CN106928158B - Antimicrobial compound and its application in textile industry - Google Patents
Antimicrobial compound and its application in textile industry Download PDFInfo
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- CN106928158B CN106928158B CN201511025785.9A CN201511025785A CN106928158B CN 106928158 B CN106928158 B CN 106928158B CN 201511025785 A CN201511025785 A CN 201511025785A CN 106928158 B CN106928158 B CN 106928158B
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
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- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/38—Sulfur atoms
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- C07D—HETEROCYCLIC COMPOUNDS
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- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/44—One nitrogen atom with halogen atoms attached to the two other ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/47—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds
- D06M13/477—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds having six-membered heterocyclic rings
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
This application provides novel antimicrobial compound, active group (R) is used as antibacterial functional group as reactable functional group and betaine group (B), has general formula R-X-B structure, and wherein X is connection abutment.The chemical bonding of covalency can occur with textile fiber for such antibacterial agent, be not easy to fall off or dissolve out from textile fiber surface, with good stability, to assign textile lasting antibacterial activity.Meanwhile the preparation process of such antibacterial agent is simple, mild condition is easy to industrialization, is suitble to textile dyeing and finishing synchronous, is particularly suitable in textile industry, is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of antimicrobial compound, which it is anti-can to further relate to this enduringly in conjunction with textile
The preparation method of bacterium compound and its application in textile industry.
Background technique
Under certain temperature and humidity environment, it is very easy to cooperating microorganisms and bacterium, great Liang Fan on the textile
After growing, not only it is easy to keep fabric mouldy, brittle, the dress and use of fabric is impacted；And a large amount of microorganisms and bacterium
Attachment on the fabric easily causes the generation of the symptoms such as peculiar smell, itch, redness, allergy, the inflammation of human skin, to human body
Health care belt carrys out detrimental effect.With the development and progress of society and improvement of living standard, people resist daily textile
Bacterium performance produces great demand.Therefore, textile of the exploitation with lasting excellent antibacterial performance has greatly urgent
Property and necessity.In the clothing of the textile and dress that use in people's daily life, the overwhelming majority is all natural fiber
The textile of class, especially using cotton fiber as the cellulose fiber textile of representative, therefore mainly exploitation has anti-microbial property
Cotton fabric.
Antibacterial fabric typically refers to arrange textile using antibacterial agent, enables the textile after arranging
It enough allows the bacterium microbe of attachment on the textile dead, or is able to suppress the growth of bacterium microbe on the textile
Breeding.Currently, the antibacterial agent used both at home and abroad mainly includes four classes: (1) inorganic antibacterial agent；(2) organic antibacterial agent；(3)
Natural antimicrobial agent；(4) macromolecular antibacterial agent.
Inorganic antibacterial agent, the micro-nano granules of mainly some inorganic substances commonly include titanium dioxide, silver, gold
Equal heavy metals.Its anti-microbial property is mainly derived from the sulfhydryl-group activity that these micro-nano particles act in bacterium zymoprotein, destroys thin
The activity of bacterium zymoprotein.But the attachment fastness of this kind of antibacterial agent on the textile is low, is easy in the use process of textile
It falls off, not only reduces anti-microbial property, but also these micro-nano particles to fall off are easy to cause harm to the human body.In addition, these
After inorganic micro-nano particle arranges on the textile, it is easy the micro gap of blocking textile fiber, increases the hardness of textile,
Gas permeability, the feel for influencing fiber, to influence the snugness of fit of textile.
Organic antibacterial agent mainly includes the types such as quaternary ammonium salt, N- halogen amine, trichlorophenol, biguanides.The antibacterial agent of this type
Anti-microbial property with wide spectrum mainly generates anti-microbial property by destroying membrane structure.But this kind of antibacterial agent is easy
It falls off from textile, to reduce the antibacterial activity of textile.In addition, quaternary ammonium salt antibacterial agent skin irritation is stronger；N-
Halamine antibacterial agent is easy to produce remaining halogen in use and is easy that textile is made to turn to be yellow, and generates bad peculiar smell；Trichlorine
Phenolic antiseptic is easy to produce the carcinogenic substance containing chlorine, is prohibited from using in many countries and regions；And biguanides antibacterial agent
Light resistance, chlorine-resistant drift performance it is poor.
