CN106359383A - Bifunctional bactericide containing double bond, quaternary ammonium salt and halamine, and preparation method and application thereof - Google Patents
Bifunctional bactericide containing double bond, quaternary ammonium salt and halamine, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a bifunctional bactericide containing a double bond, a quaternary ammonium salt and halamine, and a preparation method and application thereof. The bactericide carries a C-C double bond and sterilizing bifunctional groups consisting of halamine and quaternary ammonium salt. The preparation method comprises the following steps: preparing 3-hydroxyalkyl-5,5-dimethylhydantoin at first, then carrying out a halogenation reaction to produce 3-haloalkyl-5,5-dimethylhydantoin, subjecting 3-haloalkyl-5,5-dimethylhydantoin and (dihydroxyamino)hydroxyacrylate to a quaternization reaction, and carrying out treatment by using a halogenation reagent. The bactericide provided by the invention is used through formation of a bactericidal coating on the surface of a material, wherein the bactericidal coating has a thickness of 5 nanometers to 5 micrometers. The bactericide provided by the invention forms the solid bactericidal coating through reaction on the surface of a material, is small in toxicity, wide in a bactericidal scope, long-lasting in bactericidal performance, high in bactericidal efficiency and safe to human beings, and can form the bactericidal coating on the surface of the material in a plurality of manners.
Description
Technical field
The invention belongs to synthetic organic chemical art, specifically, it is related to a kind of reactive group containing double bond and quaternary ammonium salt
With the antibacterial of the double official's sterilization group of halogen amine and its preparation method and application.
Background technology
Pathogenic bacteria is the important threat of public health.Prepare the Fungicidal substance of efficient, wide spectrum and safety, be organic synthesiss, material
The study hotspot in the field such as material and biology.
Existing antibacterial include the metallics such as copper silver or compound, antibioticses small organic molecule, with quaternary ammonium salt
For represent positively charged group, oxidisability high price halogen particle, and biological polypeptide.Metal series antibacterial has to human body cell
Evil, the resistance to Drug resistance of small organic molecule is poor, the not yet industrialization of biological polypeptide costliness.So existing more satisfactory germicide
Matter is quaternary ammonium salt or halogen amine groups, and this type antibacterial typically comprises only the separate base in quaternary ammonium salt group or halogen amine,
But the Comparison of effect on sterilization of quaternary ammonium salt antibacterial is gentle, and consume very fast during the sterilization of halogen amine, and the bactericidal range of the two
Also difference.So current antibacterial can not have the two advantage concurrently.
The method that sterilization material and products thereof can be immersed by physics or adsorb, is added to the material needing antibacterial functions
Surface, or by the method for covalent bond, the group with antibacterial functions is keyed to and needs the material of antibacterial to obtain.If logical
Cross physics immersion or the method for absorption is added to material surface, not enough formation stenlizing layer securely；From the durability of antibiotic effect and
Reduce environmental pollution aspect to consider, covalently bonded method has sizable advantage, and now needing antibacterial to carry can shape
Become the reactive group of chemical bonding.
Consider some shortcomings that the existing various antibacterial for antimicrobial coating exists up till now it is believed that opening
Send out can be prevented effectively from these shortcomings the antibacterial agent for antimicrobial coating necessary, the number of antibacterial can not only be extended
Amount, also significant to going deep into scientific research.
Content of the invention
The present invention proposes a kind of quaternary ammonium salt having different sterilization species and mechanism concurrently, halogen amine difunctionality antibacterial, can be more
Efficiently kill different types of pathogenic bacteria, carry the carbon-carbon double bond reactive group together with being available for being keyed to material surface simultaneously,
Can efficiently, the killing pathogenic bacteria of spectrum and and material form lasting stenlizing layer.
Of the present invention a kind of containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial, there is formula () structure:
Wherein, r1、r2Any one for methyl or ethyl；X is any one in cl or br；Y is in cl or br
Any one；M, n are arbitrary integer between 1～5.
Invention also provides a kind of above-mentioned preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial, bag
Include:
1) 5,5- dimethyl hydantion and alkali reaction half an hour, it is subsequently adding bromine hydroxyl alcohol and substitution reaction occurs, generate 3- hydroxyl
Alkyl -5,5- dimethyl hydantion.
2) by step 1) product that obtains of reaction carries out halogenating reaction with phosphorus trihalide, generates 3- brine alkyl -5,5- diformazan
Base glycolylurea.
3) by step 2) product that generates carries out quaternization reaction with acrylic acid dihydroxy amido hydroxyl ester.
4) by step 3) product that generates processes with halide reagent, generates halogen amine sterilization group.
