CN102875536A - Halamine antibacterial agent and synthetic method and application thereof - Google Patents
Halamine antibacterial agent and synthetic method and application thereof Download PDFInfo
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Abstract
The invention provides a halamine antibacterial agent and a synthetic method and application thereof. The halamine antibacterial agent is a compound with a structure which is shown as a formula (I) or a formula (II). The synthetic method comprises the following steps of: reacting by taking epoxy chloropropane and cyanuric acid or a derivative of the cyanuric acid as synthetic raw materials at the temperature of between 5 and 50 DEG C for 6 to 12 hours, filtering, removing impurities to obtain a halamine antibacterial agent precursor with a structure which is shown as a formula (III) or a formula (IV), and performing halogenating reaction to obtain a finished product of the halamine antibacterial agent. According to the application of the halamine antibacterial agent to the preparation of an antibacterial material, the antibacterial material is prepared by the following steps of: treating a material to be treated by a working solution prepared from the halamine antibacterial agent precursor, taking the material out, drying, treating at the temperature of between 80 and 200 DEG C for 3 to 60 minutes, and performing halogenating reaction. According to the method, reaction condition is mild, a process is simple, and raw materials are low in cost and readily available; and the halamine antibacterial agent synthesized by the method and the halamine antibacterial agent precursor are water-soluble, high in yield, safe and non-toxic, and can be prepared into antibacterial textiles with high antibacterial performance.
Description
Technical field
The invention belongs to the synthetic and antimicrobial technology field of halogen aminated compounds, be specifically related to the application in the preparation anti-biotic material of a kind of halogen amine heterocycle antiseptic-germicide and synthetic method thereof and this antiseptic-germicide.
Background technology
Exist a large amount of pathogenicly and cause the material rotten harmful microorganism that goes mouldy in the environment for human survival, the bacterium that especially pollutes and grow at the various materials such as fiber, plastics, rubber, paper and product surface consists of very large threat to the mankind's health.To prevent effectively that harmful microbe from growing, breed, spread and propagating, reduce the harm that it causes, using long-acting anti-biotic material is the simplest, safety and effective means, and the core of anti-biotic material is the antiseptic-germicide that loads on it, therefore, researcher is devoted to the development work of all kinds of antiseptic-germicides all the time.
Common antiseptic-germicide has heavy metal class, quaternary ammonium salt and nano material class etc. in the market, but has the shortcomings such as antibacterial ability is weak, sterilization speed is slow, meeting produces harmful toxic byproduct, non-renewable.For remedying the deficiency of above-mentioned traditional antiseptic-germicide, recent two decades comes the Worley professor of U.S. Auburn University and Gang professor Sun of University of California to develop a large amount of halogen amine antimicrobial agent, and its summary of benefits is as follows:
(1) strong, the has a broad antifungal spectrum of germ resistance extremely can kill the various microorganisms of material surface in the short time;
(2) its acid amides heterocycle with anti-microbial property can be combined with material by chemical bond, and antibiotic weather resistance is good;
(3) renewable, after effective halogen released, available active halogen solutions was processed and is made it to recover germ resistance;
(4) can not produce toxic byproduct, to human body and environmental safety.
What the halogen amine antimicrobial agent that above-mentioned two Research Teams are just developed was applied for reaches in tens patents, the most representative with the hydantoin derivative antiseptic-germicide, such as US Patent No. 200701592, US7335373B2 and US5882357.
Yet also there are some problems in actual applications in above-mentioned halogen amine antimicrobial agent: (1) synthesis material such as chloroethyl triethoxyl silane are expensive; (2) building-up reactions need to be carried out pyroreaction in anhydrous organic system, and energy consumption of reaction is large, long reaction time, production cost are higher; (3) most synthetic products are water-soluble relatively poor, when carrying out the antibacterial finish of material, the preparation working fluid must add a large amount of solubility promoter hydrotropies, increased arrangement cost and cost for wastewater treatment, and these inflammable organic solvents dangerous property also in the arrangement process; (4) in use still there is the problem that formaldehyde discharges in part chloramines class antiseptic-germicide.