Natural antimicrobial agent, mainly some natural extracts, most commonly chitosan have preferable bio-compatible
Property, Antibacterial Mechanism is mainly the synthesis for inhibiting bacterio protein DNA.But the pH tolerance of this kind of antibacterial agent is poor, resists
Bacterium activity is relatively low, and water-soluble poor.
High score subclass antibacterial agent mainly includes two types, is obtained one is carrying out structurally-modified to natural antimicrobial agent
Antibacterial agent, another kind of is the design feature according to organic antibacterial agent and natural antibacterial agent, the similar macromolecule of composite structure
Polymer is as antibacterial agent.The problem of thermal stability of this kind of antibacterial agents is poor, and there is also stripping properties.
The antibacterial agent of these above-mentioned types is in use, is applied on textile and is resisted generally by the method for arrangement
Bacterium textile, arrangement process are divided into treatment before dyeing and dye final finishing.After arranging, antibacterial agent is attached by way of physical action
On the textile.In the use process of textile, these antibacterial agents without immobilization are easy to be lost from textile, lead
The antibacterial activity of textile is caused to lack persistence, and the antibacterial agent being lost enters and can also cause negative shadow in environment to environment
It rings.Antibacterial agent is fixed in the form of chemical bond on the fiber of textile, antibacterial agent would not dissolve out on the textile
The losing issue of property, can assign textile lasting anti-microbial property, while avoiding negative effect of the losing issue to environment.Gram
Take current antibacterial agent existing all kinds of problem in application process, exploitation it is a kind of it is novel can immobilization it is anti-with persistence
The antibacterial agent of bacterium performance is the new development requirement in antibacterial agent field.
Summary of the invention
The purpose of the present invention is to provide a kind of novel antimicrobial compounds, such compound can be by molecular structure
Reactive functional groups firmly combined in a manner of chemical bond with textile fiber, so that textile be made to obtain lasting antibacterial
Performance.
According to the one aspect of the application, reactable glycine betaine antimicrobial compound provided by the invention is by glycine betaine function
Group (B), abutment (X), reactive functional groups (R) three parts composition, have general formula I:
R-X-B。
According to some embodiments of the application, in general formula I, the glycine betaine functional group (B) can have general formula
The structure of II:
Wherein
R1It is-H or-(CH2)mCH3, wherein m=0~17 (such as m=0,1,2 or 3)；
R2Selected from-(CH2)nNH(CH2)p, wherein n, p=0~6；-(CH2)q, wherein q=1~10 (such as q=1,2,3,
4,5 or 6)；
R3It is-H or-(CH2)mCH3, wherein m=0~17 (such as m=0,1,2 or 3)；
R4Selected from-(CH2)r, wherein r=1~6 (such as r=3), or-(CH2)sNH(CH2)t, wherein s, t=1~10 are (such as
1~6)；
Y is selected from-COO ,-SO3。
In above-mentioned general formula II, substituent R1And R3It is identical group or different groups.
According to some embodiments of the application, in above-mentioned general formula I, the glycine betaine functional group (B) can also have
There is the structure of general formula III:
Wherein,
R4Selected from-(CH2)r, wherein r=1~6 (such as r=3)；Or selected from-(CH2)sNH(CH2)t, wherein s, t=1~
10 (such as 1~6)；
Y is selected from-COO ,-SO3；
R5It selected from-O ,-S or-NH or is R2；Wherein, R2The same Formula II of definition.
