CN106118198A - The preparation method of carbon nano tube surface quaternized antibacterial in situ - Google Patents
The preparation method of carbon nano tube surface quaternized antibacterial in situ Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L101/00—Compositions of unspecified macromolecular compounds
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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Abstract
The invention discloses the preparation method of a kind of carbon nano tube surface quaternized antibacterial in situ, with acidifying CNT as carrier, first in its surface grafting polymine, and the polymine of grafting is carried out tertiary-aminated and that quaterisation formation CNT is the most quaternized quaternary ammonium salt long-acting antibiotic agent successively.The inventive method is simple and safe, to more environment-friendly, the synthetic method of antibacterial is simple, use equipment is few, antibacterial effect is excellent, safe to use, it is with a wide range of applications, can be applicable to the base materials such as coating, plastics, rubber, fiber, and material preparation and the apparatus system such as water process and air cleaning.The target product of the present invention antibacterial dosage of minimum as little as 50mg/L and 20mg/L respectively to staphylococcus aureus and large intestine bar bacillus typical bacteria.
Description
Technical field
The present invention relates to the invention discloses a kind of passing through at acidifying carbon nano tube surface grafting polyethylene imine, and original position
The method of quaternized acquisition quaternary ammonium salt long-acting antibiotic agent, belongs to technical field of function materials.
Background technology
In recent years, the concern of environmental health and germ contamination is got more and more by people.Living environment microbes contamination
An investigation show: rural area total number of bacteria is 138.94cfu/cm2, and cities and towns are 72.10cfu/cm2.Microorganism as can be seen here
The pollution causing living environment be can not ignore, and antibacterial is the most serious to the harm of health.Therefore, people are long-pending
Polar region is sought can be with permanently effective antibacterial anti-biotic material.
Anti-biotic material can be divided into natural antibacterial material due to component difference, inorganic antibacterial material, organic anti-bacterial material with
And macromolecular material.Wherein the active function groups density of polymer antibacterial agent is far above organic molecule, has and resists than little molecule
The more preferable anti-microbial property of microbial inoculum.And polymer antibacterial agent is to kill antibacterial by directly contacting with antibacterial, is not required to release
Putting active substance, therefore, the anti-microbial property of goods is lasting, and residual toxicity is substantially reduced, and safety improves, and is increasingly subject to both at home and abroad
The extensive attention of scholar.
The polymer antibacterial agent studying more at present, according to the difference of active function groups, can be divided into quaternary ammonium salt, season phosphine
Salt, organotin, halogenated amine, guanidinesalt, Chitosan-phospholipid complex etc.." Novel chitosan efficient broad-spectrum is antibacterial for Chinese invention patent
Agent " [CN 102763652A], invent a kind of ultra micro chitosan production technology, the joining of Novel chitosan efficient broad-spectrum antibacterial agent
Square and special synthesis technique, but the anti-microbial property of the chitosan antimicrobial agent of the method synthesis is relatively low.And QAS polymer
Applied research is extremely wide, and the density of its positive charge is higher, for polycationic polymers, therefore has bacterial cell surface
Effect adsorptivity is stronger.Active part can be extend into cell membrane through the okioplast wall of microbial cell and kill by polymer long-chain
Dead cell.And with compared with the quaternary ammonium salt of long alkyl chain due to higher with cell membrane binding ability, so antibacterial effect also can be more preferable.
