CN108411626A - A kind of preparation method and application of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber - Google Patents

A kind of preparation method and application of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber Download PDF

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CN108411626A
CN108411626A CN201810184321.XA CN201810184321A CN108411626A CN 108411626 A CN108411626 A CN 108411626A CN 201810184321 A CN201810184321 A CN 201810184321A CN 108411626 A CN108411626 A CN 108411626A
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fiber
polyamino
ammonium salt
quaternary ammonium
amine type
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CN108411626B (en
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聂国朝
吴艳华
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Yulin Normal University
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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Abstract

The present invention discloses a kind of preparation method and application of quaternary ammonium salt N halogen amine type antiseptic nano-fiber, after natural fiber activating pretreatment, graft reaction is carried out with polyamino high-molecular compound or the more sulfydryl high-molecular compounds of polyamino, it is crosslinked by crosslinking agent after being grafted again with quaternary ammonium salt, the quaternary ammonium salt N halogen amine type antiseptic nano-fibers of the present invention is obtained after bleaching；The antiseptic nano-fiber of the present invention possesses the difunctional antibacterial functions of contact-type and release type simultaneously, greatly accelerate sterilizing speed, it can also sterilize at normal temperatures and pressures, and antibiotic property is strong, persistent is not likely to produce drug resistance, medical care articles for use can be made in the fibre antibacterial material, such as cotton swab, cotton balls, gauze, mask, operation clothing, can be widely applied to the numerous areas such as food packaging, food fresh-keeping, medical instrument, public health, water purification system, gather around and have wide practical use.

Description

A kind of preparation method and application of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber
Technical field
The present invention relates to technical field of polymer materials, more particularly relate to a kind of quaternary ammonium salt-N- halogen amine type nano-antibacterial The preparation method and application of fiber.
Background technology
With the raising of living condition, people increasingly pay close attention to safety, nutrition, sense organ, mouthfeel and the flavor of food.As Extend main means -- such as wet-hot steam sterilizing, hot air sterilization, boiling sterilization, the pasteurization sterilizing methods of Food Shelf-life Frequently result in the quality deterioration of food, including nutritive loss, texture change, color change, taste variation, smell change etc..For The destruction of thermal sensitivity nutrition caused by avoiding heating, keeps the color of article as far as possible.In recent years, cold sterilization skill Art is studied extensively, is expected to be applied to food sterilizing, mainly there is irradiation sterilization, ultra-high pressure sterilization, ultrasonic sterilization, high-tension pulse Rush electric field sterilization, magnetic field sterilizing, sterilizing technology with pulsed light.But these cold sterilization methods often need special equipment, it is such as anti- Radiation appliance, ultra-high pressure apparatus, or can be only applied to surface sterilizing such as sterilizing technology with pulsed light or device and killed with certain Bacterium acts on, but single device bactericidal effect can't reach commercial sterilization requirement, and the volume for sterilizing material is very limited, because The devices such as this ultra-high pressure sterilization, high-voltage pulse electric field sterilization magnetic field sterilizing also have a distance apart from practical application, it is also necessary into One step research and perfect.
Generally according to the chemical composition of anti-biotic material, it is classified as inorganic antibacterial material, organic anti-bacterial material, biological antibiotic Material, composite antibacterial material etc..According to Antibacterial Mechanism, anti-biotic material can be divided into contact-type, release type, absorption-type and anti-adhesive type Four kinds of main function mechanism.Different anti-biotic materials has respective advantage and defect in independent role.Common contact-type is anti- Bacterium material such as quaternary ammonium salt, quaternary phosphonium salt have very high charge density, strong to the suction-operated and contact action of bacterium；Release Type anti-biotic material, mainly there is silver ion, halogen, antibiotic etc., wherein N- halogen amine polymer antibacterial agent as antibacterial agent, Have many advantages, such as efficient, lasting, wide spectrum, renewable, nontoxic and environmentally safe, is a kind of environmentally protective efficient antibacterial Agent.
Tree cotton, also known as Calotropis gigantea (Calotropis gigantea L.), be suitble to the torrid zone, subtropical zone stony desert, it is saline and alkaline The barren hillside fields growth such as ground, seashore beach, is novel " all-round " seeds.Fiber averagely long 34.2mm, fineness 16-28um, Close to cashmere fineness.Degree of hollowness is 80-90%, and tree cotton fibrous fracture intensity is 4.45cN/dtex, and elongation at break is 3.40%.It is pure natural fiber, the textile cloth for being suitble to production light, thin, warming.Tree cotton fiber is easy to fly in sizable application Flower, obvolvent force difference, at item hardly possible, this is the main reason for limiting tree cotton fiber extensive use.Since 20th century, foreign scholar is successive Weaving and medical value to tree cotton expand comprehensive research.In recent years, domestic and foreign scholars dramatically increase the research of tree cotton, main Concentrate on the research of active constituent extraction and application aspect.The stem micromicro of tree cotton plant is for papermaking, rope making, burlap and artificial Cotton, tree cotton kind hair filler and velvet are good fiber raw materials, can also extract fiber from the trunk of tree cotton.Tree cotton quilt It is described as the another green fiber source with wide application prospect after cotton.
Invention content
It is an object of the invention to overcome defect of the existing technology, it is anti-to provide a kind of quaternary ammonium salt-N- halogen amine type nanometer The preparation method of bacterium fiber.
To achieve the goals above, the technical solution adopted by the present invention is as follows：
The preparation method of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers of the present invention, includes the following steps：
The preparation method of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers of the present invention, includes the following steps：
A：Using epoxychloropropane and sodium hydroxide solution to natural fiber after natural fiber is impregnated with ethylenediamine solution Activating pretreatment is carried out, epocel is obtained；
B：Epocel described in step A is subjected to etherificate graft reaction with polyamino Polymer Solution, obtains polyamino Graft fibres；Or the more two thio fibres of polyamino are obtained by the reaction in polyamino graft fibres and 3,3 '-dithio dipropyl dimethyl phthalates Dimension, then two thio fibers more than polyamino are restored using zinc powder, obtain the more sulfydryl graft fibres of polyamino；
C：It is 0.04- by the more sulfydryl graft fibres of the polyamino graft fibres or polyamino of step B and molar concentration The aqueous isopropanol of the quaternary ammonium salt of 0.10mol/L hybrid reaction 3-5h at 55-65 DEG C, obtains quaternization fiber；
D：Reaction is added in the PBS buffer solution that the quaternization fiber and crosslinking agent and pH value of step C are 7.0-7.8 Kettle is heated to 45-50 DEG C and maintains 1-3h after mixing, filtering, with purified water wash off product, obtains crosslinking quaternary ammonium salt chemical fibre Dimension；
E：The crosslinking quaternization fiber of step D is soaked in the hypohalite solution that molar concentration is 0.3-0.7mol/L 10-30min is steeped, then is dried after being cleaned with purified water, quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers are obtained.
Preferably, the natural fiber is one in tree cotton fiber, bamboo fibre, flaxen fiber, cotton fiber or silk fiber Kind or more than one mixing.
Preferably, the natural fiber is tree cotton fiber and/or cotton fiber.
Preferably, the step A to natural fiber carry out pre-activate processing the specific steps are：Natural fiber is pressed 1: The bath raio of 55-75 is soaked into the ethylenediamine solution that mass fraction is 70-80%, and heating water bath is to 35-45 DEG C, after heating 3-5h Using alternately washing natural fiber 2-3 times of ethyl alcohol and purified water, epoxychloropropane is added in natural fiber and molar concentration is The sodium hydroxide solution of 0.005-0.015mol/L, is stirred to react 8-12h at 28-32 DEG C, then with purifying water washing 1-3 times, It is dry at 55-65 DEG C to be put into baking oven, the epocel activated；
The bath raio of the natural fiber and epoxychloropropane is 1：3-5；The bath of the natural fiber and sodium hydroxide solution Than being 1：6-8.
