CN110499091A - A kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-and its preparation method - Google Patents
A kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-and its preparation method Download PDFInfo
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Abstract
The present invention relates to antimicrobial coating technical fields, and disclose a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-and its preparation method, including formula as below raw material: 2, bis--carboxylphenylsulphonyl chloride of 6-, ammonium nitrate, catalyst, sodium hydroxide, the concentrated sulfuric acid, initiator, chitosan, nano silver, dispersing agent.A kind of chitin modified polyphenyl sulfonamide antimicrobial coating of the nano silver-and its preparation method, sulphonyl imine group in poly- carboxybenzenesulfonamide has very strong reproducibility, make antimicrobial coating that there is good bacteriostasis, chitosan has a large amount of reactive-OH groups, the higher electron-withdrawing group ester group of chemical energy is formed with the carboxyl esterification in poly- carboxybenzenesulfonamide, electrophilic ester group reduces the cloud density of sulfonyl by electronic effect, enhance the chemical energy of sulfonyl, improve the chemical stability and thermal stability of poly- carboxybenzenesulfonamide, make antimicrobial coating be not easy by air dioxygen oxidation or light degradation.
Description
Technical field
The present invention relates to antimicrobial coating technical field, and specially a kind of chitin modified polyphenyl sulfonamide antibacterial of nano silver-applies
Layer and its preparation method.
Background technique
Antibiotic paint is that there is the coating of antibacterial action to be known as antibiotic paint, build mildew resistant paint be mainly characterized by it is this kind of
Coating had both had excellent fungicidal properties, the attention with the mankind to self health status, the living environment that we are together morning and night
Also more and more attention has been paid to antibiotic paint can be directly painted in a variety of materials, and coating antibacterial agent mainly has natural anti-at present
Microbial inoculum, organic antibacterial agent and inorganic antiseptic three categories.Inorganic antiseptic especially nano silver, anti-microbial property are also far longer than biography
The silver ion disinfectant of system such as silver nitrate and flamazine, are novel high-efficient antibacterial agents, and organic antibacterial agent refers to organic
The organic matters such as acids, phenols, quaternary ammonium salt, benzimidazole are the antibacterial agent of antibacterial material.Organic antibacterial agent is many kinds of, root
Fungicide, preservative and mould inhibitor are commonly divided into according to its purposes.
But current nano silver antimicrobials are reduced and are received since nano silver is easy to that agglomeration formation Argent grain occurs
The specific surface area of meter Yin reduces the contact area of nano silver and mushroom, affects the antibacterial effect of nano silver, while organic anti-
The thermal stability and chemical stability of microbial inoculum are poor, and organic antibacterial agent is made to be easy to be thermally decomposed in actual application, or
By the dioxygen oxidation in air, material is made to lose anti-microbial property.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of chitin modified polyphenyl sulfonamide antibacterials of nano silver-to apply
Layer and its preparation method solve nano silver and are easy to that agglomeration formation Argent grain occurs, reduce the specific surface area of nano silver, drop
The problem of low contact area of nano silver and mushroom, while solving the thermal stability and chemical stability of organic antibacterial agent again
It is poor, make organic antibacterial agent be easy to be thermally decomposed in actual application, or the problem of by dioxygen oxidation in air.
(2) technical solution
To achieve the above object, the invention provides the following technical scheme: a kind of chitin modified polyphenyl sulfonamide of nano silver-
Antimicrobial coating and its preparation method, the formula material including following parts by weight proportion: 30-35 part 2, bis--carboxylphenylsulphonyl chloride of 6-,
32-38 parts of ammonium nitrate, 0.5-1.5 parts of catalyst, 3-6 parts of sodium hydroxides, the 0.4-1 parts of concentrated sulfuric acids, 0.1-0.5 parts of initiators, 10-
30 parts of chitosans, 3.5-6 parts of nano silvers, 0.5-2 dispersing agent.Preparation method includes and following experimental drug: absolute diformazan is sub-
Sulfone, ethyl acetate, distilled water, ethylene glycol, dilute hydrochloric acid.
Preferably, 2,6-, bis--carboxylphenylsulphonyl chloride structural formula isIts mass fraction is >=96.5%.
Preferably, NH in the ammonium nitrate4NO3Mass fraction be >=94.2%.
Preferably, the catalyst is palladium acetate (COO-)2Pd2+。
Preferably, mass fraction >=95.8% of the sodium hydroxide in NaOH.
Preferably, the chitosan is β-(1-4) -2-amino-2-deoxy-D-Glucose, and monomer molecule formula is
(C6H11NO4) N, molecular weight 350000-380000, deacetylation 70-80%.
Preferably, H in the concentrated sulfuric acid2SO4Mass fraction is >=92.5%.