In order to more play consistently the antibacterial effect of quaternary ammonium salt, physical blending or chemical method can be passed through by antibacterial base
Group is attached on carrier, has the antibacterial of excellent antibacterial performance with preparation.Chinese invention patent " a kind of novel fabric quaternary ammonium
The preparation method of salt copolymer/nano-ZnO complex antimicrobials " [CN 102787497A], with vinyl monomer, by water-soluble
Liquid radical polymerization synthesis quaternized copolymer, is blended with nano zine oxide further, prepares quaternized copolymer/nanometer
ZnO composite, processes for antibacterial fabric.The antibacterial antiplaque agent composition that the method obtains is to be mixed into base by physical method
In body material, long-term stability is poor, and antimicrobial component is difficult to mix homogeneously；And by the method for chemical graft by macromolecule season
Ammonium salt is attached in stabilized matrix, then can avoid this problem.Chinese invention patent " antibacterial production technology, antibacterial and
Paper " [CN 103467632A], its technique is to crosslink first with alcohol compound and coupling agent to be reacted to give with part
The stable alcohols cross linked polymer of hydroxy functional group, is grafted to described afterwards by the epoxy radicals antibacterial group of polymeric quaternary ammonium salt
Have on the alcohols crosslink polymer molecules chain of rock-steady structure, antibacterial to obtain having the alcohols cross linked polymer of anti-microbial property
Agent.But the method chemical reaction is complicated, and reaction condition is harsher, and the preparation of carrier is also required to pre-synthesis, therefore finds
A kind of be used directly for be grafted quaternary ammonium salt group carrier, and explore one prepared by simple and environmentally-friendly easy-operating method
Antibacterial be necessary.
Coming out from CNT, scholars has started the various action oriented researchs of the material special to this structure, its
The ability of good absorption antibacterial and will not develop immunity to drugs that to be all CNT provide condition as the carrier of anti-biotic material.
And with the acidifying CNT containing carboxylic group as carrier, be directly grafted by simple chemical method and there is excellent antibacterial effect
The high molecular quaternary of fruit, can obtain antibacterial activity higher, anti-microbial property lasting stability and the high antibacterial of safety.
Summary of the invention
It is an object of the invention to provide a kind of preparation method being acidified carbon nano tube surface quaternized antibacterial in situ, this
Bright method is simple and safe, environmentally friendly, prepared antibacterial antiplaque agent robust consistent, all has excellent to antibacterial and fungus
Different anti-microbial property, and the antibacterial prepared by the inventive method can recycle.
For reaching above-mentioned purpose, the technical solution used in the present invention is: a kind of acidifying CNT grafting polymer quaternary ammonium
The preparation method of salt antibacterial, to be acidified CNT as carrier, first in its surface grafting polymine, and to grafting
Polymine carries out tertiary-aminated and that quaterisation formation CNT is the most quaternized quaternary ammonium salt long-acting antibiotic agent successively,
Including following key step:
(1) CNT grafting polyethylene imine: acidifying CNT and polymine are dispersed in deionization respectively
In water, CNT is mass ratio 1:1～1:3 with the proportioning of polymine, and mixing ultrasonic Treatment make it disperse subsequently
Uniformly, being stirred at room temperature 8～12h, make polymine fully react with acidifying CNT, reaction gained solid produces
Thing is successively through ethanol, water washing, and sucking filtration obtains the CNT of grafting polyethylene imine after separating；
(2) tertiary-aminated reaction: step (1) gained CNT grafting polyethylene imine is disperseed in deionized water, stirs
Mixing uniformly, be slowly dropped in dispersion liquid by tertiary-aminated reagent, at 0～3 DEG C, stirring reaction 6～8h, filters the solid separated
Thing with ethanol, water washing, obtains CNT after sucking filtration separation and is grafted tertiary-aminated polymine successively；
(3) quaterisation: the tertiary-aminated polymine of step (2) gained CNT grafting is distributed to tert-pentyl alcohol
In, it being slowly added dropwise quaternizing agent, the mol ratio of tertiary-aminated reagent used is 1～2:1 to quaternizing agent with step (2)；?
Stirring reaction 10～14h at 50～70 DEG C, filters the solids separated successively with ethanol, water washing, sucking filtration separate after in 40～
80 DEG C of vacuum drying obtain target product carbon nano tube surface quaternized antibacterial in situ.
Further, in step (1), the molecular weight 600 of polymine PEI.Equally, in step (1), time ultrasonic
Between control 1～2h, power is 100～250W.
Further, in step (2), described tertiary-aminated reagent is expoxy propane, and it is 1 with the mass ratio of polymine
～2.5:1.
Further, one or more during described quaternizing agent is iodomethane, bromoethane or bromohexadecane.