Summary of the invention
The applicant provides a kind of halogen amine antimicrobial agent for antiseptic-germicide in the above-mentioned prior art and synthetic method Shortcomings thereof.This antiseptic-germicide has superior anti-microbial property.
Another object of the present invention is to provide the synthetic method of above-mentioned halogen amine antimicrobial agent.This synthesising method reacting condition is gentle, the reaction times is short, technique is simple, raw material is cheap and easy to get, production cost is low, by the synthetic halogen amine antimicrobial agent of the method and presoma thereof be water-soluble, product yield is high, safety non-toxic.
A further object of the present invention is to provide the application of above-mentioned halogen amine antimicrobial agent in the preparation anti-biotic material.Antiseptic-germicide of the present invention is applied to prepare anti-biotic material, and gained antiseptic-germicide textiles has excellent anti-microbial property, and antimicrobial efficiency is high.
Purpose of the present invention realizes by following technical proposals:
A kind of halogen amine antimicrobial agent is characterized in that: be the compound of structure shown in formula I or the formula II:
Wherein, X
1, X
2Be selected from respectively chlorine, bromine or methylol, and X
1And X
2Have at least one to be selected from chlorine or bromine in the two;
Wherein, X
3Be selected from chlorine or bromine.
The invention provides a kind of synthetic method of halogen amine antimicrobial agent, step is as follows: cyanuric acid or cyanuric acid derivative are dissolved in alkali lye, until completely dissolved, slowly add epoxy chloropropane, in 5～50 ℃ of lower abundant stirring reaction 6～12h; PH to 6.5 behind the conditioned reaction～7.5, evaporate to dryness is moisture wherein, and with the gained dissolution of solid in organic solvent, filtering and impurity removing, the described organic solvent in the evaporate to dryness filtrate obtains halogen amine antimicrobial agent presoma again; At last described presoma is added mass percentage concentration and be in 0.01～5% the clorox or sodium hypobromite solution, in room temperature standing and reacting 1h, reaction finishes, and filters also oven dry, obtains halogen amine antimicrobial agent finished product; Wherein the cyanuric acid derivative is the compound that an one hydrogen atom is replaced by methylol; Require in the higher situation, behind the described organic solvent in evaporate to dryness filtrate, also can carry out purification processes to the thick product of gained halogen amine antimicrobial agent precursor.
Its further technical scheme is:
The mol ratio of described epoxy chloropropane and cyanuric acid or derivatives thereof is 1:1～3:1.
Described alkali lye is selected from sodium hydroxide, potassium hydroxide, yellow soda ash or solution of potassium carbonate, and its mass percentage concentration is 1～30%.
Described organic solvent is selected from ethanol, dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC) or dimethyl sulfoxide (DMSO) (DMSO).
Described halogen amine antimicrobial agent presoma is the compound of structure shown in formula III or the formula IV:
Wherein, X
4Be selected from hydrogen or methylol;
The invention provides the application of a kind of halogen amine antimicrobial agent in the preparation anti-biotic material, it is 1～20% working fluid that the halogen amine antimicrobial agent presoma of formula III or the described structure of formula IV or any mixture of the two are mixed with respectively mass percentage concentration, is preferably 1～10%; Pending material soaking in described working fluid, or is sprayed described working fluid/be applied on the pending material, be as the criterion with drenched material; Take out material and oven dry, in 80～200 ℃ of pyroprocessing 3min～60min, preferred process temperature is 100～180 ℃; Material soaking after the pyroprocessing is carried out halogenating reaction in the solution that contains reactive halogen, take out washing and oven dry, make anti-biotic material; When above-mentioned materials is textiles, can adopt two traditional two methods of rolling of soaking that this textiles is processed, pick-up is 70～120%; The modes such as above-mentioned pyroprocessing can bake by baking oven, hot air treatment, high temperature flatiron and roller process realize.