According to some embodiments of the application, in above-mentioned general formula I, the reactable glycine betaine antimicrobial compound
In abutment functional group X be-NH- ,-O- ,-S- or be not present；
According to some embodiments, the antimicrobial compound of the application is expressed from the next:
Wherein, R4、R5Definition with Y is the same as defined in formula III as above.
In some embodiments, the R in formula IV5For-NH- ,-O- or-S-.
According to some embodiments of the application, in above-mentioned general formula I, the reactive functional groups R includes: s-triazine
Class, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) class, miazines and their combination.
In above-mentioned general formula I, the reactive functional groups R can be s-triazine reactive functional groups, have general formulae IV:
Wherein, Z1=F, Cl；Z2=F, Cl (Z1、Z2Can be identical, such as be all Cl)；Or Z1、Z2Having one is F or Cl；Separately
One is vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) reactive functional groups described in general formula II or III, e.g.
Wherein q=0.
In above-mentioned general formula I, the reactive functional groups R is also possible to pyrimidine reactive functional groups, has general formula V:
Wherein, Z3=F, Cl；Z4=F, Cl；Z5=F, Cl (Z3~Z5Can be identical, such as be all Cl)；Or Z3、Z4、Z5In have one
It is a or two are vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) reactive functional groups described in general formula II or III, e.g.
Wherein q=0；Remaining is F or Cl.
In above-mentioned general formula I, the reactive functional groups R is also possible to vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) reactive functional groups, has as follows
Structure (is commonly referred to as general formula VI):
In the above formulas, X is selected from-NH- ,-O- or-S-；Q is selected from 0~10；
R6Selected from-OH ,-NH2,-NO2,-O (CH2)mCH3,-(CH2)mCH3,-(XCH2CH2)mCH3；Wherein, X is selected from-NH-
Or-O-；M is selected from 0~17.
According to some embodiments of the application, in general formula VI, as q=0, indicate that number is that the group of q is not present；When
When q=1~10, q for example can be 1~6,1~2.Similarly, it as m=0, indicates that number is that the group of m is not present, works as m=
When 1~17, m for example can be 1~6,1~2).
According to some embodiments, the antimicrobial compound of the application is selected from following compound:
According to the another aspect of the application, this application provides a kind of systems of above-mentioned reactable glycine betaine antimicrobial compound
Preparation Method comprising step:
The betaine compound structure containing hydroxyl or amino is produced, and it is provided with described in general formulae IV, V, VI
The reactant of reactive functional groups structure reacts 1~48 hour under conditions of 0~70 DEG C of temperature.By above-mentioned reactant through supersalt
Analysis, filtering or centrifuge separation purification, obtain target product.
The above-mentioned betaine compound containing hydroxyl or amino the preparation method comprises the following steps: by the chemical combination containing tertiary amine or pyridine
Object reacts 1~72 hour under conditions of 10~120 DEG C of temperature with acid compound.Above-mentioned acid compound is in propane sulfonic acid
Ester, butyl sultone, acrylic acid, β-propiolactone, X1(CH2)uSO3 -Or X1(CH2)uCO2 -One of, wherein X1Be F, Cl,
Br or I, u are the integer (integer of such as 1-10,1-6) equal to or more than 1.
The novel antibacterial compounds of the application have reactive functional groups --- active group, can occur with textile fiber
Covalent bonding assigns the anti-microbial property lasting by the textile material arranged to avoid the dissolution and loss of antibacterial agent.It should
The synthesis technology of the novel antibacterial agent of class is simple, and mild condition is easily controllable, has extensive industrial application prospect.As it can be seen that
The antimicrobial compound of the application can be used in textile industry, especially in textile.
Embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
It is of the invention in limiting.