Preferably, the epocel of the step B carries out the specific step of etherificate graft reaction with polyamino Polymer Solution Suddenly it is：
Epocel and volume fraction are pressed 1 for the polyamino Polymer Solution of 8-12%:After the bath raio mixing of 45-55, It is heated to 65-75 DEG C, is stirred to react 3.5-5h, then uses ethyl alcohol and purified water to replace washing reaction product, then at 45-60 DEG C Drying, obtains polyamino graft fibres；
The preparation method of the polyamino Polymer Solution includes the following steps：
F：By methyl acrylate and methanol according to 1:The molar ratio of 3.8-6.2 is uniformly mixed, and obtains mixed solution；
G：Methyl acrylate and enamine are pressed into 3-5：After the molar ratio mixing of 4-6 under 0-3 DEG C of nitrogen atmosphere, side stirring While methyl acrylate and mixed solution are added dropwise in enamine, continue to be stirred to react 20-28h at room temperature after being added dropwise, It is then heated to 50-60 DEG C and is stirred to react 3-5h, the methanol in low-temperature evaporation hybrid reaction system obtains faint yellow sticky Liquid；
H：The faint yellow viscous fluid of step G and ethyl alcohol are pressed 1:The volume ratio of 8-10 be mixed it is even after, obtain polyamino high score Sub- solution；
The enamine is triethylene tetramine, four ethylene triamines or five ethylene tetramines；
The molar ratio of the methyl acrylate of the step F and the methyl acrylate of step G is 1：1.2-2.
Preferably, more ammonia are obtained by the reaction in the polyamino graft fibres and 3 of the step B, 3 '-dithio dipropyl dimethyl phthalates Two thio fiber of Quito, then two thio fibers more than polyamino are restored using zinc powder, it is fine to obtain the more sulfydryls grafting of polyamino Dimension the specific steps are：
I：By 1-1.5：It is 5- that mass fraction, which is added, in the solid-liquid ratio of 10-15 in 3,3 '-dithio dipropyl dimethyl phthalates 10% sodium carbonate liquor, by 1 after stirring evenly：Polyamino graft fibres are added in the bath raio of 50-70, are stirred at 20-30 DEG C anti- 36-60h is answered, is filtered, replaces cleaning product with ethyl alcohol and purified water, obtains the more two thio fibers of polyamino；
J：By 1:The bath raio of 50-60 is by two thio fibers more than the polyamino of step I and acetic acid that volume fraction is 7-12% Solution after mixing, zinc powder is added at 40-50 DEG C and carries out reduction reaction, filters after reaction, with purifying while stirring Net products are washed, the more sulfydryl graft fibres of polyamino are obtained；
The mass ratio of the more two thio fibers of step J polyaminos and zinc powder is 1:1-1.5.
Preferably, quaternary ammonium salt described in step C is 2,3- epoxypropyltrimethylchloride chlorides, methylacryoyloxyethyl-benzyl Base-alkyl dimethyl ammonium chloride, acrylyl oxy-ethyl-benzyl-dimethyl ammonium chloride, methylacryoyloxyethyl-benzyl-diethyl chlorine Change ammonium, acrylyl oxy-ethyl-benzyl-diethylammonium chloride, methylacryoyloxyethyl-trimethyl ammonium chloride, acryloyl-oxy second Any one in base-trimethyl ammonium chloride, two acrylyl oxy-ethyls-benzyl-methyl ammonium chloride.
Preferably, the crosslinking agent described in step D is water cape jasmine extract Geniposide or glutaraldehyde；The dosage of the crosslinking agent For the 0.01-5% of quaternization fiber quality.
Preferably, the hypohalite solution described in step E is that liquor natrii hypochloritis, postassium hypochlorite solution, sodium hypobromite are molten One or more kinds of mixtures in liquid, potassium hypobromite solution；The dosage of the hypohalite is crosslinking quaternary ammonium salt chemical fibre Tie up the 0.01-0.1% of quality.
The present invention also provides the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers in food packaging, food-pasteurization, medical treatment Purposes in terms of instrument, public health, water purification system.
Preferably, the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers are in the application process of food-pasteurization purposes：By season Ammonium salt-N- halogen amine type antiseptic nano-fibers are immersed in liquid food, or quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers are placed in In low-voltage direct container, liquid food is set to flow through the container, you can to reach and sterilize to fluid food in normal temperature and pressure；
Quaternary ammonium salt-N- halogen amine type the antiseptic nano-fibers are in the application process of medical instrument purposes：By the season Ammonium salt-N- halogen amine type antiseptic nano-fibers are used to prepare the medical and health uses such as cotton swab, cotton balls, gauze, mask and operation clothing Product.
The present invention is by adopting the above-described technical solution, have the advantages that：
(1) antiseptic nano-fiber of the invention is using natural fiber as carrier, using the hollow characteristic of fiber, by activating, It is grafted active group, assigns its excellent contact-type and the multi-functional Synergistic antimicrobial potential of release type, passes through letter in a mild condition After single activation process, then by etherificate, cross-linking reaction, fiber surface be easy the upper different-grain diameter of grafting nanosizing polyamines base or More sulfydryl branches or protrusion, fiber become coarse surface by original smooth surface obvolvent force difference, can be between reinforcing fiber Interaction force improves spinnability, increases application field.
(2) antiseptic nano-fiber of the invention is through acute oral toxicity test, heavy metal analysis, preservative detection, detection The result shows that antiseptic nano-fiber of the invention is nontoxic, no Determination of common preservatives, heavy metal free ion, antibiotic property is strong, and effect is held Long, it is not likely to produce drug resistance and renewable, which can be made medical care articles for use, such as cotton swab, cotton balls, gauze, mouth Cover, operation clothing etc., largely make up the deficiency of traditional medical anti-biotic material manufactured goods, bring glad tidings to hospitalized patients； It also can be widely used to the numerous areas such as food packaging, food fresh-keeping, medical instrument, public health, water purification system.
(3) present invention also uses water cape jasmine extract Geniposide as crosslinking agent, Geniposide as natural biological crosslinking agent, Being followed successively by the composite fibre that crosslinking agent is prepared has higher tensile strength, inoxidizability and lower moisture expansivity and friendship Connection degree, secondly, covalent cross-linking is prepared antiseptic nano-fiber of the invention twice with Geniposide by etherificate, than general ester Key, the stability of amido bond are high, and wherein tree cotton antibacterial derives from a wealth of sources cheap, and tree cotton fiber is through washing 100 times or more, Active Chlorine Power of regeneration is higher than common cotton fibre grafting work chlorine recovery capability up to 90% or more；In addition, quaternary ammonium salt sun is by stable Ehter bond is grafted on fiber, with common washing methods be difficult dissociate come, so general grafting anti-bacterial fibre is compared, nanometer Stability and recyclability of the chemical fibre dimension with height.
(4) antiseptic nano-fiber of the invention possesses the difunctional antibacterial functions of contact-type and release type simultaneously, will be double Functional group's fiber is placed in low-voltage direct container, and low-voltage DC will produce active oxygen or Active Chlorine to prevent the production of biomembrane It is raw, since biofilm structure feature is that have certain mobility, makes to increase between bacterium all to take identical charge, prevent bacterium It unites, prevents that the formation of upper bacterial biof iotalm, bacterium deform upon under electric field action, easily acted on, greatly speed up by antibacterial group Sterilizing speed；Or liquid food is made to flow through the container or difunctional fiber is immersed directly in liquid food, you can Reach the sterilization fresh effect under room temperature, normal pressure；It solves such as wet-hot steam sterilizing of traditional sterilizing methods, hot air sterilization, boil Boiling sterilizing, pasteurization etc. lead to the quality deterioration of food, including nutritive loss, texture change, color change, and taste changes, The problems such as smell changes.In order to avoid the destruction of thermal sensitivity nutrition caused by heating, keep as far as possible the color of article, perfume (or spice), Taste；And the difunctional Antibacterial Mechanism due to possessing contact-type and release type, sterilizing speed is greatly accelerated, to golden yellow grape The sterilization time of coccus shortens to or so half an hour by monofunctional 6-8 hours, and Staphylococcus aureus is replaced with Escherichia coli Bacterium carries out similar experiment, the results showed that and difunctional nanosizing fiber also can quickly kill Escherichia coli in 10-30min, this The anti-bacterial fibre of invention has significant antibacterial action to gram-positive bacteria and Gram-negative bacteria.