Preferably, Ag in the nano silver2CO3Mass fraction >=98.2%.
Preferably, the dispersing agent is the mixture of stearmide and n-octyl alcohol, mass ratio 1-1.5:2-3.
Preferably, the substance withdrawl syndrome of the dilute hydrochloric acid is 1.5-2mol/L.
Preferably, absolute dimethyl sulfoxide water content≤0.05%.
Preferably, the chitin modified polyphenyl sulfonamide antimicrobial coating of the nano silver-, preparation method the following steps are included:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed,
400mL absolute dimethyl sulfoxide is being added, then is successively weighing 30-35 part 2, bis--carboxylphenylsulphonyl chloride of 6- and 32-38 parts of nitric acid
Ammonium after mixing evenly, then is successively slowly added to 3-6 parts of sodium hydroxides and 0.5-1.5 parts of catalyst, three-necked bottle is placed in water-bath
In be heated to 60-65 DEG C, and in N224-28h is at the uniform velocity stirred to react in atmosphere, reaction is observed by TLC thin layer chromatography
After fully reacting, the solution in three-necked bottle is transferred in 2000mL separatory funnel for reaction result, be added 500mL distilled water and
The extraction of 800mL ethyl acetate, takes ethyl acetate organic layer, and add 500mL distilled water and be extracted twice, will obtain ethyl acetate
Being evaporated under reduced pressure by Rotary Evaporators for organic layer removes ethyl acetate, then carries out concentration mixture by silica gel column chromatography
TLC separation, eluant, eluent are petroleum ether: ethyl acetate=3:1, and the isolated eluant, eluent containing product is enriched with, and
It is filtered by Rotary Evaporators vacuum distillation and oil pump, carries out that removing eluant, eluent is concentrated under reduced pressure, obtain product 2,6- bis--carboxyl benzene
Sulfonamide.
(2) it prepares poly- carboxybenzenesulfonamide and is added 200mL distilled water and 300mL ethylene glycol into 1000mL beaker, and according to
2,6-, bis--carboxybenzenesulfonamide, 10-30 part chitosan made from secondary addition and 0.1-0.5 parts of initiator sodium peroxydisulfates, and slowly
The 0.4-1 parts of concentrated sulfuric acids are added dropwise, are transferred the material into high temperature hydrothermal reaction kettle after mixing evenly, and reaction kettle is placed in reaction kettle
It is heated to 160-165 DEG C of reaction 10-12h in heater, is cooled to room temperature after fully reacting, the solution in reaction kettle is passed through into cloth
Family name's funnel filters removing solvent and obtains gray solid floccule, then is successively distilled using 200mL ethyl acetate and 3000-4000mL
Water washing solid floccule, is subsequently placed in baking oven and is heated to 80-85 DEG C, and dry moisture 8-10h obtains chitin modified poly- carboxylic
Base benzsulfamide.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL is added into 1000mL beaker
Distilled water and 100mL substance withdrawl syndrome are 1.5-2mol/L dilute hydrochloric acid, sequentially add poly- carboxyl made from above-mentioned steps (2)
Benzsulfamide, 3.5-6 part nano silver and 0.5-2 powder stearmide and n-octyl alcohol mixture, place the beaker ultrasonic processor
In, it is heated to 80-85 DEG C, supersonic frequency 28KHz carries out ultrasonic treatment 6-8h, is completely dispersed material uniformly, then will burn
Cup, which is placed in baking oven, is heated to 65-70 DEG C, slowly removes moisture, controls solid-to-liquid ratio 40-48%, obtains nano silver-chitosan and change
The antimicrobial coating of property polyphenyl sulfonamide.
(3) beneficial technical effect
Compared with prior art, the present invention has following beneficial technical effect:
1, a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of the nano silver-and its preparation method, pass through poly- carboxyl benzene sulfonyl
Matrix of the amine as coating, sulphonyl imine group therein have very strong reproducibility, and antimicrobial coating is made to have suppression well
Bacterium effect, while by chitin modified poly- carboxybenzenesulfonamide, chitosan has a large amount of activity hydroxy-OH group, and poly-
Carboxyl dehydration in carboxybenzenesulfonamide is esterified to form the higher electron-withdrawing group ester group of chemical energy, and the ester group of electron-withdrawing group is logical
Crossing electronic effect reduces the cloud density of sulfonyl, enhances the chemical energy of sulfonyl, to improve poly- carboxyl benzene sulphur
The chemical stability and thermal stability of amide, make antimicrobial coating be not easy by air dioxygen oxidation or light degradation, and
The polycation of chitosan is easy the group effect negatively charged with fungal cell surface, changes the stream of pathogen cell membrane
Dynamic property and permeability, to play the antibacterial and sterilization effect for promoting antimicrobial coating.
