CN101250815A - Method for manufacturing halogen amine antimicrobial material - Google Patents
Method for manufacturing halogen amine antimicrobial material Download PDFInfo
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- CN101250815A CN101250815A CNA2008100151909A CN200810015190A CN101250815A CN 101250815 A CN101250815 A CN 101250815A CN A2008100151909 A CNA2008100151909 A CN A2008100151909A CN 200810015190 A CN200810015190 A CN 200810015190A CN 101250815 A CN101250815 A CN 101250815A
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- solution
- hydantoin derivative
- preparation
- hydantoin
- halamine
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Abstract
The invention discloses a method for preparing N-halamine antibiotic material, which comprises the following steps: (a) soaking a to-be-treated material in the solution which contains hydantoin derivant or sprinkling/daubing the solution which contains hydantoin derivant on the to-be-treated material to entables the to-be-treated material to adsorb hydantoin derivant, (b) enabling hydantoin derivant to combine on the material by raising temperature, (c) soaking the material after (b) process in the solution which contains active halogen solution or sprinkling/daubing the solution which contains active halogen on the material to make the material activate and be provided with antibiotic activity.
Description
Technical field:
The present invention relates to the preparation of amine (N-halamine) anti-biotic material, belong to field of new.
Background technology:
Anti-biotic material particularly anti-bacterial fibre material has application widely.Use sheet, quilt cover and medical worker's that anti-bacterial fibre makes Work Clothes in hospital, can reduce and infect and the transmission of disease probability, footwear made from antibiotic cotton fiber and socks can prevent that beriberi and pin are smelly.With the handle of public place door, the packing ring of computor-keyboard, toilet is made with anti-biotic material, helps reducing the popular of infectious disease.
Although the multiple product of claiming antibacterial action is arranged in the market, that developed recently gets up, than the anti-biotic material of other classes (as based on nano material, heavy metal, quaternary ammonium salt) that everybody was familiar with unique advantage is arranged based on the N-halmine anti-biotic material of halogen atom antibacterial activity:
(1) can directly kill the various microorganisms (comprising virus) that contact with it with very fast speed.Compare with other anti-biotic material, it has stronger, the sterilizing ability of wide spectrum more;
(2) pathogen does not produce drug resistance to it;
(3) their bactericidal action meeting can be fallen by microbial consumption because of the halogen atom that plays bactericidal action in the molecule or the long period of soaking of ultraviolet long-term irradiation, water is lost, and new halogen atom is added on the material again regenerate but can contain active halogen (as clorox) solution or other simple methods by sprinkling.
(4) in environment, do not discharge harmful substance.
Many researchs about halogen amine antimicrobial polymer aspect have been done by the Worley of U.S. Auburn university professor's seminar.Gang professor Sun who reaches the University of California has done many researchs about halogen amine antimicrobial polymer aspect, and has applied for tens of relevant patents.The Halosource company of the U.S. is that series of products have been developed on the basis with relevant patent: as the Halopure of drinking water treatment aspect, antibacterial fabric and health coating aspect Haloshields, the CoolentXtenderHalofresh of machining cutting fluid stink control usefulness.
In preparation N-halamine bacterium material, comparatively general strategy be with the grafting of N-halamine precursor molecule to material surface.In general need to have in the precursor molecule " active group " of energy and material surface combination.Active group in US2007015921 and WO2006099567 (A3) is an epoxide ring.
Its structural formula of compound is as follows:
(R1 herein and R2 are alkyl, cycloalkyl or the phenyl of C1-C8; X is Cl or Br) or
(R herein
1And R
2Be C
1-C
8Alkyl, cycloalkyl or phenyl; X is Cl or Br)
Because the epoxide ring instability still stores all relatively difficulty so prepare.As in preparation, needing under the low temperature high vacuum distillation to remove solvent; And the dressing liquid for preparing can not long term storage, according to present inventor's result of the test, generally will use in a week, otherwise prepare the reduction of anti-biotic material antibacterial activity.The difficulty and the cost of anti-biotic material preparation have been increased like this.
Summary of the invention:
Deficiency at above-mentioned prior art N-halamine anti-biotic material manufacturing technique exists the invention discloses a kind of new N-halamine anti-biotic material preparation method, prepares anti-biotic material with the present invention and has overcome above-mentioned true point.
The invention provides new being used for and do the another kind of compound of N-halamine precursor molecule, hydroxyl and the halogen atom that links to each other with alkyl are arranged in its molecular structure.Concrete structure is as follows:
(R herein
1And R
2Be C
1-C
8Alkyl, cycloalkyl or phenyl; X is Cl or Br) or
(R herein
1, R
2, R
3, R
4Be C
1-C
8Alkyl, cycloalkyl or phenyl; X is Cl or Br)
Such N-halamine compound is compared with the N-halamine compounds that has epoxy-activated group, has production, stores and use the characteristics that all are easy to.
Hydantoin derivative described here can be by by document (Angew.Makromol.Chem.; 35; 1974; 9,17; US2007015921, WO2006099567; GB3975397) the step of giving or to press the improved method of the step of being given synthetic, also can obtain by commercial sources.