(5) any antiseptic need not be added in antiseptic nano-fiber of the invention, but on substrate molecule chain, group is loaded onto By preferred antibacterial functions group, the heavy metal pollution of inorganic metal anti-biotic material is avoided, when small molecule drug effect being avoided to continue Between it is short, avoid natural biological anti-biotic material from being easy to be degraded by enzymes or the drawbacks such as poor heat resistance, there is high-efficiency broad spectrum, safe and non-toxic, Effect is lasting, it is at low cost the features such as, and material have excellent processability, be easy large-scale production and price advantage；It can also be anti- Multiple to use, this keeps food nutrition, reduction food sterilizing cost to have important meaning to preventing fluid food pathogenic microorganisms from infecting Justice.The antiseptic nano-fiber of the present invention is safe to use, and antibiotic property is strong, and preparation method is simple, and raw material is cheap and easily-available, has wide Market prospects.
Description of the drawings
Fig. 1 be the embodiment of the present invention 2 tree cotton before modified after infrared spectrogram.
Fig. 2 is pattern and scanning mirror figure before and after the tree cotton fibre grafting of the embodiment of the present invention 2.
Fig. 3 is inhibition of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers of the embodiment of the present invention 4 to staphylococcus aureus Effect.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, preferred embodiment is enumerated below, to this hair Bright further description.However, it is necessary to illustrate, many details listed in specification are used for the purpose of making reader to this There are one thorough explanations for the one or more aspects of invention, can also realize the present invention's even without these specific details These aspects.
Embodiment 1
The preparation method of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers of the present invention, includes the following steps：
A：The composite fibre of tree cotton fiber and cotton fiber is pressed 1:55 bath raio is soaked into the second two that mass fraction is 70% In amine aqueous solution, heating water bath uses alternately washing tree cotton fiber 2 times of ethyl alcohol and purified water, in tree cotton fibre to 35 DEG C after heating 3h 1 is pressed in dimension:Epoxychloropropane is added in 3 bath raio, and presses 1:The hydroxide that molar concentration is 0.005mol/L is added in 6 bath raio Sodium solution is stirred to react 8h at 28 DEG C, then is cleaned with purified water, is put into baking oven drying, the epoxy activated at 55 DEG C Fiber；
B：The polyamino Polymer Solution that the epocel of step A and volume fraction are 8% is pressed 1:45 bath raio mixing Afterwards, 65 DEG C are heated to, 3.5h is stirred to react, then uses ethyl alcohol and purified water to replace washing reaction product, then dried at 45 DEG C, Obtain polyamino graft fibres；
C：It is the 2,3- glycidyl front threes of 0.04mol/L by the polyamino grafting tree cotton fiber of step B and molar concentration The aqueous isopropanol of ammonium chloride presses 1:After 45 bath raio mixing, 3h is reacted at 55 DEG C, obtains quaternization fiber；
D：The PBS buffer solution for being 7.0 by the quaternization fiber of step C and water cape jasmine extract Geniposide and pH value Reaction kettle is added, is heated to 45 DEG C after mixing and maintains 1h, filters, with purified water wash off product, obtains crosslinking quaternary ammonium salt Chemical fibre is tieed up；
E：The crosslinking quaternization fiber of step D is impregnated in the liquor natrii hypochloritis that molar concentration is 0.3mol/L 30min, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers；
The dosage of the water cape jasmine extract Geniposide is the 0.01% of quaternization fiber quality；
The dosage of the sodium hypochlorite is be crosslinked quaternization fiber quality 0.01%；
The preparation method of the polyamino Polymer Solution includes the following steps：
F：By methyl acrylate and methanol according to 1:3.8 molar ratio is uniformly mixed, and obtains mixed solution；
G：Methyl acrylate and triethylene tetramine are pressed 3：After 4 molar ratio mixing under 0 DEG C of nitrogen atmosphere, side stirring While methyl acrylate and mixed solution are added dropwise in triethylene tetramine, continue to be stirred to react at room temperature after being added dropwise 20h, is then heated to 50 DEG C and is stirred to react 3h, and the methanol in low-temperature evaporation hybrid reaction system obtains faint yellow viscous fluid；
H：The faint yellow viscous fluid of step G and ethyl alcohol are pressed 1:8 volume ratio be mixed it is even after, it is molten to obtain polyamino macromolecule Liquid；
The molar ratio of the methyl acrylate of the step F and the methyl acrylate of step G is 1：1.2.
The application process of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers is：It uses it for preparing medical cotton stick.
Embodiment 2
The preparation method of the quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers of the present invention, includes the following steps：
A：Tree cotton fiber is pressed 1:57 bath raio is soaked into the ethylenediamine solution that mass fraction is 72%, and heating water bath is extremely 37 DEG C, alternately washing tree cotton fiber 3 times of ethyl alcohol and purified water are used after heating 3.3h, 1 is pressed in tree cotton fiber:3.4 bath raio Epoxychloropropane is added, and presses 1:The sodium hydroxide solution that molar concentration is 0.007mol/L is added in 6.3 bath raio, 28.5 It is stirred to react 8.4h at DEG C, then is cleaned with purified water, is put into baking oven drying, the asphalt mixtures modified by epoxy resin cotton fiber activated at 57 DEG C；
B：The polyamino Polymer Solution that the asphalt mixtures modified by epoxy resin cotton fiber of step A and volume fraction are 8.6% is pressed 1:48 bath After mixing, 68 DEG C are heated to, is stirred to react 3.8h, then uses ethyl alcohol and purified water to replace washing reaction product, then at 48 DEG C Lower drying obtains polyamino grafting tree cotton fiber；
C：It is the methylacryoyloxyethyl-of 0.05mol/L by the polyamino grafting tree cotton fiber of step B and molar concentration The aqueous isopropanol of benzyl-dimethyl ammonium chloride presses 1:After 50 bath raio mixing, 3.2h is reacted at 56 DEG C, obtains quaternization Tree cotton fiber；
D：The quaternization tree cotton fiber of step C is placed in reaction kettle, PBS buffer solution and the water that pH value is 7.5 is added Capejasmine extract Geniposide heats and maintains centrifugal treating 0.7h at 46 DEG C, filtering, with water washing is purified 4 times, is crosslinked Quaternization tree cotton fiber；
E：It is molten that the crosslinking quaternization tree cotton fiber of step D is immersed in the postassium hypochlorite that molar concentration is 0.35mol/L 28min in liquid, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers；
The dosage of the water cape jasmine extract Geniposide is the 0.1% of quaternization tree cotton fiber quality；
The dosage of the postassium hypochlorite is be crosslinked quaternization tree cotton fiber quality 0.02%；
The preparation method of the polyamino Polymer Solution includes the following steps：
F：By methyl acrylate and methanol according to 1:4 molar ratio is uniformly mixed, and obtains mixed solution；
G：Methyl acrylate and four ethylene triamines are pressed 3.5：After 4.6 molar ratio mixing under 1 DEG C of nitrogen atmosphere, side Methyl acrylate and mixed solution is added dropwise in four ethylene triamines in stirring side, and it is anti-to continue stirring after being added dropwise at room temperature 21.5h is answered, be then heated to 51 DEG C and is stirred to react 3.3h, the methanol in low-temperature evaporation hybrid reaction system obtains faint yellow Viscous fluid；
H：The faint yellow viscous fluid of step G and ethyl alcohol are pressed 1:8.6 volume ratio be mixed it is even after, obtain polyamino macromolecule Solution；
The molar ratio of the methyl acrylate of the step F and the methyl acrylate of step G is 1：1.3.
