CN104497338A - Halamine antibacterial nanometer cellulose membrane and preparation method thereof - Google Patents

Halamine antibacterial nanometer cellulose membrane and preparation method thereof Download PDF

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Publication number
CN104497338A
CN104497338A CN201410769240.8A CN201410769240A CN104497338A CN 104497338 A CN104497338 A CN 104497338A CN 201410769240 A CN201410769240 A CN 201410769240A CN 104497338 A CN104497338 A CN 104497338A
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China
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cellulose film
preparation
halamine
bacteria cellulose
germicide
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CN201410769240.8A
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Chinese (zh)
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姚琛
周宾
王怡红
温智理
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Southeast University
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Southeast University
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Abstract

The invention relates to a halamine antibacterial nanometer cellulose membrane and a preparation method thereof. The preparation method comprises the following steps: by taking a phosphorylated bacterial cellulose membrane as a base membrane and adopting a chemical oxidative polymerization method, initiating polymerization of a heterocyclic N-halamine antibacterial agent monomer, thereby obtaining a high polymer halamine antibacterial agent composite nanometer cellulose membrane by virtue of a halogenating reaction. The method disclosed by the invention is mild in reaction conditions and simple in process, and the halamine antibacterial nanometer cellulose membrane provided by the invention has the characteristics of high antibacterial performance, renewability, good air permeability, high tensile strength, high elasticity modulus and the like and has wide application prospects in the fields of filtering separation and biomedicines.