Preferably, described step 1) in bromine hydroxyl alcohol used there is formula () structure:
Preferably, the response time of described solution is 2～20 hours；Reaction temperature is 20～100 DEG C.
Invention also provides the above-mentioned application containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial, antibacterial with
The form forming sterilization coating in material surface uses, and stenlizing layer thickness is at 5 nanometers～5 microns.
Present invention also offers a kind of face coat containing the antibacterial as described in formula.
Halogen amine and quaternary ammonium salt are outstanding sterilization groups, and the two sterilization mechanism is different with species.Wherein, halogen amine passes through ionization
Go out positively charged halogen, penetrate into pathogenic bacteria, and then aoxidize the sterilization of the principle such as pathogenic bacteria protein and dna；Quaternary ammonium salt is by itself
Positive charge, rely on electrostatic attraction, cut negatively charged pathogenic bacteria cell wall and sterilize.Halogen amine is to Gram-positive and negative bacterium
It is respectively provided with good killing effect, but consume during sterilization, renewable after consumption；Quaternary ammonium salt is insensitive to gram negative bacteria,
Do not consume during sterilization, sterilizing ability is more lasting.Because the sterilization mechanism of the two is different with species, there is synergistic function, after combination
Can more efficient, broadly sterilize.
Carbon-carbon double bond is active reactive group, and multiple reactions such as addition polymerization, addition, silicon hydrogenation can occur.For example, material list
Face high-energy rays, after such as uv, plasma, gamma-rays etc. are processed, may result from by reactive groups such as base and peroxide,
These reactive groups cause double bond to occur from epontic polyreaction；Double bond containing material is penetrating into material surface, permissible
Polymer is generated by polyreaction；When material surface has si-h bond, can be acted on double bond by silicon hydrogenation, sterilization
Material is keyed to material surface；If double bond first passes through reaction and changes into other groups, and the possible bonded mode of material just has
More more options.
The present invention has synthesized halogen amine and quaternary ammonium salt combination type Fungicidal substance, and has the high double bond of reactivity, with convenient
Form sterilization coating in material surface.
Present invention preparation has the quaternary ammonium salt of double bond, the principle of the antibacterial of halogen amine difunctional is:
The dimethyl hydantion of 5,5- first and alkali reaction half an hour, Deca bromine hydroxyl alcohol generation nucleophilic substitution thereto,
3- hydroxyl alkyl -5 that will generate, 5- dimethyl hydantion carries out bromine substitution reaction, this product is entered with acrylic acid dihydroxy amido hydroxyl ester
Row quaternization reacts, and carries out halogenation treatment using organic halogenation reagent, final antibacterial has quaternary ammonium salt and halogen amine simultaneously
Sterilization group, and contain double bond, can be connected on other materials.
1) 5,5- dimethyl hydantion pass through alkalization, with bromine hydroxyl alcohol occur substitution reaction:
M is integer, m=1～5.
2) step 1) product through phosphorus trihalide occur halogenation, generate 3- brine alkyl -5,5- dimethyl hydantion:
3) by step 2) product that generates carries out quaternization reaction with double bond containing tertiary amine, generates quaternary ammonium salt:
N is integer, n=1～5；
r1、r2It is respectively any one in methyl or ethyl.
4) by step 3) product organic halogenation agent treated, generate halogen amine sterilization group:
X is any one in cl or br；Y is any one in cl or br.
The sterilization group of the present invention, has notable superiority on germicidal efficiency and sterilization persistency.Using sterilization standard
Method " sandwich " compares, and in the case that the antibacterial of same molar ratio is contained on surface, comprises only killing of quaternary ammonium salt
Bacterium surface requires more than 1 hour and could kill concentration is 107The escherichia coli of cfu/ml or golden yellow staphylococcus；Comprise only halogen amine
Sterilization surface, requires more than the antibacterial that could kill same concentration and species for 15 minutes.And the present invention has quaternary ammonium salt and halogen amine concurrently
Group, can kill the whole antibacterials under similarity condition in 10 minutes.
, so that antibacterial can be connected to material surface by chemical bond, it is lasting to be formed for the double bond of antibacterial of the present invention
Stenlizing layer.In the method using " grafting from ", it is polymerized the antibacterial of the present invention from material surface, after forming stenlizing layer
There is excellent stability.Stenlizing layer is carrying out washing experiment using aatcc 61-1996 method, (is equivalent to after washing 5 times
Conventional laundry apparatus wash 50 times), still there is 86% antibacterial to be connected to surface.And typically pass through the stenlizing layer that absorption is formed, by
In connecting with material surface not by chemical bond, very insecure.After washed once, antibacterial is just completely from surface
Come off, material loses bactericidal effect, and the antibacterial coming off pollutes environment and causes the pathogenic bacteria in environment to develop immunity to drugs.