The application process of the quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers is：It uses it for preparing medical cotton Ball.
Embodiment 3
The preparation method of the quaternary ammonium salt-N- halogen amine type nano-antibacterial flaxen fibers of the present invention, includes the following steps：
A：Flaxen fiber is pressed 1:60 bath raio is soaked into the ethylenediamine solution that mass fraction is 73%, heating water bath to 38 DEG C, alternately washing flaxen fiber 2 times of ethyl alcohol and purified water are used after heating 3.7h, 1 is pressed in flaxen fiber:Ring is added in 3.7 bath raio Oxygen chloropropane, and press 1:The sodium hydroxide solution that molar concentration is 0.008mol/L is added in 6.6 bath raio, is stirred at 29 DEG C 8.8h is reacted, then is cleaned with purified water, baking oven drying, the epoxy flaxen fiber activated at 59 DEG C are put into；
B：The polyamino Polymer Solution that the epoxy flaxen fiber of step A and volume fraction are 9% is pressed 1:50 bath raio is mixed After conjunction, 69 DEG C are heated to, is stirred to react 4.2h, then uses ethyl alcohol and purified water to replace washing reaction product, then dried at 50 DEG C It is dry, obtain polyamino grafted fibrilia；
C：It is acrylyl oxy-ethyl-benzyl-of 0.06mol/L by the polyamino grafting bamboo fibre of step B and molar concentration The aqueous isopropanol of alkyl dimethyl ammonium chloride presses 1:After 52 bath raio mixing, 3.5h is reacted at 57 DEG C, it is fine to obtain quaternization fiber crops Dimension；
D：Reaction kettle is added in the PBS buffer solution that the quaternization flaxen fiber and glutaraldehyde and pH value of step C are 7.1, It is heated to 47 DEG C after mixing and maintains 0.9h, filters, with purified water wash off product, obtains crosslinking quaternization flaxen fiber；
E：The crosslinking quaternization flaxen fiber of step D is immersed in the sodium hypobromite solution that molar concentration is 0.4%mol/L Middle 25min, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type nano-antibacterial flaxen fibers；
The dosage of the glutaraldehyde is the 0.5% of quaternization flaxen fiber quality；
The dosage of the sodium hypobromite is be crosslinked quaternization flaxen fiber quality 0.03%；
The preparation method of the polyamino Polymer Solution includes the following steps：
F：By methyl acrylate and methanol according to 1:4.3 molar ratio is uniformly mixed, and obtains mixed solution；
G：Methyl acrylate and five ethylene tetramines are pressed 3.9：After 5 molar ratio mixing under 2 DEG C of nitrogen atmosphere, while stirring It mixes side and methyl acrylate and mixed solution is added dropwise in five ethylene tetramines, continue to be stirred to react at room temperature after being added dropwise 23h, is then heated to 53 DEG C and is stirred to react 3.6h, and the methanol in low-temperature evaporation hybrid reaction system obtains faint yellow sticky Liquid；
H：The faint yellow viscous fluid of step G and ethyl alcohol are pressed 1:8.8 volume ratio be mixed it is even after, obtain polyamino macromolecule Solution；
The molar ratio of the methyl acrylate of the step F and the methyl acrylate of step G is 1：1.4.
The application process of the quaternary ammonium salt-N- halogen amine type nano-antibacterial flaxen fibers is：It uses it for preparing hospital gauze.
Embodiment 4
The preparation method of the quaternary ammonium salt-N- halogen amine type nano antibiotic cotton fibers of the present invention, includes the following steps：
A：Cotton fiber is pressed 1:63 bath raio is soaked into the ethylenediamine solution that mass fraction is 74%, heating water bath to 39 DEG C, alternately washing cotton fiber 3 times of ethyl alcohol and purified water are used after heating 4h, 1 is pressed in cotton fiber:Epoxy is added in 3.9 bath raio Chloropropane, and press 1:The sodium hydroxide solution that molar concentration is 0.009mol/L is added in 6.8 bath raio, is stirred at 30 DEG C anti- 9.2h is answered, then with water washing is purified 2 times, is put into baking oven drying, the epoxy cotton fiber activated at 60 DEG C；
B：The polyamino Polymer Solution that the epoxy cotton fiber of step A and volume fraction are 10% is pressed 1:51 bath raio is mixed After conjunction, 72 DEG C are heated to, is stirred to react 4.6h, then uses ethyl alcohol and purified water to replace washing reaction product, then dried at 57 DEG C It is dry, obtain polyamino crafted cotton fibers；
C：It is methylacryoyloxyethyl-benzyl of 0.08mol/L by the polyamino crafted cotton fibers of step B and molar concentration The aqueous isopropanol of base-diethylammonium chloride presses 1:After 54 bath raio mixing, 3.8h is reacted at 59 DEG C, obtains quaternization cotton Fiber；
D：The PBS that the quaternization cotton fiber of step C and water cape jasmine extract Geniposide and pH value are 7.2 is buffered Reaction kettle is added in liquid, is heated to 48 DEG C after mixing and maintains 1.1h, filters, and with purified water wash off product, obtains crosslinking season Salified cotton fiber；
E：The crosslinking quaternization cotton fiber of step D is immersed in the potassium hypobromite solution that molar concentration is 0.5%mol/L Middle 22min, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type nano antibiotic cotton fibers；
The dosage of the water cape jasmine extract Geniposide is the 0.1% of quaternization cotton quality；
The dosage of the potassium hypobromite is be crosslinked quaternization cotton quality 0.04%；
The preparation method of the polyamino Polymer Solution includes the following steps：
F：By methyl acrylate and methanol according to 1:4.7 molar ratio is uniformly mixed, and obtains mixed solution；
G：Methyl acrylate and triethylene tetramine are pressed 4.2：After 5.5 molar ratio mixing under 3 DEG C of nitrogen atmosphere, side Methyl acrylate and mixed solution is added dropwise in stirring side in triethylene tetramine, and it is anti-to continue stirring after being added dropwise at room temperature 55 DEG C should be then heated to and be stirred to react 3.9h for 24 hours, the methanol in low-temperature evaporation hybrid reaction system, is obtained faint yellow viscous Magma；
H：The faint yellow viscous fluid of step G and ethyl alcohol are pressed 1:9.3 volume ratio be mixed it is even after, obtain polyamino macromolecule Solution；
The molar ratio of the methyl acrylate of the step F and the methyl acrylate of step G is 1：1.5.
The application process of the quaternary ammonium salt-N- halogen amine type nano antibiotic cotton fibers is：It uses it for preparing sterile mask.