Description

A kind of halogen amine antimicrobial nano-cellulose film and preparation method thereof
Technical field
The present invention relates to a kind of halogen amine antimicrobial nano-cellulose film and preparation method thereof, belong to the association area such as filtering separation, bio-medical material.
Background technology
Halamine antibacterial agent receives much attention because of its exclusive renewable performance and excellent broad spectrum.Halogen amine antiseptic-germicide is the organic compound that a class contains nitrogen halogen (N-X) functional group.Owing to there is oxidisability by the halogen atom be covalently bonded on nitrogen-atoms with positive charge.According to their chemical structure, halogen amine compound can be divided into amine halogen amine, amides halogen amine, sub-amides halogen amine three class.According to the literature, amides halogen amine reactivity is the highest, and the amine stabilized property of acid imide halogen is then best.These halogen amine compound are all that oxidation state halogen atom is consumed and causes N-X key be transformed into N-H key and lose activity in antibacterial process, but after the simple rinsing of sodium hypochlorite solution (effective constituent is hypochlorite) that over-richness is very rare, N-H key is oxidized to again N-X key and regains sterilizing function (recyclability).Abundant experimental results shows, halogen amine antimicrobial excellent performance wide spectrum, can kill the common germs such as most staphylococcus, intestinal bacteria, Pseudomonas aeruginosa in a short period of time, even also have killing action to some virus.
But be the important factor affecting halogen amine antimicrobial efficiency with the contact area of bacterium, the anti-microbial property of halogen amine is strongly depend on its surface-area and duration of contact.The carrier of cotton fibre, polyacrylonitrile fibre membrane Chang Zuowei Halamine antibacterial agent.Chinese patent CN103276596A discloses a kind of preparation method of quaternized halogen amine antibiotic cotton fiber, is grafted on cotton, obtains antibacterial cotton cloth by quaternized, halogenation by the haloalkyl silane after hydrolysis.Chinese patent CN102877288A is hydrolyzed by polyacrylonitrile fibre, Surface Creation amide group, imide etc., gives fibre antibacterial through halogenation.Except with except matrix surface radical reaction, also can increase the density of halogen amine groups in material using halogen amine polymer as grafting antiseptic-germicide, improve its anti-microbial property.Chinese patent CN103524652A discloses a kind of halogen amine polymer antiseptic-germicide containing quaternary ammonium salt group and preparation method thereof, by containing quaternary ammonium salt and nitrogen halogen bifunctional monomer polymerization, as the antibiotic finishing solution of textiles.Chinese patent CN103554367A discloses the preparation method of halogen amine multipolymer antiseptic-germicide, copolymerization is carried out with double bond containing maleic anhydride modified beta-cyclodextrin with containing double bond halogen amine monomers, compound, electrostatic spinning are carried out to multipolymer, obtains antibacterial nano fiber material.
Nanometer bacteria cellulose is a kind of natural biological superpolymer synthesized by fermentable, there is biological activity, biodegradability, biological fitness, and the physics of many uniquenesses such as high-crystallinity, high retentiveness, high-tensile and Young's modulus, chemistry and mechanical property.Especially, the superfine nano fibrous texture of bacteria cellulose is always by investigator is paid close attention to.Therefore, based on a kind of halogen amine nano fibrous membrane with high anti-microbial property of nanometer bacteria cellulose film exploitation, all have a wide range of applications in the field such as filtering separation, biomedicine etc.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of halogen amine antimicrobial nano-cellulose film and preparation method thereof.Nano-cellulose film prepared by the method has high anti-microbial property, good ventilation property, high-tensile and Young's modulus.
Technical scheme: with phosphorylation bacteria cellulose film for basement membrane, adopts chemical oxidative polymerization method, obtains the nano fibrous membrane of surface recombination polymer heterocyclic N-halamine amine antiseptic-germicide.
Wherein, basement membrane is phosphorylation bacteria cellulose film, by one or more in acetobacter xylinum, root nodule bacterium, glucose bacillus, product acetobacter, acetify bacillus, Acetobacter pasteurianus, Agrobacterium, sarcina, pseudomonas, Alcaligenes or vinelandii after fermentation, being separated alkalization purification, obtained through urea seeding phosphorylation.
Wherein, heterocyclic N-halamine amine antiseptic-germicide monomer is one or more of glycolylurea, malonyl urea, 2-imidazolidone, 2-thioxo-4-thiazolidinone and derivative thereof.
The preparation method of described halogen amine antimicrobial nano-cellulose film, step is as follows:
1) bacteria cellulose film obtained fermenting extrudes after institute's water content through mechanically compress, immerses in urea-containing DMF solution, dropwise adds phosphoric acid, and mixed solution was 100-150 DEG C of reaction more than 4 hours.React rear deionized water and fully clean phosphorylation bacteria cellulose film, lyophilize;
2) by step 1) in obtained basement membrane to be dipped in concentration be in the heterocycle antiseptic-germicide monomer solution of 0.5 ~ 20g/L, add a certain amount of oxygenant, polyreaction 24-48 hour, clean the monomer solution of surface residual with deionized water;