The present invention, relative to prior art, has the advantage that and effect:
The present invention, with CNT as carrier, uses aqua-solution method grafting polyethylene imine, then by N-alkylated reaction
Obtain quaternary ammonium salt, prepare a kind of carbon nano tube surface quaternized anti-biotic material in situ.
(1) the antibacterial antiplaque agent effect prepared by the inventive method is more preferable.At present the most commonly by inorganic antiseptic or
Little molecule antibacterial is attached on CNT prepare complex antimicrobials, but the active function groups density of polymer antibacterial agent is remote
Higher than organic molecule, there is the little more preferable anti-microbial property of molecule antibacterial of ratio, here organic polymer antibacterial is attached to
On carbon pipe, improve it to antibacterial and the anti-microbial property of fungus.
(2) antimicrobial agent stability prepared by the inventive method and persistency are good.With common inorganic antiseptic or little point
Sub-antibacterial is compared, and polymer antibacterial agent can kill antibacterial by direct contact the with antibacterial, is not required to discharge active matter
Matter, and after being grafted on CNT, antibacterial group is stable, is not easily decomposed, therefore, the anti-microbial property lasting stability of goods.
(3) antibacterial prepared by the inventive method can be recycled.High molecular quaternary is during antibacterial in structure
Will not change, and after use a period of time, washing removes the antibacterial remains of surface adsorption, and anti-microbial property just can be made to recover, because of
This can recycle, and has good advantage on cost.
(4) the inventive method is simple and safe, simple operation.From technical scheme, carry out N-alkylation by iodomethane,
The most quaternized acquisition high molecular quaternary, method is simple and safe, to more environment-friendly.The synthetic method letter of this antibacterial
Easily, use equipment few, be with a wide range of applications, can be applicable to the base materials such as coating, plastics, rubber, fiber, and water processes
With the preparation of the material such as air cleaning and apparatus system.
Accompanying drawing explanation
Fig. 1 is the technical schematic diagram of CNT grafting polymer quaternary ammonium salt antiseptic of the present invention.
Fig. 2 is each step gained sample of CNT grafting polymer quaternary ammonium salt antiseptic in the embodiment of the present invention 1
Thermogravimetric curve.
Fig. 3 is each step gained sample of CNT grafting polymer quaternary ammonium salt antiseptic in the embodiment of the present invention 1
Infared spectrum.
Fig. 4 is the X of each step gained sample of CNT grafting polymer quaternary ammonium salt antiseptic in the embodiment of the present invention 1
The full spectrogram of X-ray photoelectron spectroscopy X.
Fig. 5 is the X of each step gained sample of CNT grafting polymer quaternary ammonium salt antiseptic in the embodiment of the present invention 1
X-ray photoelectron spectroscopy X High-Resolution Map, wherein: figure (a) is the energy spectrogram of C1s in raw material acid carbon nano tube, and figure (b) (c) is carbon
The energy spectrogram of C1s and N1s in nanotube grafting polyethylene imine, figure (b) (c) is that CNT grafting polymer quaternary ammonium salt is antibacterial
In agent, C1s's and N1s can spectrogram.
Fig. 6 be in the embodiment of the present invention 1 CNT grafting polymer quaternary ammonium salt antiseptic to escherichia coli and golden yellow
Staphylococcic antibacterial effect figure；Wherein: figure (a) (b) (c) (d) be respectively blank sample, dosage be the acidifying of 800mg/L
CNT, dosage are the CNT grafting polymer quaternary ammonium salt antiseptic of 20mg/L and dosage is the CNT of 50mg/L
Grafting polymer quaternary ammonium salt antiseptic is to colibacillary antibacterial effect figure；Figure (e) (f) (g) (h) be respectively blank sample,
Dosage is the CNT grafting polymer quaternary ammonium salt antiseptic mediating recipe that acidifying CNT, dosage are 20mg/L of 800mg/L
The CNT grafting polymer quaternary ammonium salt antiseptic that amount the is 50mg/L antibacterial effect figure to staphylococcus aureus.
Fig. 7 be in each embodiment of the present invention CNT grafting polymer quaternary ammonium salt antiseptic to escherichia coli and golden yellow
Color staphylococcus minimum antibacterial statistics of variables table.