Specific embodiment
Embodiment 1
Add 10.65 parts of 5,5- dimethyl hydantion, 4.65 parts of potassium hydroxide and 150 parts of ethanol in 250ml there-necked flask,
Under the device equipped with stirring magneton and condensing tube, half an hour is stirred at room temperature, continues to add 11.5 parts of 3- in there-necked flask
Bromo- 1- propanol, reacts 12 hours under conditions of 60 DEG C, is removed by filtration the kbr generate in course of reaction, does eluant with ethanol
Remove unreacted 5,5- dimethyl hydantion by crossing pillar, glycolylurea alcohol is obtained by rotary evaporation.Will be molten for the glycolylurea alcohol generating
Solution in 30 parts of oxolanes, under conditions of ice-water bath, 50 parts of pbr of Deca thereto3, continuously stirred 2 hours, water-bath was slowly
Heating, is warming up to 75 DEG C and is incubated 3 hours, track to reaction with thin layer chromatography and finish, be cooled to room temperature, slowly drip under ice-water bath
Plus 200 parts of distilled water, separate organic layer, aqueous phase is extracted two to three times with 30 parts of dichloromethane, merge organic faciess and with saturation
Sodium bicarbonate solution neutralizes so as to ph value is 7-8, and concentrated by rotary evaporation obtains the brominated glycolylurea of yellow.Equipped with stirring magneton with cold
15.75 parts of brominated glycolylureas, 9.1 parts of dimethylamino ethyl acrylate and 100 parts of second are added in the 250ml three neck round bottom flask of solidifying pipe
Alcohol, reacts 8 hours under conditions of 75 DEG C, is spin-dried for Rotary Evaporators.Finally make solvent with dichloromethane, add 30 parts bromines
Tert-butyl acrylate reacts 6 hours, and decompression leaches out the small molecules such as organic bromine, dichloromethane, obtains double containing double bond, quaternary ammonium salt and halogen amine
Sense antibacterial, has a structure shown below:
Embodiment 2
3.55 parts of 5,5- dimethyl hydantion, 1.55 parts of potassium hydroxide and 50 parts of ethanol are added in 100ml there-necked flask,
Equipped with the device with condensing tube for the stirring magneton, half an hour is stirred at room temperature, continues the bromo- 1- of 4 parts of 4- of addition in there-necked flask
Butanol, reacts 12 hours under conditions of 60 DEG C, is removed by filtration the kbr generate in course of reaction, with ethanol elution, by crossing post
Son removes unreacted 5,5- dimethyl hydantion, is evaporated under reduced pressure and obtains glycolylurea alcohol.The glycolylurea alcohol of generation is dissolved in 10 parts of tetrahydrochysenes
In furan, under conditions of ice-water bath, 18 parts of pcl of Deca thereto3, continuously stirred 2 hours, water-bath was slowly heated, and is warming up to
75 DEG C are incubated 3 hours, track to reaction with thin layer chromatography and finish, are cooled under room temperature, ice-water bath and are slowly added dropwise 65 parts of distillations
Water, separates organic layer, and aqueous phase is extracted two to three times with 10 parts of dichloromethane, merges organic faciess the sodium bicarbonate solution with saturation
Neutralization so as to ph value is 7-8, concentrated by rotary evaporation obtain lurid containing chlordantoin.In the 100ml equipped with stirring magneton and condensing tube
5.25 parts of brominated glycolylureas, 3.5 parts of acrylic acid Of and 30 parts of ethanol are added in three neck round bottom flask, anti-at 75 DEG C
Answer 8 hours, be spin-dried for Rotary Evaporators.Finally make solvent with dichloromethane, add 10 parts of sodium hypobromites to react 6 hours, decompression
Leach out the small molecules such as organic bromine, dichloromethane, obtain, containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial, there is following institute
The structure shown:
Embodiment 3
10.65 parts of 5,5- dimethyl hydantion, 4.65 parts of Sodium ethylate and 150 parts of ethanol are added in 250ml there-necked flask,
Equipped with the device with condensing tube for the stirring magneton, half an hour is stirred at room temperature, continues to add 11.5 parts of 2- bromo- in there-necked flask
1- ethanol, reacts 12 hours under conditions of 60 DEG C, is removed by filtration the sodium bromide generate in course of reaction, does eluting with ethanol
Agent, removes unreacted 5,5- dimethyl hydantion and unnecessary Sodium ethylate by crossing pillar, obtains glycolylurea alcohol by being evaporated under reduced pressure.