3) subsequently film being dipped in mass percent concentration is 5-20% chlorine bleach liquor 6-12 hour, with the nanometer bacteria cellulose film namely obtaining surface recombination polymer heterocyclic N-halamine amine antiseptic-germicide after washed with de-ionized water.
4) the antimicrobial nano bacteria cellulose film after using only need be dipped in mass percent concentration for 5-20% chlorine bleach liquor 6-12 hour, again with namely renewable after washed with de-ionized water.
Beneficial effect: compared to prior art, the present invention (1) with phosphorylation bacteria cellulose film for basement membrane, bacteria cellulose film perviousness after phosphatizing treatment significantly improves, and is conducive to N-halamine antiseptic-germicide monomer molecule diffusion inner to bacteria cellulose film.Antibacterial group not only fully covers the surface of bacteria cellulose film, is also evenly distributed on the inside of film, effectively increases the contact of antibacterial group and bacterium.(2) main component of bacteria cellulose film is Mierocrystalline cellulose, containing great amount of hydroxy group, easily makes N-halamine antiseptic-germicide monomer molecule be evenly distributed on fiber surface with hydrogen bond action, makes follow-up chemical oxidising polymerisation have the feature of template polymerization.(3) polymer heterocyclic N-halamine amine antiseptic-germicide is compared with small molecules Halamine antibacterial agent, has the advantages such as antibacterial group is more, more stable.(4) chemical oxidising polymerisation adopted is simple to operate, avoids using hazardous solvent, meets environmental requirement, and obtained antibacterial nano fiber element membrane structure is even, and performance is given prominence to.The inventive method is suitable for industrialization and produces.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
To ferment to obtain bacteria cellulose film through acetobacter xylinum, extrude after institute's water content, immerse in the DMF solution containing 20% urea, dropwise add phosphoric acid through mechanically compress, mixed solution was 130 DEG C of reactions 4 hours.React rear deionized water and fully clean phosphorylation bacteria cellulose film, lyophilize.Subsequently film being dipped in concentration is in the 1-methyl hydantoin monomer solution of 5g/L, adds oxygenant iron(ic) chloride, polyreaction 24 hours.React complete, clean the monomer solution of surface residual with deionized water.Film is dipped in 10% chlorine bleach liquor 6 hours, with the nanometer bacteria cellulose film namely obtaining surface recombination after washed with de-ionized water and gather 1-methyl hydantoin antiseptic-germicide.
Embodiment 2
Obtain bacteria cellulose film through Agrobacterium fermentation, extrude after institute's water content, immerse in the DMF solution containing 10% urea, dropwise add phosphoric acid through mechanically compress, mixed solution was 110 DEG C of reactions more than 6 hours.React rear deionized water and fully clean phosphorylation bacteria cellulose film, lyophilize.Film being dipped in concentration is in the barbituric acid monomer solution of 10g/L, adds oxygenant ammonium persulphate, polyreaction 24 hours.React complete, clean the monomer solution of surface residual with deionized water.Film is dipped in 10% chlorine bleach liquor 6 hours, with namely obtaining poly-barbituric acid composite Nano bacteria cellulose film after washed with de-ionized water.Adopt spread plate evaluating combined nano-cellulose film to the antibacterial effect of gram positive bacterium streptococcus aureus (S.aureus) and gram negative bacterium intestinal bacteria (E.coli), nano-cellulose film demonstrates excellent antibacterial effect to these two kinds of bacteriums, and half an hour, sterilizing rate was all greater than 99.99%.Poly-barbituric acid composite Nano bacteria cellulose film after using is dipped in 10% chlorine bleach liquor 6 hours again, and after so repeating five circulations, antimicrobial efficiency is still constant.
Embodiment 3
The bacteria cellulose film obtained that fermented by acetobacter xylinum extrudes after institute's water content through mechanically compress, and immerse in the DMF solution containing 20% urea, dropwise add phosphoric acid, mixed solution was 150 DEG C of reactions 4 hours.React rear deionized water and fully clean phosphorylation bacteria cellulose film, lyophilize.Film being dipped in concentration is in the 2-imidazolidone monomer solution of 5g/L, and add oxygenant ammonium persulphate, polyreaction 24 hours, cleans the monomer solution of surface residual with deionized water.Film is dipped in 10% chlorine bleach liquor 6 hours, with the nanometer bacteria cellulose film namely obtaining surface recombination polymer halogen amine antiseptic-germicide after washed with de-ionized water.
Embodiment 4
The bacteria cellulose film obtained that fermented by acetobacter xylinum extrudes after institute's water content through mechanically compress, and immerse in the DMF solution containing 25% urea, dropwise add phosphoric acid, mixed solution was 150 DEG C of reactions 4 hours.React rear deionized water and fully clean phosphorylation bacteria cellulose film, lyophilize.Be dipped in by film in rhodanine that concentration is 20g/L, malonyl urea monomer mixture solution, add hydrogen peroxide, polyreaction 24 hours, cleans the monomer solution of surface residual with deionized water.Film is dipped in 10% chlorine bleach liquor 6 hours, with obtaining high-molecular anti-bacteria nano-cellulose film after washed with de-ionized water.