Its further technical scheme is:
For improving the connection rate of described antiseptic-germicide presoma on described textiles, can in described working fluid, add alkaline agent or bridging property material; Described alkaline agent is selected from sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood, and its mass percentage concentration in described working fluid is 0.1～10%, is preferably 0.5～3%; Described bridging property material is selected from polycarboxylic acid, Resins, epoxy, amides resin, urethane, siloxanes, aldehydes or polysiloxane compounds, and its mass percentage concentration in described working fluid is 1～20%.
Described pending material comprises a kind of in natural fiber or synthetic textile, plastics, sponge, natural rubber, synthetic rubber, timber, paper, coating, chitosan or the chitin.
The described solution that contains reactive halogen is selected from clorox, sodium hypobromite or calcium hypochlorite solution, and its mass percentage concentration is 0.01～5%, and being preferably 0.01～0.5%, pH value is 4.0～12.0.
Compared with prior art, the present invention has following beneficial effect:
1. halogen amine antimicrobial agent of the present invention selects epoxy chloropropane cheap and easy to get, cyanuric acid (or derivatives thereof) as synthesis material, greatly reduces production cost;
2. compare with halogen amine antimicrobial agent synthetic method of the prior art, the inventive method reaction conditions is gentle, can carry out building-up reactions in aqueous phase system under the condition of normal temperature or a little heating, and the reaction times is short, energy consumption of reaction is low, and technological process is simple;
3. be water-soluble by the inventive method synthetic halogen amine antimicrobial agent and presoma thereof, product yield is high, in the process of follow-up preparation working fluid, need not add the organic solvent hydrotropy, reduced antibacterial finish cost and cost for wastewater treatment, avoided simultaneously in the prior art owing to the danger of using inflammable organic cosolvent to cause; And above-mentioned halogen amine antimicrobial agent and presoma thereof be formaldehydeless release, safety non-toxic in use;
4. halogen amine antimicrobial agent of the present invention is applied to prepare anti-biotic material, the gained antibacterial fabric has excellent anti-microbial property, antimicrobial efficiency is high, its available chlorine content can reach 0.33%, after inoculated bacteria contacted, the antibiotic rate to streptococcus aureus and Escherichia coli O 157: H7 in 5min can reach 100%.
Description of drawings
Fig. 1 is the synthetic route chart of halogen amine antimicrobial agent presoma and halogen amine antimicrobial agent in the embodiment of the invention 1.
Fig. 2 is the chemical principle figure of the application of halogen amine antimicrobial agent in the preparation antibacterial fabric in the Application Example 1 of the present invention.
Fig. 3 is textiles Infrared spectroscopy figure.
Embodiment
Below in conjunction with accompanying drawing, and by embodiment the present invention is specifically described.
As shown in Figure 1, take cyanuric acid and epoxy chloropropane as synthesis material, under the condition of low temperature (25 ℃) and alkaline matter (NaOH) existence, hydrogen on the cyanuric acid is replaced by the propylene oxide propyl group, generate halogen amine antimicrobial agent precursor 1-epoxypropyl-S-triazinetrione, finally by the superchlorination reaction, introduce oxidisability chlorine atom at above-mentioned presoma, generation has the halogen amine antimicrobial agent 1 of anti-microbial property, 3-two chloro-5-epoxypropyl-S-triazinetriones.
As shown in Figure 2, above-mentioned halogen amine antimicrobial agent presoma 1-epoxypropyl-S-triazinetrione is applied to prepare antibacterial fabric.Under the condition that high temperature (100 ℃) bakes, the hydroxyl (HO-Cellulose) of epoxypropyl on the described antiseptic-germicide presoma on pending textile fiber macromole is combined with the form of ehter bond, so that above-mentioned antiseptic-germicide presoma is connected to this textile surface; By chlorination reaction, introduce oxidisability chlorine atom at the antiseptic-germicide presoma that is connected in textile surface, so that this textiles possesses anti-microbial property at last.