Embodiment 1
44.6g N is weighed, N- dimethylethanolamine is dissolved in 150mL dehydrated alcohol, and is added to mechanical stirring
In the round-bottomed flask of reflux unit, the ethanol solution 300mL containing 61.5g propane sultone is added under stiring.Add
Room temperature continues to stir 2h after complete, obtains white depositions, after being centrifugated, washing purifying, ethyl alcohol recycling, obtains containing hydroxyl
The tertiary amine glycine betaine of base.The tertiary amine glycine betaine is dissolved in 500mL deionized water and is added to churned mechanically round-bottomed flask
In, 5~10 DEG C are cooled to, 92g Cyanuric Chloride fine powder is added under stiring.After mixing evenly, it is added in batches under stiring
26g sodium carbonate is dissolved in the solution of 50mL deionized water.The reaction was continued after adding 2~3h.Then it is slowly added into the reaction solution
Potassium acetate to product is precipitated, and after filtering and being washed with dehydrated alcohol, vacuum drying is obtained with Cyanuric Chloride active group
Tertiary amine glycine betaine antibacterial agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines saturation C-H absorption peak
2992cm-1, triazine ring absorption peak 1600cm-1, sulfonic group absorption peak 1193 and 1036cm-1, consistent with above structure.
Embodiment 2
Using N, N in TMSDMA N dimethylamine base ethanethiol hydrochloride alternate embodiment 1, N- dimethylethanolamine can be made
Above-mentioned antibacterial agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines saturation C-H absorption peak 2991cm-1, three
Piperazine ring absorption peak 1599cm-1, sulfonic group absorption peak 1193 and 1037cm-1, consistent with above structure.
Embodiment 3
Using N-BOC-N, sweet tea can be made in N in N- dimethyl-ethylenediamine alternate embodiment 1, N- dimethylethanolamine
Dish alkali antibacterial agent.It is dissolved in water, adjusts pH value of solution to 1 or so, after stirring 2 hours, be cooled to 5~10 DEG C, stirring
The lower Cyanuric Chloride fine powder and sodium carbonate liquor that equimolar amounts is added.After having reacted, after the processing method of embodiment 1
Reason, obtains the glycine betaine antibacterial agent of above structure.Its characteristic group's structure is analyzed using infrared spectroscopy, determines N-H
Absorption peak 3474cm-1, saturation C-H absorption peak 2993cm-1, triazine ring absorption peak 1601cm-1, 1193 and of sulfonic group absorption peak
1036cm-1, consistent with above structure.
Embodiment 4
It weighs 103g 4- (N, N- dimethylamino) phenyl-beta-hydroxyethyl sulfone sulfate and is dissolved in 300mL dehydrated alcohol
In, and be added in the round-bottomed flask with mechanical stirring and reflux unit, it is kept stirring.It is added at room temperature and contains 41g third
The ethanol solution 200mL of sultones.The reaction was continued after adding 3h, obtains white depositions, by being centrifugated, washing
After purifying, ethyl alcohol recycling, obtain containing vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) active group tertiary amine glycine betaine antibacterial agent.Using infrared spectroscopy to its feature function
Unity structure is analyzed, and determines unsaturation C-H absorption peak 3042cm-1, saturation C-H absorption peak 2778cm-1, aromatic ring absorption peak
1608cm-1, sulfonic group absorption peak 1155 and 1037cm-1, consistent with above structure.
Embodiment 5
The tertiary amine glycine betaine containing hydroxyl is prepared according to the method for embodiment 1.The tertiary amine glycine betaine is dissolved in 500mL
Deionized water is simultaneously added to in churned mechanically round-bottomed flask, being cooled to about 10 DEG C.108.5g 2,4 is added under stiring,
5,6- tetrachloro-pyrimidine fine powders are added 26g sodium carbonate in batches under stiring and are dissolved in the molten of 50mL deionized water after mixing evenly
Liquid.The reaction was continued after adding 3~5h.Then it is slowly added into potassium acetate to product into the reaction solution to be precipitated, by filtering, is used in combination
After dehydrated alcohol washing, vacuum drying obtains the tertiary amine glycine betaine antibacterial agent with trichloropyrimidine active group.Using infrared spectroscopy
Its characteristic group's structure is analyzed, determines saturation C-H absorption peak 2993cm-1, pyrimidine ring absorption peak 1598cm-1, sulfonic acid
Base absorption peak 1192 and 1034cm-1, consistent with above structure.