Claims (6)

1. a halogen amine antimicrobial nano-cellulose film, is characterized in that: this cellulose membrane for basement membrane with phosphorylation bacteria cellulose film, adopts chemical oxidative polymerization method, obtains the nano fibrous membrane of surface recombination polymer heterocyclic N-halamine amine antiseptic-germicide.
2. halogen amine antimicrobial nano-cellulose film according to claim 1, it is characterized in that: described basement membrane is phosphorylation bacteria cellulose film, by one or more in acetobacter xylinum, root nodule bacterium, glucose bacillus, product acetobacter, acetify bacillus, Acetobacter pasteurianus, Agrobacterium, sarcina, pseudomonas, Alcaligenes or vinelandii after fermentation, being separated alkalization purification, obtained through urea seeding phosphorylation.
3. halogen amine antimicrobial nano-cellulose film according to claim 1, is characterized in that: the monomer of heterocyclic N-halamine amine antiseptic-germicide be glycolylurea, malonyl urea, 2-imidazolidone or 2-thioxo-4-thiazolidinone and derivative thereof one or more.
4. a preparation method for halogen amine antimicrobial nano-cellulose film as claimed in claim 1, it is characterized in that, this preparation method comprises the steps:
1) bacteria cellulose film obtained fermenting extrudes after institute's water content through mechanically compress, immerse urea-containing N, in dinethylformamide solution, dropwise add phosphoric acid, mixed solution was 100-150 DEG C of reaction more than 4 hours, react rear deionized water and fully cleaned phosphorylation bacteria cellulose film, lyophilize, obtain basement membrane;
2) by step 1) in obtained basement membrane to be dipped in concentration be in the heterocycle antiseptic-germicide monomer solution of 0.5 ~ 20g/L, add oxygenant, polyreaction 24-48 hour, clean the monomer solution of surface residual with deionized water;
3) film being dipped in mass percent concentration is subsequently 5-20% chlorine bleach liquor 6-12 hour again, with the nanometer bacteria cellulose film namely obtaining surface recombination polymer heterocyclic N-halamine amine antiseptic-germicide after washed with de-ionized water.
5. the preparation method of halogen amine antimicrobial nano-cellulose film according to claim 4, it is characterized in that: described nanometer bacteria cellulose film, only mass percent concentration again need be dipped in for 5-20% chlorine bleach liquor 6-12 hour, with namely renewable after washed with de-ionized water after using.
6. the preparation method of halogen amine antimicrobial nano-cellulose film according to claim 4, is characterized in that: described oxygenant is the one in iron(ic) chloride, ammonium persulphate or hydrogen peroxide.
CN201410769240.8A 2014-12-12 2014-12-12 Halamine antibacterial nanometer cellulose membrane and preparation method thereof Pending CN104497338A (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
KR20160084906A (en) * 2015-01-06 2016-07-15 영남대학교 산학협력단 cellulose filters for water disinfection and preparation method thereof
CN109232953A (en) * 2018-08-08 2019-01-18 西南交通大学 A kind of polyethyleneimine amido chloramines type antibacterial cellulose film, preparation method and application
CN112089685A (en) * 2020-09-18 2020-12-18 江南大学 Preparation method of temperature response type bacterial cellulose antibacterial nanogel
CN112520722A (en) * 2020-12-02 2021-03-19 深圳大学 Titanium dioxide coated biomass charcoal composite anode material and preparation method and application thereof
CN113952489A (en) * 2021-10-27 2022-01-21 湖南恩源生态农业发展有限公司 Sterilizing system for vehicles in farm
CN114214749A (en) * 2021-11-29 2022-03-22 江苏辰安泰生物医药研究院有限公司 Antibacterial halamine derivative modified acrylic fiber and preparation method thereof

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CN102877287A (en) * 2012-10-19 2013-01-16 常州大学 Preparation method of halamine-containing antibacterial cellulose fabric
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CN102219997A (en) * 2011-04-29 2011-10-19 南京理工大学 Method for preparing polypyrrole coated bacterial cellulose nanometer electric-conduction composite material by utilizing bacterial cellulose as template
CN102877287A (en) * 2012-10-19 2013-01-16 常州大学 Preparation method of halamine-containing antibacterial cellulose fabric
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160084906A (en) * 2015-01-06 2016-07-15 영남대학교 산학협력단 cellulose filters for water disinfection and preparation method thereof
KR101701204B1 (en) 2015-01-06 2017-02-02 영남대학교 산학협력단 cellulose filters for water disinfection and preparation method thereof
CN109232953A (en) * 2018-08-08 2019-01-18 西南交通大学 A kind of polyethyleneimine amido chloramines type antibacterial cellulose film, preparation method and application
CN109232953B (en) * 2018-08-08 2020-11-03 西南交通大学 Polyvinimidyl chloramine type antibacterial cellulose membrane, preparation method and application
CN112089685A (en) * 2020-09-18 2020-12-18 江南大学 Preparation method of temperature response type bacterial cellulose antibacterial nanogel
CN112520722A (en) * 2020-12-02 2021-03-19 深圳大学 Titanium dioxide coated biomass charcoal composite anode material and preparation method and application thereof
CN113952489A (en) * 2021-10-27 2022-01-21 湖南恩源生态农业发展有限公司 Sterilizing system for vehicles in farm
CN114214749A (en) * 2021-11-29 2022-03-22 江苏辰安泰生物医药研究院有限公司 Antibacterial halamine derivative modified acrylic fiber and preparation method thereof

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