The glycolylurea alcohol of generation is dissolved in 30 parts of oxolanes, under conditions of ice-water bath, 50 parts of pcl of Deca thereto3, persistently stir
Mix 2 hours, water-bath is slowly heated, be warming up to 75 DEG C and be incubated 3 hours, track to reaction with thin layer chromatography and finish, be cooled to room
Temperature, is slowly added dropwise 200 parts of distilled water, separates organic layer under ice-water bath, aqueous phase is extracted two to three times with 30 parts of dichloromethane, merges
Organic faciess are simultaneously neutralized so as to ph value is 7～8 with the sodium bicarbonate solution of saturation, and concentrated by rotary evaporation obtains the brominated glycolylurea of yellow.?
Add 15.75 parts of brominated glycolylureas, 10 parts of propylene diethylammonium salts equipped with the 250ml three neck round bottom flask with condensing tube for the stirring magneton
Base propyl ester and 100 parts of ethanol, react 8 hours under conditions of 75 DEG C, are spin-dried for Rotary Evaporators.Finally made molten with dichloromethane
Agent, adds 30 parts of t-butyl hypochlorates to react 6 hours, decompression leaches out the small molecules such as organochlorine, dichloromethane, obtains containing double
Key, quaternary ammonium salt and halogen amine difunctionality antibacterial, have a structure shown below:
The Application Example containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial of present invention synthesis is as follows:
Application example 1:
The difunctionality antibacterial that prepare embodiment 1 in 1g specific embodiment and 0.04g azodiisobutyronitrile are dissolved in
In 30ml toluene, it is subsequently adding the polystyrene microsphere of the crosslinking that 20g average diameter is 10 microns, stir 30 minutes under room temperature,
Then toluene is removed under reduced pressure, reaction 10 minutes at 100 DEG C is so that penetrate into the difunctional sterilization of crosslinked polystyrene microsphere
The double-bond polymerization of agent, is obtained the polystyrene microsphere with sterilizing ability.Stenlizing layer thickness is 20 microns.Microsphere is loaded diameter
For 0.5cm, in the glass tubing of high 10cm, make Filter column, filtering golden yellow staphylococcus and e. coli concentration is 106-107cfu/
The aqueous solution of ml, under flow velocity is for 4ml/min, can kill in water 99.999% antibacterial.
Application example 2:
The difunctionality antibacterial of example 2 preparation in 2g specific embodiment, Ran Houjia is added in 100ml there-necked flask bottle
Enter 0.6g containing hydrogen silicone oil, 0.1ml platinum catalyst, the anhydrous benzophenone of 50ml, under nitrogen atmosphere, under conditions of 110 DEG C, reaction 5 is little
When, be there is silicon hydrogenation in the double bond of the si-h key of containing hydrogen silicone oil and antibacterial, prepare polysiloxanes antibacterial.Reaction knot
Restraint and cool down, cotton is soaked in this solution 10min.After immersion finishes, take out cotton and dry, stenlizing layer thickness is received for 90
Rice.Depletion Huang staphylococcus and each 100 μ l of escherichia coli, concentration is 1.3 × 106The solution of cfu/ml, Deca is in two pieces of 2cm2Coating
On the cotton of upper polysiloxanes antibacterial, after contact 10min, the mortality rate of escherichia coli and staphylococcus aureus can reach
100%.Using uncoated cotton as a control group, colibacillary mortality rate is 7%, and the mortality rate of golden yellow staphylococcus is
8%, these mortality rates are that natural death causes.
Application example 3:
0.1g specification for 5dtex polypropylene fiber put into the heptane containing 5ml 10wt.% benzophenone and dehydrated alcohol (5:
1), in solution, soak 10 hours.Then the ultraviolet using 365 nanometers of wavelength irradiates 30 minutes under argon protection.After immersion
Fiber is put in the ethanol solution of difunctionality antibacterial of example 3 preparation in the specific embodiment of 10wt%, continues purple
External exposure 30 minutes, is finally incubated 5 hours at 55 DEG C.1 micron of the polymer of monomer 2 and polypropylene are connected on polypropylene fiber
IPN layer, this fiber is put in the open marine site that water temperature is 20 DEG C, in 2 weeks, no algae and Mollusca are attached to fiber
On.The silk screen of this cellosilk preparation longer can keep clean, frequently need not remove aquatic animals and plants, thus reducing labor
Fatigue resistance.