Embodiment 5
The preparation method of the quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers of the present invention, includes the following steps：
A：Silk fiber is pressed 1:66 bath raio is soaked into the ethylenediamine solution that mass fraction is 75%, and heating water bath is extremely 40 DEG C, alternately washing silk fiber 2 times of ethyl alcohol and purified water are used after heating 4.2h, 1 is pressed in silk fiber:4.2 bath raio Epoxychloropropane is added, and presses 1:The sodium hydroxide solution that molar concentration is 0.01mol/L is added in 7 bath raio, at 31 DEG C It is stirred to react 9.5h, then is cleaned with purified water, baking oven drying, the epoxy silk fiber activated at 62 DEG C are put into；
B：The polyamino Polymer Solution that the epoxy silk fiber of step A and volume fraction are 12% is pressed 1:55 bath raio After mixing, 75 DEG C are heated to, is stirred to react 5h, then uses ethyl alcohol and purified water to replace washing reaction product, then dried at 60 DEG C It is dry, obtain polyamino grafting silk fiber；
C：It is acrylyl oxy-ethyl-benzyl of 0.09mol/L by the polyamino grafting silk fiber of step B and molar concentration The aqueous isopropanol of base-diethylammonium chloride presses 1:After 59 bath raio mixing, 4h is reacted at 60 DEG C, obtains quaternization silk Fiber；
D：The PBS for being 7.3 by the quaternization silk fiber of step C and water cape jasmine extract Geniposide and pH value is slow Reaction kettle is added in fliud flushing, is heated to 49 DEG C after mixing and maintains 1.2h, filters, with purified water wash off product, is crosslinked Quaternization silk fiber；
E：The crosslinking quaternization silk fiber of step D is immersed in the hypobromous acid by molar concentration for 0.55%mol/L Potassium solution and molar concentration are 20min in the mixture of the postassium hypochlorite solution composition of 0.4%mol/L, then are cleaned with purified water After dry, obtain quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers；
The dosage of the water cape jasmine extract Geniposide is the 0.15% of quaternization silk fiber quality；
The dosage of the mixture of the potassium hypobromite and postassium hypochlorite is crosslinking quaternization silk fiber quality 0.05%；
The preparation method of the polyamino Polymer Solution includes the following steps：
F：By methyl acrylate and methanol according to 1:6.2 molar ratio is uniformly mixed, and obtains mixed solution；
G：Methyl acrylate and triethylene tetramine are pressed 5：After 6 molar ratio mixing under 3 DEG C of nitrogen atmosphere, side stirring While methyl acrylate and mixed solution are added dropwise in triethylene tetramine, continue to be stirred to react at room temperature after being added dropwise 28h, is then heated to 60 DEG C and is stirred to react 5h, and the methanol in low-temperature evaporation hybrid reaction system obtains faint yellow viscous fluid；
H：The faint yellow viscous fluid of step G and ethyl alcohol are pressed 1:10 volume ratio be mixed it is even after, obtain polyamino macromolecule Solution；
The molar ratio of the methyl acrylate of the step F and the methyl acrylate of step G is 1：2.
The application process of the quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers is：It uses it for preparing sterile hand Art takes and aseptic operation cap.
Embodiment 6
The preparation method of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers of the present invention, includes the following steps：
A：The composite fibre of tree cotton fiber and cotton fiber is pressed 1:68 bath raio is soaked into the second two that mass fraction is 76% In amine aqueous solution, heating water bath uses alternately washing composite fibre 3 times of ethyl alcohol and purified water after heating 4.3h, is mixing to 41 DEG C 1 is pressed in fiber:Epoxychloropropane is added in 4.3 bath raio, and presses 1:It is 0.011mol/L's that molar concentration, which is added, in 7.2 bath raio Sodium hydroxide solution is stirred to react 10h at 32 DEG C, then with water washing is purified 2 times, is put into baking oven drying at 63 DEG C, obtains The epocel of activation；
B：The epocel of step A and polyamino Polymer Solution are obtained into polyamino grafting after being grafted etherification reaction Fiber；
By 1：It is 5% sodium carbonate liquor that mass fraction, which is added, in 10 solid-liquid ratio in 3,3 '-dithio dipropyl dimethyl phthalates, By 1 after stirring evenly：Polyamino graft fibres are added in 50 bath raio, and 36h is stirred to react at 20 DEG C, filter, with ethyl alcohol and pure Change water and replace cleaning product, obtains the more two thio fibers of polyamino；
By 1:50 bath raio by two thio fibers more than polyamino be 7% with volume fraction acetum after mixing, At 40 DEG C while stirring be added with polyamino more than two thio fiber homogenous quantities zinc powder carry out reduction reaction, take out after reaction Filter, with purified water wash off product, obtains the more sulfydryl graft fibres of polyamino；
C：It is the methacryloxypropyl second of 0.04mol/L by the more sulfydryl graft fibres of the polyamino of step B and molar concentration Base-trimethyl ammonia chloride ammonium salt solution presses 1:After 64 bath raio mixing, 4.2h is reacted at 61 DEG C, obtains quaternization fiber；
D：The PBS buffer solution for being 7.4 by the quaternization fiber of step C and water cape jasmine extract Geniposide and pH value Reaction kettle is added, is heated to 50 DEG C after mixing and maintains 1.4h, filters, with purified water wash off product, obtains crosslinking quaternary ammonium Salinization fiber；
E：The crosslinking quaternization fiber of step D is immersed in the postassium hypochlorite solution by molar concentration for 0.6%mol/L 18min in the mixture formed for the liquor natrii hypochloritis of 0.5%mol/L with molar concentration, then dried after being cleaned with purified water, Obtain quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers；
The dosage of the water cape jasmine extract Geniposide is the 0.5% of quaternization fiber quality；
The dosage of the mixture of the sodium hypochlorite and postassium hypochlorite is be crosslinked quaternization fiber quality 0.06%；
The preparation method such as embodiment 1 of polyamino Polymer Solution and polyamino polyamino graft fibres described in step B It is described；
The application process of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers is：It is immersed in fluid food, i.e., It can reach and sterilize to fluid food in normal temperature and pressure.
Embodiment 7
The preparation method of the quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers of the present invention, includes the following steps：
A：Tree cotton fiber is pressed 1:70 bath raio is soaked into the ethylenediamine solution that mass fraction is 77%, and heating water bath is extremely 42 DEG C, alternately washing tree cotton fiber 2 times of ethyl alcohol and purified water are used after heating 4.5h, 1 is pressed in tree cotton fiber:4.5 bath raio Epoxychloropropane is added, and presses 1:The sodium hydroxide solution that molar concentration is 0.012mol/L is added in 7.4 bath raio, at 28 DEG C Under be stirred to react 10.4h, then with purifying water washing 3 times, be put into that baking oven is dry at 64 DEG C, the epoxy tree cotton activated is fine Dimension；
B：The asphalt mixtures modified by epoxy resin cotton fiber of step A and polyamino Polymer Solution are obtained into polyamino after being grafted etherification reaction It is grafted tree cotton fiber；
By 1.2：It is that 6% sodium carbonate is molten that mass fraction, which is added, in 11 solid-liquid ratio in 3,3 '-dithio dipropyl dimethyl phthalates Liquid, by 1 after stirring evenly：53 bath raio is added polyamino and is grafted tree cotton fiber, and 42h is stirred to react at 22 DEG C, filters, uses second Alcohol and purified water replace cleaning product, obtain the more two thio tree cotton fibers of polyamino；
By 1:Two thio tree cotton fibers more than polyamino are uniformly mixed by 52 bath raio with the acetum that volume fraction is 8% Afterwards, be added while stirring at 42 DEG C the zinc powder that quality is two 1.1 times of thio tree cotton fiber qualities more than polyamino restore it is anti- It answers, filters after reaction, with purified water wash off product, obtain the more sulfydryl grafting tree cotton fibers of polyamino；
C：It is the acryloyl-oxy second of 0.05mol/L by the more sulfydryl grafting tree cotton fibers of the polyamino of step B and molar concentration The aqueous isopropanol of base-trimethyl ammonium chloride presses 1:After 66 bath raio mixing, 4.5h is reacted at 62 DEG C, obtains quaternization tree Cotton fiber；
D：Reaction is added in the PBS buffer solution that the quaternization tree cotton fiber and glutaraldehyde and pH value of step C are 7.5 Kettle is heated to 48 DEG C and maintains 1.6h after mixing, filtering, with purified water wash off product, obtains crosslinking quaternization tree cotton Fiber；
E：The crosslinking quaternization tree cotton fiber of step D is immersed in the postassium hypochlorite that molar concentration is 0.65%mol/L 16min in solution, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers；
The dosage of the glutaraldehyde is the 1.5% of quaternization tree cotton fiber quality；
The dosage of the sodium hypochlorite is be crosslinked quaternization tree cotton fiber quality 0.07%；
The preparation method such as implementation of polyamino Polymer Solution and polyamino polyamino grafting tree cotton fiber described in step B Described in example 2；
The application process of the quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers is：It is immersed in fluid food In, you can reach and sterilizes to fluid food in normal temperature and pressure.