According to the present invention, the preparation of hydantoin derivative can directly be prepared with the higher highly finished product derivative of purity or with the lower semifinished product derivative of purity or with the reactant liquor of preparation hydantoin derivative.
Compound method with highly finished product is, takes by weighing the hydantoin derivative that needs, and adds alkali lye stirring and evenly mixing that needs water gaging or add requirement or the alkali that adds requirement and water stirring and evenly mixing and gets final product; Will know the concentration that contains hydantoin derivative in the raw material earlier with the semifinished product preparation or with the direct preparation of reactant liquor, concentration as required adds then needs water gaging/alkali stirring and evenly mixing.
After the preparation of hydantoin derivative solution, with material to be processed, as natural fabric, synthetic fiber, blend fibre, the crust fiber, synthetic rubber etc. are fed in the liquid that contains hydantoin derivative, after soaking certain hour, take out, make it adsorb a certain amount of hydantoin derivative by conventional used the soaking of dyeing and finishing industry-roll-soak-rolling method then, pick-up is generally 70～150%, by intensification hydantoin derivative is attached on the material by chemical reaction then, the material that will combine hydantoin derivative again immerses or sprays the solution that contains certain density active chlorine or active bromine and makes its activation and have antibacterial activity.Soak time described here is not a key factor, as long as drenched or drenched material surface need 10 minutes generally speaking, for abundant wetted materials, can stir, stir.Here said alkali can be NaOH, KOH, Na
2CO
3, K
2CO
3But do not limit to them, concentration is 0.001～10mol/L alkali, is preferably lmol/L～3mol/L.Here said " intensification is attached on the material hydantoin derivative " can use baking oven, and baking box also can use the hot-air method; The temperature of baking is generally 40～220 ℃, and the best is 130～170 ℃, can be to toast under higher temperature after removing most of water at low temperatures earlier again; The method of baking can be conventional methods such as industrial hot-air or baking box.
In the association reaction of hydantoin derivative and material generation chemical reaction, the time of reaction is relevant with temperature, is needing 30min below 130 ℃ at least; Get final product at 150～165 ℃ of baking 5～10min; Temperature surpasses 170 ℃, and some material may be destroyed.So select temperature should consider the high-temperature stability of material, generally select 60～200 ℃ of baking 3～200min, but preferably earlier at 60～120 ℃, after most of water baking is removed, again at 130～170 ℃ of baking 60～30min.
Containing the active group less material for some, as polyester fiber, in order to increase the binding capacity of material and glycolylurea, make the antibacterial activity height, can be 0.001～10mol/L alkali at the concentration of lye of concentration earlier at material to be processed, is preferably lmol/L～3mol/L.Soak in advance to drop into again after a period of time and contain in the liquid of hydantoin derivative, handle by above-mentioned method again.It is relevant with the temperature and the concentration of soaking alkali lye to soak a period of time in advance, is generally 3～48 hours under the at room temperature best alkali concn.
When using the activation of active chlorine or active bromine, but active chlorine solutions hypochlorous sodium, sodium hypobromite or contain the liquid of its composition, as 84 thimerosals, clorox.The concentration of active chlorine/active bromine is 0.01～1%, and the best is 0.05～0.3%.
Can obtain the N-halamine anti-biotic material by above-mentioned processing.Contain active chlorine with iodometric determination, show that the active chlorine content that obtains the N-halamine anti-biotic material with said method is generally 0.12～0.22%, active chlorine content given in this active chlorine content and the document (US2007015921) is suitable; So, should have good antibacterial activity with gained anti-biotic material of the present invention according to document.But find out that from foregoing description and embodiment the used method of the present invention has remarkable advantages: hydantoin derivative solution preparation easily, can long term storage, production cost is low
The specific embodiment:
The described method preparation of the following example is an example just, does not limit the present invention.
Embodiment 1
To in the round-bottomed flask of 5000mL, add 128g 5, the 5-DMH, the 3840ml epoxychloropropane, 0.5g phenyl triethyl ammonium chloride, 120 ℃ of heating 3 hours, go out excessive epoxychloropropane 60～65 ℃ of decompression distillation then, the cooling back adds the NaOH of 1000ml 2%, gets hydantoin derivative solution.Get the textile cloth of 50g and immerse aforesaid liquid, placed 45 minutes, the intermediate gap is stirred 3～5 times.After the taking-up, be extruded onto and no longer include tangible liquid and drip downwards, prior to baking in 90 ℃ of baking ovens 45 minutes, again in 145 ℃ of bakings 30 minutes.Take out the back with the running water washing, being distributed in after will wash then contains in 0.1% the clorox soaked 45 minutes, used the running water rinsing once, dried or was no more than 55 ℃ of oven dry.With iodometric determination must this cloth on chlorinty 0.18% (being to contain active chlorine 0.18g on the 100g cloth).According to experience in the past, this cloth should have good antibacterial action.
Embodiment 2
With replacing textile cloth among the embodiment 1 through 100% polyester fiber of 2%NaOH solution soaking after 12 hours in advance, identical among other processes and the embodiment 1.Chlorinty is 0.14%.