Detailed description of the invention
Embodiment 1:
(1) CNT grafting polyethylene imine: be the polymine of 70000 by acidifying CNT and molecular weight
(CNT and the mass ratio 1:3 of polymine) disperses in deionized water respectively, mixes subsequently, ultrasonic Treatment 1h,
Power is 250W so that it is is uniformly dispersed, and is stirred at room temperature 12h, makes polymine fully occur with acidifying CNT
Reaction, reaction gained solid product is successively through ethanol, water washing, and sucking filtration obtains the carbon nanometer of grafting polyethylene imine after separating
Pipe.
(2) tertiary-aminated reaction: the CNT grafting polyethylene imine of preparation in step (1) is dispersed in deionized water
In, stir, be the proportioning of 5:3 according to expoxy propane and polymine mass ratio, tertiary-aminated reagent expoxy propane is delayed
Slowly being added drop-wise in dispersion liquid, stirring reaction 7h at 3 DEG C, filter the solids separated and use the washing of ethanol, water successively, sucking filtration separates
After obtain CNT be grafted tertiary-aminated polymine.
(3) quaterisation: the CNT of preparation in step (2) is grafted tertiary-aminated polymine and is distributed to uncle penta
In alcohol, it is the proportioning of 2:1 according to iodomethane and expoxy propane mol ratio, is slowly added dropwise quaternizing agent iodomethane, stirs at 60 DEG C
Mixing reaction 14h, filter the solids separated and wash with ethanol, water successively, sucking filtration obtains carbon in 60 DEG C of vacuum drying after separating and receives
Nanotube surface quaternized antibacterial in situ.This antibacterial is respectively provided with the antibacterial effect of excellence to staphylococcus aureus and escherichia coli
Really, minimum antibacterial dosage has respectively reached 50mg/L and 20mg/L.
Embodiment 2:
(1) CNT grafting polyethylene imine: by acidifying CNT and the polymine (carbon that molecular weight is 600
Nanotube and the mass ratio 1:3 of polymine) disperse respectively in deionized water, mix subsequently, ultrasonic Treatment 1h, power
For 250W so that it is be uniformly dispersed, and it is stirred at room temperature 12h, makes polymine fully react with acidifying CNT,
Reaction gained solid product is successively through ethanol, water washing, and sucking filtration obtains the CNT of grafting polyethylene imine after separating.
(2) tertiary-aminated reaction: the CNT grafting polyethylene imine of preparation in step (1) is dispersed in deionized water
In, stir, be the proportioning of 5:3 according to expoxy propane and polymine mass ratio, tertiary-aminated reagent expoxy propane is delayed
Slowly being added drop-wise in dispersion liquid, stirring reaction 7h at 3 DEG C, filter the solids separated and use the washing of ethanol, water successively, sucking filtration separates
After obtain CNT be grafted tertiary-aminated polymine.
(3) quaterisation: the CNT of preparation in step (2) is grafted tertiary-aminated polymine and is distributed to uncle penta
In alcohol, it is the proportioning of 2:1 according to iodomethane and expoxy propane mol ratio, is slowly added dropwise quaternizing agent iodomethane, stirs at 50 DEG C
Mixing reaction 10h, filter the solids separated and wash with ethanol, water successively, sucking filtration obtains carbon in 80 DEG C of vacuum drying after separating and receives
Nanotube surface quaternized antibacterial in situ.This antibacterial is respectively provided with the antibacterial effect of excellence to staphylococcus aureus and escherichia coli
Really, minimum antibacterial dosage has respectively reached 500mg/L and 400mg/L.
Embodiment 3:
(1) CNT grafting polyethylene imine: be the polymine of 70000 by acidifying CNT and molecular weight
(CNT and the mass ratio 1:1 of polymine) disperses in deionized water respectively, mixes subsequently, ultrasonic Treatment 1h,
Power is 250W so that it is is uniformly dispersed, and is stirred at room temperature 12h, makes polymine fully occur with acidifying CNT
Reaction, reaction gained solid product is successively through ethanol, water washing, and sucking filtration obtains the carbon nanometer of grafting polyethylene imine after separating
Pipe.