Consider from operation and use angle, halogen amine antimicrobial agent presoma is directly applied to the preparation anti-biotic material, and in the end carry out halogenating reaction, more more convenient than the agent of direct application halogen amine antimicrobial, have more practicality.
Halogen amine antimicrobial agent and synthetic method embodiment thereof:
Embodiment 1
Halogen amine antimicrobial agent 1,3-two chloro-5-epoxypropyl-S-triazinetriones synthetic
Taking by weighing 6.45g(0.05mol) cyanuric acid places the 250mL Florence flask, add the 100mL deionized water, with the glass stick rear adding 4g sodium hydroxide that stirs, continuing to be stirred to cyanuric acid dissolves fully, slowly drip 4.63g(0.05mol) epoxy chloropropane, in the abundant stirring reaction 6h of room temperature (25 ℃), and with pH to 6.5 behind the dilute hydrochloric acid conditioned reaction; With Rotary Evaporators except the moisture in the solution after the dereaction, and with the gained dissolution of solid in dimethyl formamide (DMF), filter according to ordinary method, remove synthesising by-product sodium-chlor, remove DMF in the filtrate by Rotary Evaporators again, obtain water-soluble colorless oily halogen amine antimicrobial agent presoma 1-epoxypropyl-S-triazinetrione; At last this presoma is added mass percentage concentration and be 0.1% chlorine bleach liquor, in room temperature (25 ℃) standing and reacting 1h, reaction finishes, filter and oven dry, namely get halogen amine antimicrobial agent finished product 1,3-two chloro-5-epoxypropyl-S-triazinetriones, this antiseptic-germicide finished product is water-soluble, productive rate 72%.
Embodiment 2
Halogen amine antimicrobial agent 1-chloro-3,5-diepoxy propyl group-S-triazinetrione synthetic
Taking by weighing 6.45g(0.05mol) cyanuric acid places the 250mL Florence flask, add the 100mL deionized water, with the glass stick rear adding 5.6g potassium hydroxide that stirs, continuing to be stirred to cyanuric acid dissolves fully, slowly drip 9.25g(0.1mol) epoxy chloropropane, in 5 ℃ of abundant stirring reaction 12h, and with pH to 7.0 behind the dilute sulphuric acid conditioned reaction; With Rotary Evaporators except the moisture in the solution after the dereaction, and with the gained dissolution of solid in ethanol, filter according to ordinary method, remove synthesising by-product Repone K, remove ethanol in the filtrate by Rotary Evaporators again, obtain water-soluble colorless oily halogen amine antimicrobial agent presoma 1,3-diepoxy propyl group-S-triazinetrione; At last this presoma is added mass percentage concentration and be among 1% the chlorine bleach liquor, in room temperature standing and reacting 1h, reaction finishes, filter and oven dry, namely get halogen amine antimicrobial agent finished product 1-chloro-3,5-diepoxy propyl group-S-triazinetrione, it is water-soluble namely getting this antiseptic-germicide finished product of halogen amine, productive rate 88%.
Embodiment 3
Synthesizing of halogen amine antimicrobial agent 1-chloro-3-methylol-5-epoxypropyl-S-triazinetrione
Taking by weighing 15.9g(0.1mol) 1-methylol-S-triazinetrione (being the compound that one of them hydrogen atom of cyanuric acid is replaced by methylol) places the 250mL Florence flask, add the 100mL deionized water, with the glass stick rear adding 30g sodium hydroxide that stirs, continuing to be stirred to 1-methylol-S-triazinetrione dissolves fully, slowly drip 9.25g(0.1mol) epoxy chloropropane, in 50 ℃ of abundant stirring reaction 9h, and with pH to 7.5 behind the dilute sulphuric acid conditioned reaction; With Rotary Evaporators except the moisture in the solution after the dereaction, and with the gained dissolution of solid in N,N-DIMETHYLACETAMIDE (DMAC), filter according to ordinary method, remove synthesising by-product sodium-chlor, remove ethanol in the filtrate by Rotary Evaporators again, obtain water-soluble colorless oily halogen amine antimicrobial agent presoma 1-methylol-3-epoxypropyl-S-triazinetrione; At last this presoma is added mass percentage concentration and be among 5% the chlorine bleach liquor, in room temperature standing and reacting 1h, reaction finishes, filter and oven dry, namely get halogen amine antimicrobial agent finished product 1-chloro-3-methylol-5-epoxypropyl-S-triazinetrione, this antiseptic-germicide finished product is water-soluble, productive rate 81%.