Embodiment 6
Cyanuric Chloride is substituted with 2,4,5,6- tetrachloro-pyrimidines, this glycine betaine antibacterial is prepared according to the method for embodiment 2
Agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines saturation C-H absorption peak 2951cm-1, pyrimidine ring absorb
Peak 1599cm-1, sulfonic group absorption peak 1193 and 1034cm-1, consistent with above structure.
Embodiment 7
Cyanuric Chloride is substituted with 2,4,5,6- tetrachloro-pyrimidines, this glycine betaine antibacterial is prepared according to the method for embodiment 3
Agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines N-H absorption peak 3481cm-1, saturation C-H absorption peak
2990cm-1, pyrimidine ring absorption peak 1600cm-1, sulfonic group absorption peak 1193 and 1035cm-1, consistent with above structure.
Embodiment 8
It weighs 95.1g 2 hydroxy pyrimidine to be dissolved in 300mL dehydrated alcohol, and is added to mechanical stirring and reflux
In the round-bottomed flask of device, the ethanol solution 600mL containing 123g propane sultone is added under stiring.45 after adding
~50 DEG C of the reaction was continued 2h, obtain white depositions, after being centrifugated, washing purifying, ethyl alcohol recycling, obtain containing hydroxyl
Pyridine betaine.The pyridine betaine is dissolved in 1000mL deionized water and is added to churned mechanically round-bottomed flask
In, 5~10 DEG C are cooled to, 184g Cyanuric Chloride fine powder is added under stiring and is added in batches under stiring after mixing evenly
53g sodium carbonate is dissolved in the solution of 100mL deionized water.The reaction was continued after adding 3~4h.Then it is slowly added into the reaction solution
Potassium acetate to product is precipitated, and after filtering and being washed with dehydrated alcohol, vacuum drying is obtained with Cyanuric Chloride active group
Pyridine betaine antibacterial agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines unsaturation C-H absorption peak
3045cm-1, saturation C-H absorption peak 2828cm-1, heteroaromatic absorption peak 1605cm-1, sulfonic group absorption peak 1153 and 1032cm-1,
It is consistent with above structure.
Embodiment 9
2 hydroxy pyrimidine is substituted with 2- mercaptopyridine, this glycine betaine antibacterial agent is prepared according to the method for embodiment 8.It adopts
Its characteristic group's structure is analyzed with infrared spectroscopy, determines unsaturation C-H absorption peak 3044cm-1, saturation C-H absorption peak
2829cm-1, heteroaromatic absorption peak 1604cm-1, sulfonic group absorption peak 1153 and 1032cm-1, consistent with above structure.
Embodiment 10
N-BOC-N is substituted with N-BOC-2- aminopyridine, N- dimethyl-ethylenediamine is prepared into according to the method for embodiment 3
To this glycine betaine antibacterial agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines unsaturation C-H absorption peak
3045cm-1, saturation C-H absorption peak 2808cm-1, heteroaromatic absorption peak 1603cm-1, sulfonic group absorption peak 1154 and 1032cm-1,
It is consistent with above structure.
Embodiment 11
The pyridine betaine containing hydroxyl is prepared according to the method for embodiment 8.The pyridine betaine is dissolved in 750mL
Deionized water is simultaneously added to in churned mechanically round-bottomed flask, being cooled to about 10 DEG C.217g 2,4,5 is added under stiring,
6- tetrachloro-pyrimidine fine powder is added 53g sodium carbonate in batches under stiring and is dissolved in the molten of 80mL deionized water after mixing evenly
Liquid.The reaction was continued after adding about 5h.Then it is slowly added into potassium acetate to product into the reaction solution to be precipitated, by filtering, is used in combination
After dehydrated alcohol washing, vacuum drying obtains the pyridine betaine antibacterial agent with trichloropyrimidine active group.Using infrared spectroscopy
Its characteristic group's structure is analyzed, determines unsaturation C-H absorption peak 3039cm-1, saturation C-H absorption peak 2835cm-1、
Heteroaromatic absorption peak 1610cm-1, sulfonic group absorption peak 1155 and 1037cm-1, consistent with above structure.