(2) tertiary-aminated reaction: the CNT grafting polyethylene imine of preparation in step (1) is dispersed in deionized water
In, stir, be the proportioning of 2.5:1 according to expoxy propane and polymine mass ratio, by tertiary-aminated reagent expoxy propane
Being slowly dropped in dispersion liquid, stirring reaction 7h at 3 DEG C, filter the solids separated and use the washing of ethanol, water successively, sucking filtration divides
Obtain CNT after from and be grafted tertiary-aminated polymine.
(3) quaterisation: the CNT of preparation in step (2) is grafted tertiary-aminated polymine and is distributed to uncle penta
In alcohol, it is the proportioning of 1.5:1 according to iodomethane and expoxy propane mol ratio, is slowly added dropwise quaternizing agent iodomethane, at 60 DEG C
Stirring reaction 12h, filters the solids separated and uses the washing of ethanol, water successively, and sucking filtration obtains carbon in 40 DEG C of vacuum drying after separating
Nanotube surface quaternized antibacterial in situ.This antibacterial is respectively provided with the antibacterial of excellence to staphylococcus aureus and escherichia coli
Effect, minimum antibacterial dosage has respectively reached 100mg/L and 50mg/L.
Embodiment 4:
(1) CNT grafting polyethylene imine: be the polymine of 70000 by acidifying CNT and molecular weight
(CNT and the mass ratio 1:3 of polymine) disperses in deionized water respectively, mixes subsequently, ultrasonic Treatment 2h,
Power is 100W so that it is is uniformly dispersed, and is stirred at room temperature 8h, makes polymine fully occur instead with acidifying CNT
Should, reaction gained solid product is successively through ethanol, water washing, and sucking filtration obtains the CNT of grafting polyethylene imine after separating.
(2) tertiary-aminated reaction: the CNT grafting polyethylene imine of preparation in step (1) is dispersed in deionized water
In, stir, be the proportioning of 5:3 according to expoxy propane and polymine mass ratio, tertiary-aminated reagent expoxy propane is delayed
Slowly being added drop-wise in dispersion liquid, stirring reaction 7h at 0 DEG C, filter the solids separated and use the washing of ethanol, water successively, sucking filtration separates
After obtain CNT be grafted tertiary-aminated polymine.
(3) quaterisation: the CNT of preparation in step (2) is grafted tertiary-aminated polymine and is distributed to uncle penta
In alcohol, it is the proportioning of 2:1 according to iodomethane and expoxy propane mol ratio, is slowly added dropwise quaternizing agent iodomethane, stirs at 60 DEG C
Mixing reaction 10h, filter the solids separated and wash with ethanol, water successively, sucking filtration obtains carbon in 60 DEG C of vacuum drying after separating and receives
Nanotube surface quaternized antibacterial in situ.This antibacterial is respectively provided with the antibacterial effect of excellence to staphylococcus aureus and escherichia coli
Really, minimum antibacterial dosage has respectively reached 80mg/L and 60mg/L.
Embodiment 5:
(1) CNT grafting polyethylene imine: be the polymine of 70000 by acidifying CNT and molecular weight
(CNT and the mass ratio 1:3 of polymine) disperses in deionized water respectively, mixes subsequently, ultrasonic Treatment 1h,
Power is 250W so that it is is uniformly dispersed, and is stirred at room temperature 12h, makes polymine fully occur with acidifying CNT
Reaction, reaction gained solid product is successively through ethanol, water washing, and sucking filtration obtains the carbon nanometer of grafting polyethylene imine after separating
Pipe.
(2) tertiary-aminated reaction: the CNT grafting polyethylene imine of preparation in step (1) is dispersed in deionized water
In, stir, be the proportioning of 1:1 according to expoxy propane and polymine mass ratio, tertiary-aminated reagent expoxy propane is delayed
Slowly being added drop-wise in dispersion liquid, stirring reaction 6h at 3 DEG C, filter the solids separated and use the washing of ethanol, water successively, sucking filtration separates
After obtain CNT be grafted tertiary-aminated polymine.