Application example 4:
The thin slice that 8 × 8 centimetres of poly- (TFE copolymer-hexafluoropropene), is 13.56mhz with frequency, pressure is
60pa, power is the o of 40w2Plasma, all processes 60 seconds to two sides.Then this thin slice is put into containing 40 parts of specific embodiment parties
Example 1 product in formula, 0.001 part of 2,2'- azo is double (4- methoxyl group -2,4- methyl pentane nitrile), 0.01 part of dithiobenzoic acid
In withered ester, and the 50ml methanol solution of 5 parts of dimethylanilines, react 6 hours at 80 DEG C, poly- (TFE copolymer-hexafluoro third
Alkene) it is grafted the polymer of example 1 product in 15 nanometers of specific embodiment.Take the culture e coil k 1 pneumonia of 18 hours
Bacterium, with the phosphate buffered solution for 6.8 for the ph value be formulated as 50ml, concentration be 1.50 × 105The solution of cfu/ml.Connect above-mentioned
On branch, stenlizing layer thin slice is put in this Klebsiella pneumonia solution, shakes 1 hour at 25 DEG C.99.99% lung in solution
Scorching klebsiella is killed.Using the matched group of non-grafted poly- (TFE copolymer-hexafluoropropene) thin slice, pneumonia gram
Because of the reason natural death, mortality rate is only 1% to the primary Salmonella of thunder.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial it is characterised in that: there is formula () structure:
Wherein, r1、r2Be respectively methyl or ethyl any one；
X is any one in cl or br；
Y is any one in cl or br；
M, n are arbitrary integer between 1～5.
2. a kind of preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial according to claim 1, its feature
It is, comprise the following steps:
1) 5,5- dimethyl hydantion and alkali reaction half an hour, it is subsequently adding bromine hydroxyl alcohol and nucleophilic substitution occurs, generate 3- hydroxyl
Alkyl -5,5- dimethyl hydantion；
2) by step 1) product that obtains of reaction carries out halogenating reaction with phosphorus trihalide, generates 3- brine alkyl -5,5- dimethyl sea
Cause；
3) by step 2) product that generates carries out quaternization reaction with acrylic acid dihydroxy amido hydroxyl ester；
4) by step 3) product that generates processes with halide reagent, and the n-h key of amide in glycolylurea ring is generated halogen amine sterilization group
N-x key.
3. a kind of preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial according to claim 2, its feature
Be, described step 1) in bromine hydroxyl alcohol there is formula () structure:
Wherein, m is integer, m=1～5.
4. a kind of preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial according to claim 2, its feature
Be, described step 3) in acrylic acid dihydroxy amido hydroxyl ester there is formula () structure:
Wherein, n is integer, n=1～5；
r1、r2Any one for methyl or ethyl.
5. a kind of preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial according to claim 2, its feature
Be, described step 1) in alkali used be any one in potassium hydroxide or Sodium ethylate.
6. a kind of preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial according to claim 2, its feature
Be, described step 3) in adopt halide reagent be: t-butyl hypochlorate, the Hydrogen oxybromide (HOBr) tert-butyl ester, sodium hypochlorite or Hydrogen oxybromide (HOBr)
Any one in sodium.
7. a kind of preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial according to claim 2, its feature
It is, the response time of described solution is 2～20 hours.
8. a kind of preparation method containing double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial according to claim 2, its feature
It is, the reaction temperature of described solution is 20～100 DEG C.
9. a kind of application containing as claimed in claim 1 double bond, quaternary ammonium salt and halogen amine difunctionality antibacterial it is characterised in that
Antibacterial is used in the form of forming sterilization coating in material surface, and stenlizing layer thickness is at 5 nanometers～5 microns.
10. a kind of containing as claim 1) face coat of antibacterial as described in formula ().
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| CN113336783A (en) * | 2021-06-22 | 2021-09-03 | 山东科技大学 | Multifunctional silane bactericide with surface migration characteristic and preparation and application thereof |
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| CN113336783A (en) * | 2021-06-22 | 2021-09-03 | 山东科技大学 | Multifunctional silane bactericide with surface migration characteristic and preparation and application thereof |
| CN113336783B (en) * | 2021-06-22 | 2022-07-15 | 山东科技大学 | Multifunctional silane bactericide with surface migration characteristic and preparation and application thereof |
| CN115340698A (en) * | 2022-08-16 | 2022-11-15 | 常州工业职业技术学院 | Medical antibacterial material and preparation method and application thereof |
| CN115340698B (en) * | 2022-08-16 | 2023-10-27 | 常州工业职业技术学院 | Medical antibacterial material and preparation method and application thereof |
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