In sum, embodiment 2 has the highest productive rate, is most preferred embodiment.
Halogen amine antimicrobial agent Application Example:
Application Example 1
It is 1% working fluid that the halogen amine antimicrobial agent presoma 1-epoxypropyl that embodiment 1 is synthetic-S-triazinetrione is mixed with mass percentage concentration, contains mass percentage concentration in the working fluid and be 1% sodium hydroxide; With pending Nature Fibre Textile product (pure cotton fabric, available from Zhejiang Guandong Dyeing and Garment Co., Ltd.) impregnated in above-mentioned working fluid 15min, take out pure cotton fabric, the control solid carbon dioxide divides to dripping without obvious drop, in dryer, dry 50min in 80 ℃, then in baker, bake 60min in 100 ℃; Pure cotton fabric after taking-up bakes is 0.5% standard soap flakes solution and a large amount of its surfaces of washed with de-ionized water with mass percentage concentration, dries in room temperature; It is (with dilute sulphuric acid regulator solution pH value to 7.0) in 0.01% the calcium hypochlorite solution that pure cotton fabric after will drying is soaked in mass percentage concentration, take out pure cotton fabric also with a large amount of clear water cleanings after soaking 1h, in dryer, dry 2h in 45 ℃, make antibiotic pure cotton fabric.The available chlorine content that records this antibiotic pure cotton fabric with iodimetry,iodometry is 0.10%.
Application Example 2
It is 10% working fluid that the halogen amine antimicrobial agent presoma 1 that embodiment 2 is synthetic, 3-diepoxy propyl group-S-triazinetrione are mixed with mass percentage concentration, contains mass percentage concentration in the working fluid and be 6% bridging property material citric acid; Nature Fibre Textile product (pure cotton fabric is available from Zhejiang Guandong Dyeing and Garment Co., Ltd.) be impregnated in this working fluid 15min, and two soak two rolls, and then dries 10min in 80 ℃ in dryer, bakes 10min in 170 ℃ in baker again; Pure cotton fabric after taking-up bakes is 0.5% standard soap flakes solution and a large amount of its surfaces of washed with de-ionized water with mass percentage concentration, dries in room temperature; It is (with dilute sulphuric acid regulator solution pH value to 12.0) among 0.5% the chlorine bleach liquor that pure cotton fabric after will drying is soaked in mass percentage concentration, take out pure cotton fabric also with a large amount of clear water cleanings after soaking 1h, in dryer, dry 2h in 45 ℃, make antibiotic pure cotton fabric.The available chlorine content that records this antibiotic pure cotton fabric with iodimetry,iodometry is 0.33%.