Embodiment 3
The dressing liquid for preparing by embodiment 1 was placed after 30 days, prepared anti-bacteria cloth by embodiment 1 method, and recording active chlorine content is 0.19%.
Claims (5)
1. the preparation method of a halogen amine (N-halamine) anti-biotic material is characterized in that:
(a) pending material is soaked in containing the solution of hydantoin derivative, maybe will contain the spray solution of hydantoin derivative/be applied to and make pending material be adsorbed with hydantoin derivative on the pending material;
(b) by elevated temperature hydantoin derivative is attached on the material;
(c) will be immersed in through the material that (b) handles and contain reactive halogen solution and maybe will contain reactive halogen spray solution/be applied to and make the material activation on the material and have antibacterial activity.
2. the structure of hydantoin derivative according to claim 1 is:
R wherein
1And R
2Be C
1-C
8Alkyl or cycloalkyl or phenyl; X is H or Cl or Br.
Or:
R wherein
1, R
2, R
3, R
4Be C
1-C
8Alkyl or cycloalkyl or phenyl; X is H or Cl or Br.
3. preparation method according to claim 1 is characterized in that: described pending material is: natural fabric or synthetic fiber, synthetic plastic, synthetic rubber, chitin or chitin, coating and their mixture.
4. preparation method according to claim 1 is characterized in that: described temperature is 50-220 ℃.
5. reactive halogen solution according to claim 1 is active chlorine or active bromine solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100151909A CN101250815A (en) | 2008-03-24 | 2008-03-24 | Method for manufacturing halogen amine antimicrobial material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100151909A CN101250815A (en) | 2008-03-24 | 2008-03-24 | Method for manufacturing halogen amine antimicrobial material |
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| Publication Number | Publication Date |
|---|---|
| CN101250815A true CN101250815A (en) | 2008-08-27 |
Family
ID=39954398
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|---|---|---|---|
| CNA2008100151909A Pending CN101250815A (en) | 2008-03-24 | 2008-03-24 | Method for manufacturing halogen amine antimicrobial material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453974A (en) * | 2010-10-15 | 2012-05-16 | 远东新世纪股份有限公司 | Highly water-absorbing antibacterial fiber |
| CN102677224A (en) * | 2011-03-14 | 2012-09-19 | 武汉纺织大学 | Preparation method of modified polyolefin antibacterial nanofiber |
| CN103147288A (en) * | 2013-02-22 | 2013-06-12 | 江南大学 | Method for preparing halamine antibacterial material based on cyanuric chloride |
| TWI451882B (en) * | 2012-02-17 | 2014-09-11 | Far Eastern New Century Corp | Tooth-whitening gel |
| CN106488702A (en) * | 2014-05-05 | 2017-03-08 | 曹正兵 | Antimicrobial surface coating |
| CN109403021A (en) * | 2018-10-31 | 2019-03-01 | 郑州人造金刚石及制品工程技术研究中心有限公司 | A kind of nanometer carbon crystal pure cotton antibacterial surface fiber and preparation method thereof |
| CN116622051A (en) * | 2023-07-25 | 2023-08-22 | 苏州久翔纺织整理有限公司 | Preparation method and application of antibacterial aqueous polyurethane emulsion |
| CN117385490A (en) * | 2023-11-02 | 2024-01-12 | 江苏威之盾安防科技有限公司 | Antibacterial fabric based on modified polyester fiber |
-
2008
- 2008-03-24 CN CNA2008100151909A patent/CN101250815A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453974A (en) * | 2010-10-15 | 2012-05-16 | 远东新世纪股份有限公司 | Highly water-absorbing antibacterial fiber |
| CN102677224A (en) * | 2011-03-14 | 2012-09-19 | 武汉纺织大学 | Preparation method of modified polyolefin antibacterial nanofiber |
| CN102677224B (en) * | 2011-03-14 | 2015-05-27 | 武汉纺织大学 | Preparation method of modified polyolefin antibacterial nanofiber |
| TWI451882B (en) * | 2012-02-17 | 2014-09-11 | Far Eastern New Century Corp | Tooth-whitening gel |
| CN103147288A (en) * | 2013-02-22 | 2013-06-12 | 江南大学 | Method for preparing halamine antibacterial material based on cyanuric chloride |
| WO2014127713A1 (en) * | 2013-02-22 | 2014-08-28 | 江南大学 | Method for preparing cyanuric chloride-based halogenoamine antibacterial material |
| CN106488702A (en) * | 2014-05-05 | 2017-03-08 | 曹正兵 | Antimicrobial surface coating |
| CN109403021A (en) * | 2018-10-31 | 2019-03-01 | 郑州人造金刚石及制品工程技术研究中心有限公司 | A kind of nanometer carbon crystal pure cotton antibacterial surface fiber and preparation method thereof |
| CN116622051A (en) * | 2023-07-25 | 2023-08-22 | 苏州久翔纺织整理有限公司 | Preparation method and application of antibacterial aqueous polyurethane emulsion |
| CN117385490A (en) * | 2023-11-02 | 2024-01-12 | 江苏威之盾安防科技有限公司 | Antibacterial fabric based on modified polyester fiber |
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Application publication date: 20080827 |