(3) quaterisation: the CNT of preparation in step (2) is grafted tertiary-aminated polymine and is distributed to uncle penta
In alcohol, it is the proportioning of 1:1 according to iodomethane and expoxy propane mol ratio, is slowly added dropwise quaternizing agent iodomethane, stirs at 70 DEG C
Mixing reaction 12h, filter the solids separated and wash with ethanol, water successively, sucking filtration obtains carbon in 60 DEG C of vacuum drying after separating and receives
Nanotube surface quaternized antibacterial in situ.This antibacterial is respectively provided with the antibacterial effect of excellence to staphylococcus aureus and escherichia coli
Really, minimum antibacterial dosage has respectively reached 100mg/L and 100mg/L.
Embodiment 6:
(1) CNT grafting polyethylene imine: be the polymine of 70000 by acidifying CNT and molecular weight
(CNT and the mass ratio 1:3 of polymine) disperses in deionized water respectively, mixes subsequently, ultrasonic Treatment 1h,
Power is 250W so that it is is uniformly dispersed, and is stirred at room temperature 12h, makes polymine fully occur with acidifying CNT
Reaction, reaction gained solid product is successively through ethanol, water washing, and sucking filtration obtains the carbon nanometer of grafting polyethylene imine after separating
Pipe.
(2) tertiary-aminated reaction: the CNT grafting polyethylene imine of preparation in step (1) is dispersed in deionized water
In, stir, be the proportioning of 5:3 according to expoxy propane and polymine mass ratio, tertiary-aminated reagent expoxy propane is delayed
Slowly being added drop-wise in dispersion liquid, stirring reaction 7h at 2 DEG C, filter the solids separated and use the washing of ethanol, water successively, sucking filtration separates
After obtain CNT be grafted tertiary-aminated polymine.
(3) quaterisation: the CNT of preparation in step (2) is grafted tertiary-aminated polymine and is distributed to uncle penta
In alcohol, it is the proportioning of 1:1 according to bromohexadecane and expoxy propane mol ratio, is slowly added dropwise quaternizing agent bromohexadecane,
At 60 DEG C, 12h is reacted in stirring, filters the solids separated successively with ethanol, water washing, in 60 DEG C of vacuum drying after sucking filtration separation
Obtain carbon nano tube surface quaternized antibacterial in situ.This antibacterial is respectively provided with excellence to staphylococcus aureus and escherichia coli
Antibacterial effect, minimum antibacterial dosage has respectively reached 60mg/L and 30mg/L.
Reference examples 1: for acidifying CNT, it is entered under same experiment condition with same antibacterial detection method
Row anti-microbial property detects.Testing result shows to be acidified CNT to staphylococcus aureus and colibacillary antibacterial effect relatively
Difference, minimum antibacterial dosage is all higher than 800mg/L.And the antibacterial effect that is acidified carbon nano tube surface in situ quaternized antibacterial is relative
In acidifying CNT, then tool is significantly improved.
Reference examples 2: for pure CNT, it is entered under same experiment condition with same antibacterial detection method
Row anti-microbial property detects.Testing result shows that pure nano-carbon tube is to staphylococcus aureus and colibacillary antibacterial effect the most relatively
Difference, minimum antibacterial dosage is all higher than 1000mg/L.And it is acidified the antibacterial effect phase of carbon nano tube surface quaternized antibacterial in situ
For pure CNT, same tool is significantly improved.
Antibacterial experiment is with reference to antibacterial quantity measuring method detection minimum in " disinfection technology standard " (2002 editions).
As shown in Figure 6, the CNT grafting polymer quaternary ammonium salt antiseptic of optimum process is to golden yellow for antibacterial experiment result
The antibacterial dosage of minimum of color Fructus Vitis viniferae ball is 50mg/L, and dosage antibacterial to colibacillary minimum is 20mg/L, shows CNT
The quaternized antibacterial of surface in situ has good antibacterial effect.