Application Example 3
It is 20% working fluid that the halogen amine antimicrobial agent presoma 1-methylol that embodiment 3 is synthetic-3-epoxypropyl-S-triazinetrione is mixed with mass percentage concentration, contains mass percentage concentration in the working fluid and be 6% bridging property material citric acid; This working fluid is applied on the pending Nature Fibre Textile product (pure cotton fabric is available from Zhejiang Guandong Dyeing and Garment Co., Ltd.), is as the criterion with drenched fabric; Then in dryer, dry 50min in 80 ℃, in baker, bake 3min in 200 ℃ again; Pure cotton fabric after taking-up bakes is 0.5% standard soap flakes solution and a large amount of its surfaces of washed with de-ionized water with mass percentage concentration, dries in room temperature; It is (with dilute sulphuric acid regulator solution pH value to 7.0) among 1% the chlorine bleach liquor that pure cotton fabric after will drying is soaked in mass percentage concentration, take out pure cotton fabric also with a large amount of clear water cleanings after soaking 1h, in dryer, dry 2h in 45 ℃, make antibiotic pure cotton fabric.The available chlorine content that records this antibiotic pure cotton fabric with iodimetry,iodometry is 0.38%.
In sum, the available chlorine content of Application Example 2 made antibiotic pure cotton fabrics is higher and the fabric intensity damage is less, is best applications embodiment.
Pure cotton fabric FT-IRATR Infrared spectroscopy:
Adopt Fourier's attenuated total reflectance attenuated total refraction spectrum (FT-IRATR) method of testing to test.Get pure cotton fabric (with Application Example 1～Application Example 3), carry out antibacterial finish according to Application Example 2 described methods, but without last halogenating reaction as blank sample; Above-mentioned blank sample and Application Example 2 made antibiotic pure cotton fabrics without halogenating reaction are carried out Infrared spectroscopy, and with without the above-mentioned pure cotton fabric of antibacterial finish as experimental control, test result is referring to Fig. 3.
As shown in Figure 3: (A) be infrared spectrogram without the pure cotton fabric of antibacterial finish; (B) be the infrared spectrogram of Application Example 3 made antibiotic pure cotton fabrics; (C) be the infrared spectrogram of blank sample.Compare with the fabric without antibacterial finish, the infrared spectra of blank sample is at 1744cm
-1New absorption peak (carbonyl absorption peak) has appearred in the place, prove that antiseptic-germicide presoma (1-methylol-3-epoxypropyl-S-triazinetrione) without halogenating reaction and fabric have carried out chemical reaction and be connected on this fabric; Appear at 1749cm through carbonyl absorption peak on its infrared spectra of fabric (Application Example 3 made antibiotic pure cotton fabrics) of halogenating reaction
-1The place, reason is that the N-H key before the halogenation has become the N-Cl key through after the halogenating reaction.
The test of pure cotton fabric anti-microbial property:
Test according to revising the described method of AATCC 100-1999 anti-microbial property testing standard.Get pure cotton fabric (with Application Example 1～Application Example 3), carry out antibacterial finish according to Application Example 2 described methods, but without last halogenating reaction as blank sample; Above-mentioned blank sample and Application Example 3 made antibiotic pure cotton fabrics without halogenating reaction are carried out the anti-microbial property test, and inoculated bacteria is streptococcus aureus and Escherichia coli O 157: H7, and test result is referring to table 1 and table 2.
The antibiotic pure cotton fabric of table 1 is to the anti-microbial property of streptococcus aureus
Annotate: the inoculum density of streptococcus aureus: 9.67 * 10
6Cfu
Table 2 antibacterial fabric is to the anti-microbial property of Escherichia coli O 157: H7
Annotate: the inoculum density of Escherichia coli O 157: H7: 2.50 * 10
7Cfu
The test data of table 1 and table 2 shows, antiseptic-germicide of the present invention is applied to prepare anti-biotic material, and made antibiotic pure cotton fabric has excellent anti-microbial property, and antimicrobial efficiency is high; After inoculated bacteria contacted, above-mentioned antibiotic pure cotton fabric antibiotic rate to streptococcus aureus and Escherichia coli O 157: H7 in 5min can reach 100%.
The related raw material of above embodiment and Application Example and reagent are the commercially available prod, and institute's use industrial equipments is this area conventional equipment.
Above-described only is preferred implementation of the present invention, the invention is not restricted to above embodiment.Be appreciated that other improvement and variation that those skilled in the art directly derive or associate under the prerequisite that does not break away from spirit of the present invention and design, all should think to be included within protection scope of the present invention.