Embodiment 12
Cyanuric Chloride is substituted with 2,4,5,6- tetrachloro-pyrimidines, this glycine betaine antibacterial is prepared according to the method for embodiment 9
Agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines unsaturation C-H absorption peak 3044cm-1, saturation C-H
Absorption peak 2830cm-1, heteroaromatic absorption peak 1611cm-1, sulfonic group absorption peak 1155 and 1032cm-1, consistent with above structure.
Embodiment 13
Cyanuric Chloride is substituted with 2,4,5,6- tetrachloro-pyrimidines, this glycine betaine antibacterial is prepared according to the method for embodiment 10
Agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines unsaturation C-H absorption peak 3081cm-1, saturation C-H
Absorption peak 2837cm-1, heteroaromatic absorption peak 1613cm-1, sulfonic group absorption peak 1155 and 1032cm-1, consistent with above structure.
Embodiment 14
The pyridine betaine antibacterial agent with Cyanuric Chloride active group is prepared according to the method for embodiment 8.Weigh 1/4
Product prepared by part embodiment 4, is dissolved in 800mL deionized water.Then, 70.3g 4- aminobenzene is added into the reaction solution
Base-beta-hydroxyethyl sulfone sulfate and 13.3g sodium carbonate aqueous solution, the reaction was continued at 50~55 DEG C 3h.After the reaction was completed, to
It is slowly added into potassium acetate to product in the reaction solution to be precipitated, after filtering and being washed with dehydrated alcohol, vacuum drying is obtained
Double-active radical glycine betaine antibacterial agent with Cyanuric Chloride active group and ethylene sulfuryl active group.Using infrared spectroscopy to its feature
Structure of functional groups is analyzed, and determines unsaturation C-H absorption peak 3044cm-1, saturation C-H absorption peak 2826cm-1, aromatic ring absorb
Peak 1606cm-1, sulfonic group absorption peak 1153 and 1034cm-1, consistent with above structure.
Embodiment 15
2 hydroxy pyrimidine is substituted with 2- mercaptopyridine, this glycine betaine antibacterial is prepared according to the method for embodiment 8 and 14
Agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines unsaturation C-H absorption peak 3044cm-1, saturation C-H
Absorption peak 2778cm-1, aromatic ring absorption peak 1607cm-1, sulfonic group absorption peak 1154 and 1036cm-1, consistent with above structure.
Embodiment 16
2 hydroxy pyrimidine is substituted with N-BOC-2- aminopyridine, this beet is prepared according to the method for embodiment 8 and 14
Alkali antibacterial agent.Its characteristic group's structure is analyzed using infrared spectroscopy, determines unsaturation C-H absorption peak 3045cm-1, it is full
With C-H absorption peak 2829cm-1, aromatic ring absorption peak 1606cm-1, sulfonic group absorption peak 1153 and 1032cm-1, with above structure one
It causes.
The test of antibacterial activity
Cotton fabric to be arranged is impregnated in the aqueous solution of compound 1.5% obtained by above-described embodiment, is taken out after 3 minutes
60 DEG C drying, through over cleaning, dry after obtain the cotton fabric with sustainable antimicrobial activity.(every time according to the test method of AATCC
Washing 9 minutes), its antibacterial activity is tested using colony counting method, the results are shown in Table 1.
The Analysis of Antimicrobial Activity of the antimicrobial compound of 1 embodiment 1-16 of table
E.coli: Escherichia coli 8099；Staphylococcus aureus (S.aureas): ATCC 6538.
