h, and reaction is clarified with washed with de-ionized water to solution after accomplishing; Place 80 ℃ of dry 2h of air dry oven, make modified activated carbon.Every gram activated carbon supported 2.14 * 10
-5The mol quaternary ammonium salt.
Embodiment 5
This instance is the antibiotic effect test of the antibiotic polyquaternium modified activated carbon of non-dissolution type.
Experiment selects for use Escherichia coli and staphylococcus aureus as bacteria tested, and every kind of bacterium cooked 4 groups of experiments: (every gram active carbon contains 1.07 * 10 for blank, unmodified active carbon, modified activated carbon A
-4The mol quaternary ammonium salt), (every gram active carbon contains 4.29 * 10 to modified activated carbon B
-5The mol quaternary ammonium salt).Every group of experiment takes by weighing 0.75 gram sample and puts into 250 milliliters of conical flasks (except the blank control group); Add 75 milliliters of PBS cushioning liquid and 0.75 milliliter of bacterium liquid of cultivating 24 hours; The concussion tank that places 37 ℃ is with the concussion of the rotating speed of 200r/min; When 30min, 90min, get 1 milliliter of supernatant respectively and make gradient dilution, adopt dull and stereotyped count plate to measure the bacterium colony crowd number of viable bacteria.The computing formula of antibiotic rate is:
Antibiotic rate (%)=[(initial bacterium number-one-tenth viable count)/initial bacterium number] * 100%
The antibiotic effect test result is seen table 1:
Claims (9)
1. the preparation method of the antibiotic polyquaternium modified activated carbon of non-dissolution type is characterized in that, comprises following steps:
(1) quaternary ammonium salt siloxanyl monomers compound is synthetic
Alkylhalide group siloxanes and the tertiary amine mol ratio by 1:1～5:1 is joined in the organic solvent, under nitrogen or inert gas shielding, 40 ℃～150 ℃ reactions 4 to 72 hours; Unreacted alkylhalide group siloxanes and tertiary amine and solvent are removed in decompression distillation, obtain quaternary ammonium salt siloxanyl monomers compound.
(2) the quaternary ammonium salt siloxanyl monomers is at the polymerized in-situ of activated carbon surface
Active carbon and quaternary ammonium salt siloxanyl monomers compound are mixed with hydrochloric acid solution, reacted 1 to 72 hour down at 0～100 ℃; Active carbon and quaternary ammonium salt siloxanyl monomers compound weight ratio are 10:1～10000:1, and concentration of hydrochloric acid solution is 0.001～10mol/L, obtain antibiotic polyquaternium modified activated carbon and oven dry behind the filtration washing.
2. the preparation method of the antibiotic polyquaternium modified active of non-dissolution type according to claim 1 carbon surface is characterized in that, the chemical constitution of described alkylhalide group siloxanes is suc as formula shown in (I):
R wherein
1, R
2And R
3Be C
1～C
8Alkyl or hydroxyl; X is Cl, Br or I; N is 1～12 integer.
3. the preparation method of the antibiotic polyquaternium modified active of non-dissolution type according to claim 2 carbon surface is characterized in that R
1, R
2And R
3Be C
1～C
8Alkyl.
4. the preparation method of the antibiotic polyquaternium modified active of non-dissolution type according to claim 1 carbon surface is characterized in that, the chemical constitution of described tertiary amine suc as formula shown in:
R wherein
4, R
5And R
6Be C
1～C
24Alkyl or olefin group, C
1～C
24Haloalkyl or alkenyl halide group, C
1～C
24Hydroxy alkyl, perhaps, R
4With R
5, R
5With R
6Perhaps R
4With R
6Unite and form C
3～C
7Cycloalkyl or cycloolefin group.
5. the preparation method of the antibiotic polyquaternium modified active of the described non-dissolution type of claim 4 carbon surface is characterized in that said R
4, R
5And R
6Be C
1～C
18Alkyl.
6. the preparation method of the antibiotic polyquaternium modified active of the described non-dissolution type of claim 1 carbon surface, the organic solvent that it is characterized in that step (1) is C
1～C
6The mixture of one or more in alcohol, acetone, dioxane, oxolane, the dimethyl formamide.
7. the preparation method of the antibiotic polyquaternium modified active of the described non-dissolution type of claim 1 carbon surface; It is characterized in that in the step (1); The mol ratio of alkylhalide group siloxanes and tertiary amine is 1:1～2:1, and reaction temperature is 80 ℃～120 ℃, and the reaction time is 24～48 hours.
8. the preparation method of the antibiotic polyquaternium modified active of the described non-dissolution type of claim 1 carbon surface; The reaction temperature that it is characterized in that step (2) is 15～60 ℃; Reaction time is 4～24 hours; Concentration of hydrochloric acid solution is 0.05～1mol/L, and the amount ratio of hydrochloric acid and active carbon is 1～5mmol/g.
9. the preparation method of the antibiotic polyquaternium modified active of the described non-dissolution type of claim 1 carbon surface is characterized in that in the step (2), and active carbon and quaternary ammonium salt siloxanyl monomers compound weight ratio are 10:1～200:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103506075A (en) * | 2013-08-30 | 2014-01-15 | 蚌埠凤凰滤清器有限责任公司 | Iron ore slag modified active carbon desulfurizer and preparation method thereof |
| CN109603782A (en) * | 2019-01-21 | 2019-04-12 | 葛畅 | A kind of preparation method of the absorbent-type deodorant with sterilizing function |
| CN110226604A (en) * | 2019-07-05 | 2019-09-13 | 中国科学院南京土壤研究所 | A kind of magnetic green substance charcoal-quaternary alkylphosphonium salt sterilization material, method of preparation and use |
| CN110813234A (en) * | 2019-11-12 | 2020-02-21 | 南昌师范学院 | Preparation method of antibacterial modified wheat straw biochar with amphiphilic characteristic |
-
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| 周静茹等: "改性活性炭负载高分子季铵盐的杀菌性能", 《化工学报》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506075A (en) * | 2013-08-30 | 2014-01-15 | 蚌埠凤凰滤清器有限责任公司 | Iron ore slag modified active carbon desulfurizer and preparation method thereof |
| CN109603782A (en) * | 2019-01-21 | 2019-04-12 | 葛畅 | A kind of preparation method of the absorbent-type deodorant with sterilizing function |
| CN110226604A (en) * | 2019-07-05 | 2019-09-13 | 中国科学院南京土壤研究所 | A kind of magnetic green substance charcoal-quaternary alkylphosphonium salt sterilization material, method of preparation and use |
| WO2021004116A1 (en) * | 2019-07-05 | 2021-01-14 | 中国科学院南京土壤研究所 | Magnetic biomass carbon-quaternary phosphonium salt sterilization material, preparation method therefor and usage thereof |
| CN110813234A (en) * | 2019-11-12 | 2020-02-21 | 南昌师范学院 | Preparation method of antibacterial modified wheat straw biochar with amphiphilic characteristic |
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