Embodiment 8
The preparation method of the quaternary ammonium salt-N- halogen amine type nano-antibacterial flaxen fibers of the present invention, includes the following steps：
A：Flaxen fiber is pressed 1:71 bath raio is soaked into the ethylenediamine solution that mass fraction is 78%, heating water bath to 43 DEG C, alternately washing flaxen fiber 3 times of ethyl alcohol and purified water are used after heating 4.6h, 1 is pressed in flaxen fiber:Ring is added in 4.6 bath raio Oxygen chloropropane, and press 1:The sodium hydroxide solution that molar concentration is 0.013mol/L is added in 7.7 bath raio, is stirred at 29 DEG C 10.8h is reacted, then with water washing is purified 2 times, is put into baking oven drying, the epoxy flaxen fiber activated at 65 DEG C；
B：The epoxy bamboo fibre of step A is obtained polyamino with polyamino Polymer Solution after being grafted etherification reaction to connect Branch flaxen fiber；
By 1.3：It is 7% sodium carbonate that mass fraction, which is added, in 12.5 solid-liquid ratio in 3,3 '-dithio dipropyl dimethyl phthalates Solution, by 1 after stirring evenly：Polyamino grafted fibrilia is added in 60 bath raio, and 48h is stirred to react at 25 DEG C, filters, uses second Alcohol and purified water replace cleaning product, obtain the more two thio flaxen fibers of polyamino；
By 1:Two thio flaxen fibers more than polyamino are uniformly mixed by 55 bath raio with the acetum that volume fraction is 9% Afterwards, be added while stirring at 46 DEG C quality be polyamino more than two 1.2 times of thio flaxen fiber quality zinc powder carry out reduction reaction, It filters after reaction, with purified water wash off product, obtains the more sulfydryl grafted fibrilias of polyamino；
C：It is the acrylyl oxy-ethyl-of 0.06mol/L by the more sulfydryl grafted fibrilias of the polyamino of step B and molar concentration The aqueous isopropanol of trimethyl ammonium chloride presses 1:After 69 bath raio mixing, 4.6h is reacted at 63 DEG C, it is fine to obtain quaternization fiber crops Dimension；
D：Reaction kettle is added in the PBS buffer solution that the quaternization flaxen fiber and glutaraldehyde and pH value of step C are 7.6, It is heated to 49 DEG C after mixing and maintains 1.8h, filters, with purified water wash off product, obtains crosslinking quaternization flaxen fiber；
E：The crosslinking quaternization flaxen fiber of step D is immersed in the potassium hypobromite solution that molar concentration is 0.7%mol/L Middle 14min, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type nano-antibacterial flaxen fibers；
The dosage of the glutaraldehyde is the 3.5% of quaternization flaxen fiber quality；
The dosage of the potassium hypobromite is be crosslinked quaternization flaxen fiber quality 0.08%；
Polyamino Polymer Solution and the preparation method of polyamino grafted fibrilia described in step B is as described in Example 3；
The application process of the quaternary ammonium salt-N- halogen amine type nano-antibacterial flaxen fibers is：Place it in low-voltage direct container In, so that fluid food is flowed through the container, you can to reach and sterilize to fluid food in normal temperature and pressure.
Embodiment 9
The preparation method of the quaternary ammonium salt-N- halogen amine type nano antibiotic cotton fibers of the present invention, includes the following steps：
A：Cotton fiber is pressed 1:73 bath raio is soaked into the ethylenediamine solution that mass fraction is 79%, heating water bath to 44 DEG C, alternately washing cotton fiber 3 times of ethyl alcohol and purified water are used after heating 4.8h, 1 is pressed in cotton fiber:Ring is added in 4.8 bath raio Oxygen chloropropane, and press 1:The sodium hydroxide solution that molar concentration is 0.014mol/L is added in 7.8 bath raio, is stirred at 30 DEG C 11.5h is reacted, then with water washing is purified 1 time, is put into baking oven drying, the epoxy cotton fiber activated at 60 DEG C；
B：The epoxy cotton fiber of step A is obtained polyamino with polyamino Polymer Solution after being grafted etherification reaction to connect Branch cotton fiber；
By 1.4：It is that 9% sodium carbonate is molten that mass fraction, which is added, in 15 solid-liquid ratio in 3,3 '-dithio dipropyl dimethyl phthalates Liquid, by 1 after stirring evenly：Polyamino crafted cotton fibers are added in 65 bath raio, and 54h is stirred to react at 28 DEG C, filter, use ethyl alcohol Replace cleaning product with purified water, obtains the more two thio cotton fibers of polyamino；
By 1:Two thio cotton fibers more than polyamino are uniformly mixed by 57 bath raio with the acetum that volume fraction is 10% Afterwards, be added while stirring at 48 DEG C quality be polyamino more than 1.4 times of two thio cotton quality zinc powder carry out reduction reaction, It filters after reaction, with purified water wash off product, obtains the more sulfydryl crafted cotton fibers of polyamino；
C：It is the two acryloyl-oxy second of 0.08mol/L by the more sulfydryl crafted cotton fibers of the polyamino of step B and molar concentration The aqueous isopropanol of base-benzyl-methyl ammonium chloride presses 1:After 72 bath raio mixing, 4.8h is reacted at 64 DEG C, obtains quaternary ammonium salt Change cotton fiber；
D：Reaction kettle is added in the PBS buffer solution that the quaternization cotton fiber and glutaraldehyde and pH value of step C are 7.7, It is heated to 50 DEG C after mixing and maintains 1.9h, filters, with purified water wash off product, obtains crosslinking quaternization cotton fiber；
E：The crosslinking quaternization cotton fiber of step D is immersed in the liquor natrii hypochloritis that molar concentration is 0.5%mol/L Middle 12min, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type nano antibiotic cotton fibers；
The dosage of the glutaraldehyde is the 4% of quaternization cotton quality；
The dosage of the sodium hypochlorite is be crosslinked quaternization cotton quality 0.09%；
The preparation method such as embodiment of polyamino Polymer Solution and polyamino polyamino crafted cotton fibers described in step B Described in 4；
The application process of the quaternary ammonium salt-N- halogen amine type nano antibiotic cotton fibers is：Place it in low-voltage direct container In, so that fluid food is flowed through the container, you can to reach and sterilize to fluid food in normal temperature and pressure.