Claims (7)
1. the preparation method being acidified CNT grafting polymer quaternary ammonium salt antiseptic, it is characterised in that receive being acidified carbon
Mitron (CNTs) is carrier, first in its surface grafting polymine (PEI), and carries out the polymine of grafting successively
Tertiary-aminated and quaterisation forms the quaternary ammonium salt long-acting antibiotic agent (QPEI@CNTs) that CNT is the most quaternized, including such as
Lower key step:
(1) acidifying CNT grafting polyethylene imine: acidifying CNT and polymine are dispersed in deionization respectively
In water, acidifying CNT is mass ratio 1:1～1:3 with the proportioning of polymine, and mixing ultrasonic Treatment make it subsequently
Being uniformly dispersed, be stirred at room temperature 8～12h, make polymine fully react with acidifying CNT, reaction gained is solid
Body product is successively through ethanol, water washing, and sucking filtration obtains the acidifying CNT of grafting polyethylene imine after separating；
(2) tertiary-aminated reaction: step (1) gained acidifying CNT grafting polyethylene imine is disperseed in deionized water, stirs
Mixing uniformly, be slowly dropped in dispersion liquid by tertiary-aminated reagent, at 0～3 DEG C, stirring reaction 6～8h, filters the solid separated
Thing with ethanol, water washing, obtains being acidified CNT and is grafted tertiary-aminated polymine successively after sucking filtration separation；
(3) quaterisation: step (2) gained acidifying CNT is grafted tertiary-aminated polymine and is distributed to tert-pentyl alcohol
In, it being slowly added dropwise quaternizing agent, the mol ratio of tertiary-aminated reagent used is 1～2:1 to quaternizing agent with step (2)；?
Stirring reaction 10～14h at 50～70 DEG C, filters the solids separated successively with ethanol, water washing, sucking filtration separate after in 40～
80 DEG C of vacuum drying obtain target product carbon nano tube surface quaternized antibacterial in situ.
A kind of preparation method being acidified CNT grafting polymer quaternary ammonium salt antiseptic the most according to claim 1, its
It is characterised by: in step (1), molecular weight >=600 of polymine PEI.
A kind of preparation method being acidified CNT grafting polymer quaternary ammonium salt antiseptic the most according to claim 1, its
Being characterised by: in step (1), ultrasonic time is 1～2h, and power is 100～250W.
A kind of preparation method being acidified CNT grafting polymer quaternary ammonium salt antiseptic the most according to claim 1, its
Being characterised by: in step (2), described tertiary-aminated reagent is expoxy propane, and it is 1～2.5:1 with the mass ratio of polymine.
A kind of preparation method being acidified CNT grafting polymer quaternary ammonium salt antiseptic the most according to claim 1, its
It is characterised by: described quaternizing agent is one or more in iodomethane, bromoethane or bromohexadecane.
A kind of preparation method being acidified CNT grafting polymer quaternary ammonium salt antiseptic the most according to claim 1, its
It is characterised by: described target antibacterial has good suppression bacterial action, and typical bacteria includes but not limited to bacteria Staphylococcus
Staphylococcus and large intestine bar bacillus typical bacteria.
A kind of preparation method being acidified CNT grafting polymer quaternary ammonium salt antiseptic the most according to claim 6, its
It is characterised by: described target antibacterial antibacterial dosage minimum to staphylococcus aureus and large intestine bar bacillus typical bacteria is respectively
50mg/L and 20mg/L.
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| CN115678419A (en) * | 2022-07-19 | 2023-02-03 | 浙江工业大学 | Antibacterial water-repellent organic-inorganic hybrid coating of quaternary ammonium salt and synthetic method |
| CN115678419B (en) * | 2022-07-19 | 2023-11-24 | 浙江工业大学 | Water-repellent organic-inorganic hybrid coating with antibacterial quaternary ammonium salt and synthesis method |
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| CN115109468B (en) * | 2022-08-03 | 2023-09-08 | 浙江工业大学 | Multifunctional water-based damping paint and preparation method thereof |
| CN115232534A (en) * | 2022-08-26 | 2022-10-25 | 侯晓娜 | Antibacterial anticorrosive paint and preparation method thereof |
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