Claims (10)
1. halogen amine antimicrobial agent is characterized in that: be the compound of structure shown in formula I or the formula II:
Wherein, X
1, X
2Be selected from respectively chlorine, bromine or methylol, and X
1And X
2Have at least one to be selected from chlorine or bromine in the two;
Wherein, X
3Be selected from chlorine or bromine.
2. the synthetic method of the described halogen amine antimicrobial agent of claim 1 is characterized in that: cyanuric acid or cyanuric acid derivative are dissolved in alkali lye, until completely dissolved, slowly add epoxy chloropropane, in 5～50 ℃ of lower abundant stirring reaction 6～12h; PH to 6.5 behind the conditioned reaction～7.5, evaporate to dryness is moisture wherein, and with the gained dissolution of solid in organic solvent, filtering and impurity removing, the described organic solvent in the evaporate to dryness filtrate obtains halogen amine antimicrobial agent presoma again; At last described presoma is added mass percentage concentration and be in 0.01～5% the clorox or sodium hypobromite solution, in room temperature standing and reacting 1h, reaction finishes, and filters also oven dry, obtains halogen amine antimicrobial agent finished product; Described cyanuric acid derivative is the compound that an one hydrogen atom is replaced by methylol.
3. the synthetic method of described halogen amine antimicrobial agent according to claim 2, it is characterized in that: the mol ratio of described epoxy chloropropane and cyanuric acid or derivatives thereof is 1:1～3:1.
4. the synthetic method of described halogen amine antimicrobial agent according to claim 2, it is characterized in that: described alkali lye is selected from sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood, and its mass percentage concentration is 1～30%.
5. the synthetic method of described halogen amine antimicrobial agent according to claim 2, it is characterized in that: described organic solvent is selected from ethanol, dimethyl formamide, N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO).
6. the synthetic method of described halogen amine antimicrobial agent according to claim 2, it is characterized in that: described halogen amine antimicrobial agent presoma is the compound of structure shown in formula III or the formula IV:
Wherein, X
4Be selected from hydrogen or methylol;
7. the described halogen amine antimicrobial agent of claim 1 is characterized in that in the application of preparation in the anti-biotic material: it is 1～20% working fluid that the halogen amine antimicrobial agent presoma of formula III or the described structure of formula IV or any mixture of the two are mixed with respectively mass percentage concentration; Pending material soaking in described working fluid, or is sprayed described working fluid/be applied on the pending material, be as the criterion with drenched material; Take out material and oven dry, in 80～200 ℃ of pyroprocessing 3min～60min; Material soaking after the pyroprocessing is carried out halogenating reaction in the solution that contains reactive halogen, take out washing and oven dry, make anti-biotic material.
8. the according to claim 7 application of described halogen amine antimicrobial agent in the preparation anti-biotic material is characterized in that: for improving the connection rate of described antiseptic-germicide presoma on described textiles, can add alkaline agent or bridging property material in described working fluid; Described alkaline agent is selected from sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood, its mass percentage concentration in described working fluid is 0.1～10%, described bridging property material is selected from polycarboxylic acid, Resins, epoxy, amides resin, urethane, siloxanes, aldehydes or polysiloxane compounds, and its mass percentage concentration in described working fluid is 1～20%.
9. described halogen amine antimicrobial agent is characterized in that in the application of preparation in the anti-biotic material according to claim 7: described pending material comprises a kind of in natural fiber or synthetic textile, plastics, sponge, natural rubber, synthetic rubber, timber, paper, coating, chitosan or the chitin.
10. the according to claim 7 application of described halogen amine antimicrobial agent in the preparation anti-biotic material, it is characterized in that: the described solution that contains reactive halogen is selected from clorox, sodium hypobromite or calcium hypochlorite solution, its mass percentage concentration is that 0.01～5%, pH value is 4.0～12.0.
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