Embodiment 10
The preparation method of the quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers of the present invention, includes the following steps：
A：Silk fiber is pressed 1:75 bath raio is soaked into the ethylenediamine solution that mass fraction is 80%, and heating water bath is extremely 45 DEG C, alternately washing silk fiber 3 times of ethyl alcohol and purified water are used after heating 5h, 1 is pressed in silk fiber:5 bath raio is added Epoxychloropropane, and press 1:The sodium hydroxide solution that molar concentration is 0.015mol/L is added in 8 bath raio, is stirred at 30 DEG C 12h is reacted, then with water washing is purified 2 times, is put into baking oven drying, the epoxy silk fiber activated at 63 DEG C；
B：The epoxy silk fiber of step A and polyamino Polymer Solution are obtained into polyamino after being grafted etherification reaction Grafting silk fiber；
By 1.5：It is that 10% sodium carbonate is molten that mass fraction, which is added, in 14 solid-liquid ratio in 3,3 '-dithio dipropyl dimethyl phthalates Liquid, by 1 after stirring evenly：Polyamino grafting silk fiber is added in 70 bath raio, and 60h is stirred to react at 30 DEG C, filters, uses second Alcohol and purified water replace cleaning product, obtain the more two thio silk fibers of polyamino；
By 1:60 bath raio mixes two thio silk fibers more than polyamino with the acetum that volume fraction is 12% After even, it is that the zinc powder of two 1.5 times of thio silk fiber quality more than polyamino is restored that quality is added while stirring at 50 DEG C Reaction, filters, with purified water wash off product, obtains the more sulfydryl grafting silk fibers of polyamino after reaction；
C：It is the 2,3- epoxies third of 0.09mol/L by the more sulfydryl grafting silk fibers of the polyamino of step B and molar concentration The aqueous isopropanol of base trimethyl ammonium chloride presses 1:After 75 bath raio mixing, 5h is reacted at 65 DEG C, obtains quaternization silk Fiber；
D：The PBS for being 7.8 by the quaternization silk fiber of step C and water cape jasmine extract Geniposide and pH value is slow Reaction kettle is added in fliud flushing, is heated to 50 DEG C after mixing and maintains 2h, filters, and with purified water wash off product, obtains crosslinking season Salified silk fiber；
E：It is molten that the crosslinking quaternization silk fiber of step C is immersed in the sodium hypobromite that molar concentration is 0.6%mol/L 12min in liquid, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers；
The dosage of the water cape jasmine extract Geniposide is the 5% of quaternization silk fiber quality；
The dosage of the sodium hypobromite is be crosslinked quaternization silk fiber quality 0.1%；
The preparation method such as implementation of polyamino Polymer Solution and polyamino polyamino grafting silk fiber described in step B Described in example 5；
The application process of the quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers is：Place it in low-pressure direct fluid capacitance In device, fluid food is set to flow through the container, you can to reach and sterilize to fluid food in normal temperature and pressure.
The structural analysis of antiseptic nano-fiber
1 infrared spectrum analysis
By the untreated tree cotton fiber of the embodiment of the present invention 2, by genipin cross-linked polyamino grafting tree cotton fiber with And after quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers are dried in vacuo respectively, it is ground into powder, using 100 Fu of Spectrum In leaf infrared spectrometer (PerkinElmer companies, USA) powder method survey infrared spectrum (FT-IR).The result is shown in Figure 1.Curve in figure A is untreated tree cotton fiber；Curve B is that the polyamino by genipin cross-linked is grafted tree cotton fiber；Curve C is quaternary ammonium salt-N- Halogen amine type nano-antibacterial tree cotton fiber.
It is shown by Fig. 1 infrared spectrums, compared with untreated tree cotton (A), polyamino graft fibres that genipin cross-linked is crossed (B) and all there is the absorption peak of N-H keys and C-N keys in quaternary ammonium salt-N- halogen amine type nano-antibacterial tree cotton fibers (C).N-H keys stretch Vibration is in 3454~387cm-1, primary amine is bimodal, and secondary amine is unimodal, in 1190-1220cm-1Left and right has gone out the flexible of C-N keys and has shaken Dynamic peak.Especially (B), (C) are in 1640-1716cm-1There is carbonylic stretching vibration peak in place, illustrates occur amido bond in product.It is red External spectrum analysis shows, on fiber with corresponding quaternary ammonium salt functional group absorption peak and N- halogen amine inhale peak.By simple under room temperature It singly bleaches, so that it may to obtain the quaternary ammonium salt-N- halogen for many advantages, such as safe and non-toxic, high-efficiency broad spectrum, effect are lasting, of low cost Amine compound nano-fiber material.
2 scanning electron microscope analysis
It is fine to the untreated tree cotton fiber of the embodiment of the present invention 2 and quaternary ammonium salt-N- halogen amine type nano-antibacterials tree cotton respectively Dimension is scanned Electronic Speculum test, as a result sees Fig. 2.
As shown in Figure 2, the smooth fiber in untreated tree cotton surface (C in Fig. 2) becomes flat, coarse (D in Fig. 2).It is fine Dimension table appears in a large amount of nanometer grafted particles, and size is from several nanometers to several tens of nanometers.The scanned electron microscope analysis of product can be seen that The smooth fiber surface in original surface is all grafted the nanosizing polyamines base for having gone up different-grain diameter or more sulfydryl branches or protrusion.Fiber The problem of becoming for surface is coarse, and very strong cohesive force has been pulled with pulling, and it is smooth to solve fiber surface, obvolvent force difference improves Fiber spinnability and raising tensile strength.
The antibacterial functions of antiseptic nano-fiber are studied
1 test objective
In order to examine the present invention antiseptic nano-fiber anti-microbial property, select staphylococcus aureus as indicator bacteria, Using bacterial suspension method, the antibacterial functions of the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers of the present invention are detected.
2 test methods
It prepares staphylococcus aureus suspension and is divided into three parts, be added separately in three test tubes, wherein test tube A makees blank pair According to untreated cotton fiber is added in test tube B, and the quaternary ammonium salt-N- halogen amine type that the embodiment of the present invention 4 provides, which is added, in test tube C receives Nano antibacterial cotton fiber.Its OD600 is surveyed respectively in different incubation time points.As a result see Fig. 3.
As seen from Figure 3, the culture solution of test tube A is muddy, there is bacterial reproduction；It is untreated cotton fiber in test tube B It is muddy to be immersed in staphylococcus aureus suspension, illustrates there is bacterial reproduction；Test tube C is the quaternary ammonium salt-that the embodiment of the present invention 4 provides N- halogen amine type nano antibiotic cotton fibers, solution clarification, bacterium cannot survive.Quaternary ammonium salt-N- halogen the amine that the embodiment of the present invention 4 provides Type nano antibiotic cotton fiber contains double officials groups fiber and greatly accelerates sterilizing since N- halogen amine is release type bactericidal agent active bromine Speed.So sterilization time shortens to or so half an hour by monofunctional 6-8 hours, golden yellow grape is replaced with Escherichia coli Coccus carries out similar experiment, the results showed that and difunctional nanosizing fiber also can quickly kill Escherichia coli in 10-30min, Illustrate that the anti-bacterial fibre of the present invention has significant antibacterial action to gram-positive bacteria and Gram-negative bacteria.
Antiseptic nano-fiber toxicity and Physico-chemical tests
1 test objective
The toxic side effect of the antiseptic nano-fiber of the present invention is tested, and in use, whether there is or not poisonous and harmful substances Multifilament moves in liquid food.
1.1 toxicitys detect
Using the quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers of the embodiment of the present invention 5 as test sample, using migration Method carries out acute toxicity detection, and 10% ethyl alcohol, 4% acetic acid are that solvent leaches quaternary ammonium salt-N- halogen amine type nano-antibacterial silk fibers Extracting solution, respectively at 100 DEG C or reflux under 4 hours, 50 DEG C 10 days, 20 DEG C 10 days migration extraction three times, and close extracting solution concentration, Constant volume is to 1/3 volume, with reference to GB15193.3-2014《National food safety standard acute oral toxicity test》In limitation method, It is the death condition that observation mouse after mouse 0.4ml/10g gavages is given by test solution with this liquid, to obtain the LD of the sample50Limit Value, test result are shown in Table 1.
1 quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers of table migrate experiment condition and result
1.2 Physico-chemical tests
Quaternary ammonium salt-N- halogen amine type nano-antibacterial the bamboo fibres provided using the embodiment of the present invention 7 carry out three as test sample to it Item detection：(1) heavy metal analysis；(2) antiseptic detection is commonly used；(3) preservative detects in dairy products.Test result is shown in Table 2.