Embodiment described above is only several embodiments of the invention, and the description thereof is more specific and detailed, can not
Therefore limitations on the scope of the patent of the present invention are interpreted as.It should be pointed out that for those of ordinary skill in the art, not
Under the premise of being detached from present inventive concept, other several improvements and changes can also be made, these are all to belong to protection of the invention
Range.
Claims (8)
1. a kind of antimicrobial compound, it is characterised in that: the antimicrobial compound is by glycine betaine functional group (B), abutment (X), reaction
Property functional group's (R) three parts composition, indicated by general formula I:
R-X-B；
Wherein, the reactive functional groups R is selected from s-triazine reactive functional groups, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) reactive functional groups, pyrimidine reaction
Property functional group and their any combination；
The structure of glycine betaine functional group (B) is indicated by following general formula II:
Wherein,
R1It is-H or-(CH2)mCH3, wherein integer of the m in 0~17；
R2Selected from-(CH2)q, the wherein integer in q=1~6；Or
R3It is-H or-(CH2)mCH3, the wherein integer in m=0~17；
R4Selected from-(CH2)r, the wherein integer in r=1~6；
Y is selected from-COO or-SO3；
Substituent R1And R3It is identical group or different groups；Or
The structure of glycine betaine functional group (B) is indicated by following general formula III:
Wherein,
R4Selected from-(CH2)r, the wherein integer in r=1~6；
Y is selected from-COO or-SO3；
R5Selected from-O ,-S or-NH；
Abutment X in the antimicrobial compound is-NH- ,-O- ,-S- or is not present；
The reactive functional groups R is s-triazine reactive functional groups, with general formulae IV:
Wherein, Z1=F, Cl；Z2=F, Cl；Or Z1、Z2Having one is F or Cl；The other is
Wherein q=0；Or
The reactive functional groups R is pyrimidine reactive functional groups, has general formula V:
Wherein, Z3=F, Cl；Z4=F, Cl；Z5=F, Cl；
The vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) reactive functional groups are indicated by following structural formula:
-(CH2)qSO2CH2CH2OSO3H (1)
Wherein, integer of the q in 0~6.
2. antimicrobial compound according to claim 1, it is characterised in that: the structure of the glycine betaine functional group (B) is under
Formula indicates:
Wherein, R4、R5Definition with Y is the same as claim 1.
3. antimicrobial compound according to claim 1, it is characterised in that: the vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) reactive functional groups areWherein q=0.
4. antimicrobial compound according to claim 1, it is characterised in that:
In formula IV, Z1、Z2It is identical, it is all Cl；In Formula V, Z3~Z5It is identical, it is all Cl.
5. antimicrobial compound according to claim 1 is selected from following compound:
6. the preparation method of antimicrobial compound described in any one of claim 1 to 5 comprising following steps:
Produce the compound of the functional group containing glycine betaine containing hydroxyl, sulfydryl or amino, and by its with it is described in claim 1 anti-
Answering property structure of functional groups reacts 1~48 hour under conditions of 0~70 DEG C of temperature；Then reaction solution through oversalting, filtering or from
The heart carries out separating-purifying, obtains target product.
7. the preparation method of antimicrobial compound according to claim 6, which is characterized in that described contains hydroxyl, sulfydryl
Or the compound of the functional group containing glycine betaine of amino is made by following methods: by the compound containing tertiary amine or pyridine and acid
Compound reacts 1~72 hour under conditions of 10~120 DEG C of temperature；
Above-mentioned acid compound is selected from propane sultone, butyl sultone, acrylic acid, β-propiolactone, X1(CH2)uSO3 -Or X1
(CH2)uCO2 -One of, wherein X1It is F, Cl, Br or I, u is the integer equal to or more than 1.
8. application of the antimicrobial compound described in any one of claim 1 to 5 in textile industry.
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