2 quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber Physico-chemical tests results of table
By Tables 1 and 2 it is found that the antiseptic nano-fiber of the present invention has no toxic side effect, it to be used for the quaternary ammonium salt-N- of food antibacterial Halogen amine type antiseptic nano-fiber and the equal heavy metal free element of intermediate product, no general chemical and biological preservative, are a kind of safety Liquid food antibacterial fiber material, be also widely applied to medical and hygiene article, food fresh-keeping, public health, at Water warfare The fields such as reason, are with a wide range of applications.

Claims (10)

1. a kind of preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber, which is characterized in that include the following steps：
A：Natural fiber is carried out using epoxychloropropane and sodium hydroxide solution after natural fiber is impregnated with ethylenediamine solution Activating pretreatment obtains epocel；
B：Epocel described in step A is subjected to etherificate graft reaction with polyamino Polymer Solution, obtains polyamino grafting Fiber；Or by polyamino graft fibres and 3, the more two thio fibers of polyamino are obtained by the reaction in 3 '-dithio dipropyl dimethyl phthalates, then Two thio fibers more than polyamino are restored using zinc powder, obtain the more sulfydryl graft fibres of polyamino；
C：It is 0.04-0.10mol/L by the more sulfydryl graft fibres of the polyamino graft fibres or polyamino of step B and molar concentration Quaternary ammonium salt aqueous isopropanol at 55-65 DEG C hybrid reaction 3-5h, obtain quaternization fiber；
D：Reaction kettle is added in the PBS buffer solution that the quaternization fiber and crosslinking agent and pH value of step C are 7.0-7.8, is mixed It is heated to 45-50 DEG C after closing uniformly and maintains 1-3h, filter, with purified water wash off product, obtains crosslinking quaternization fiber；
E：The crosslinking quaternization fiber of step D is impregnated in the hypohalite solution that molar concentration is 0.3-0.7mol/L 10-30min, then dried after being cleaned with purified water, obtain quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers.
2. the preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber according to claim 1, it is characterised in that：Institute The natural fiber stated is the mixed of the one or more in tree cotton fiber, bamboo fibre, flaxen fiber, cotton fiber or silk fiber It closes.
3. the preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber according to claim 1, which is characterized in that institute State step A to natural fiber carry out pre-activate processing the specific steps are：Natural fiber is pressed 1:The bath raio of 55-75 is soaked into matter It measures in the ethylenediamine solution that score is 70-80%, heating water bath is handed over after heating 3-5h using ethyl alcohol and purified water to 35-45 DEG C For natural fiber is washed 2-3 times, in the hydrogen that epoxychloropropane is added in natural fiber and molar concentration is 0.005-0.015mol/L Sodium hydroxide solution is stirred to react 8-12h at 28-32 DEG C, then with water washing is purified 1-3 times, is put into baking oven and is done at 55-65 DEG C Epocel that is dry, being activated；
The bath raio of the natural fiber and epoxychloropropane is 1：3-5；The bath raio of the natural fiber and sodium hydroxide solution is 1：6-8.
4. the preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber according to claim 1, which is characterized in that institute State the epocel of step B and polyamino Polymer Solution carry out etherificate graft reaction the specific steps are：
Epocel and volume fraction are pressed 1 for the polyamino Polymer Solution of 8-12%:After the bath raio mixing of 45-55, heating To 65-75 DEG C, it is stirred to react 3.5-5h, then uses ethyl alcohol and purified water to replace washing reaction product, then dried at 45-60 DEG C It is dry, obtain polyamino graft fibres；
The preparation method of the polyamino Polymer Solution includes the following steps：
F：By methyl acrylate and methanol according to 1:The molar ratio of 3.8-6.2 is uniformly mixed, and obtains mixed solution；
G：Methyl acrylate and enamine are pressed into 3-5：After the molar ratio mixing of 4-6 under 0-3 DEG C of nitrogen atmosphere, exist while stirring Methyl acrylate and mixed solution are added dropwise in enamine, continues to be stirred to react 20-28h at room temperature after being added dropwise, then It is heated to 50-60 DEG C and is stirred to react 3-5h, the methanol in low-temperature evaporation hybrid reaction system obtains faint yellow viscous fluid；
H：The faint yellow viscous fluid of step G and ethyl alcohol are pressed 1:The volume ratio of 8-10 be mixed it is even after, it is molten to obtain polyamino macromolecule Liquid；
The enamine is triethylene tetramine, four ethylene triamines or five ethylene tetramines；
The molar ratio of the methyl acrylate of the step F and the methyl acrylate of step G is 1：1.2-2.
5. the preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber according to claim 1, which is characterized in that institute The polyamino graft fibres and 3 of step B are stated, the more two thio fibers of polyamino are obtained by the reaction in 3 '-dithio dipropyl dimethyl phthalates, then Two thio fibers more than polyamino are restored using zinc powder, obtain the more sulfydryl graft fibres of polyamino the specific steps are：
I：By 1-1.5：It is 5-10% carbon that mass fraction, which is added, in the solid-liquid ratio of 10-15 in 3,3 '-dithio dipropyl dimethyl phthalates Acid sodium solution, by 1 after stirring evenly：Polyamino graft fibres are added in the bath raio of 50-70, and 36- is stirred to react at 20-30 DEG C 60h is filtered, and replaces cleaning product with ethyl alcohol and purified water, obtains the more two thio fibers of polyamino；
J：By 1:The bath raio of 50-60 is by two thio fibers more than the polyamino of step I and acetum that volume fraction is 7-12% After mixing, zinc powder is added while stirring at 40-50 DEG C and carries out reduction reaction, filters after reaction, is washed with purifying Net products obtain the more sulfydryl graft fibres of polyamino；
The mass ratio of the more two thio fibers of step J polyaminos and zinc powder is 1:1-1.5.
6. the preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber according to claim 1, it is characterised in that：Step Quaternary ammonium salt described in rapid C is 2,3- epoxypropyltrimethylchloride chlorides, methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride, third Alkene acyloxyethyl-benzyl-dimethyl ammonium chloride, methylacryoyloxyethyl-benzyl-diethylammonium chloride, acrylyl oxy-ethyl- Benzyl-diethylammonium chloride, methylacryoyloxyethyl-trimethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl ammonium chloride, two Any one in acrylyl oxy-ethyl-benzyl-methyl ammonium chloride.
7. the preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber according to claim 1, it is characterised in that：Step Crosslinking agent described in rapid D is water cape jasmine extract Geniposide or glutaraldehyde；The dosage of the crosslinking agent is quaternization cellulosic The 0.01-5% of amount.
8. the preparation method of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber according to claim 1, it is characterised in that：Step Hypohalite solution described in rapid E is in liquor natrii hypochloritis, postassium hypochlorite solution, sodium hypobromite solution, potassium hypobromite solution One or more kinds of mixtures；The dosage of the hypohalite is to be crosslinked the 0.01- of quaternization fiber quality 0.1%.
9. by claim 1-8 any one of them quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers, it is characterised in that：In food Purposes in terms of packaging, food-pasteurization, medical instrument, public health, water purification system.
10. by the quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers described in claim 9, it is characterised in that：
Quaternary ammonium salt-N- halogen amine type the antiseptic nano-fibers are in the application process of food-pasteurization purposes：By quaternary ammonium salt-N- halogen amine Type antiseptic nano-fiber is immersed in liquid food, or quaternary ammonium salt-N- halogen amine type antiseptic nano-fibers are placed in low-pressure direct fluid capacitance In device, liquid food is set to flow through the container, you can to reach and sterilize to fluid food in normal temperature and pressure；
Quaternary ammonium salt-N- halogen amine type the antiseptic nano-fibers are in the application process of medical instrument purposes：By the quaternary ammonium salt- N- halogen amine type antiseptic nano-fibers are used to prepare the medical and hygiene articles such as cotton swab, cotton balls, gauze, mask and operation clothing.
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