2, a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of the nano silver-and its preparation method, by the way that nano silver is added,
When touching the albumen oxygen metabolism enzyme in bacterium or fungi, nano silver will in protease have negative electrical charge mercapto-SH
With amino-NH2Specific binding reaction occurs, has effectively pierced through the cell wall and cell membrane appearance of pathogen or bacterium, into
One step makes bacterium or the intracorporal albumen oxygen metabolism enzyme deformation of fungi, loses activity, makes pathogen or bacterium eubolism and breeding,
Sterilizing is achieved the effect that, the unique mechanism of action for making thallus be choked to death can kill most of bacteriums being in contact with it, true
The microorganisms such as bacterium, mould, spore, and the chitosan being added has a large amount of amino-NH2With hydroxyl-OH group, can adsorb
Nano silver forms stable chelate, divides nano silver equably on chitosan surface, avoids nano silver and agglomeration occurs
The phenomenon that contact area of formation Argent grain, reduction nano silver and mushroom.
Specific embodiment
To achieve the above object, the invention provides the following technical scheme: a kind of chitin modified polyphenyl sulfonamide of nano silver-
Antimicrobial coating and its preparation method, the formula material including following parts by weight proportion: 30-35 part 2, bis--carboxylphenylsulphonyl chloride of 6-,
32-38 parts of ammonium nitrate, 0.5-1.5 parts of catalyst, 3-6 parts of sodium hydroxides, the 0.4-1 parts of concentrated sulfuric acids, 0.1-0.5 parts of initiators, 10-
30 parts of chitosans, 3.5-6 parts of nano silvers, 0.5-2 dispersing agent.Preparation method includes and following experimental drug: absolute diformazan is sub-
Sulfone, ethyl acetate, distilled water, ethylene glycol, dilute hydrochloric acid, 2,6- bis--carboxylphenylsulphonyl chloride structural formulas areIts quality point
Number is >=96.5%, NH in ammonium nitrate4NO3Mass fraction be >=94.2%, catalyst be palladium acetate (COO-)2Pd2+, hydrogen-oxygen
Change sodium in mass fraction >=95.8% of NaOH, chitosan is β-(1-4) -2-amino-2-deoxy-D-Glucose, monomer molecule
Formula is (C6H11NO4) N, molecular weight 350000-380000, deacetylation 70-80%, H in the concentrated sulfuric acid2SO4Mass fraction is
>=92.5%, Ag in nano silver2CO3Mass fraction >=98.2%, dispersing agent be stearmide and n-octyl alcohol mixture,
Mass ratio is 1-1.5:2-3, and the substance withdrawl syndrome of dilute hydrochloric acid is 1.5-2mol/L, absolute dimethyl sulfoxide water content≤
0.05%, the chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-, preparation method the following steps are included:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed,
400mL absolute dimethyl sulfoxide is being added, then is successively weighing 30-35 part 2, bis--carboxylphenylsulphonyl chloride of 6- and 32-38 parts of nitric acid
Ammonium after mixing evenly, then is successively slowly added to 3-6 parts of sodium hydroxides and 0.5-1.5 parts of catalyst, three-necked bottle is placed in water-bath
In be heated to 60-65 DEG C, and in N224-28h is at the uniform velocity stirred to react in atmosphere, reaction is observed by TLC thin layer chromatography
After fully reacting, the solution in three-necked bottle is transferred in 2000mL separatory funnel for reaction result, be added 500mL distilled water and
The extraction of 800mL ethyl acetate, takes ethyl acetate organic layer, and add 500mL distilled water and be extracted twice, will obtain ethyl acetate
Being evaporated under reduced pressure by Rotary Evaporators for organic layer removes ethyl acetate, then carries out concentration mixture by silica gel column chromatography
TLC separation, eluant, eluent are petroleum ether: ethyl acetate=3:1, and the isolated eluant, eluent containing product is enriched with, and
It is filtered by Rotary Evaporators vacuum distillation and oil pump, carries out that removing eluant, eluent is concentrated under reduced pressure, obtain product 2,6- bis--carboxyl benzene
Sulfonamide.
(2) it prepares poly- carboxybenzenesulfonamide and is added 200mL distilled water and 300mL ethylene glycol into 1000mL beaker, and according to
2,6-, bis--carboxybenzenesulfonamide, 10-30 part chitosan made from secondary addition and 0.1-0.5 parts of initiator sodium peroxydisulfates, and slowly
The 0.4-1 parts of concentrated sulfuric acids are added dropwise, are transferred the material into high temperature hydrothermal reaction kettle after mixing evenly, and reaction kettle is placed in reaction kettle
It is heated to 160-165 DEG C of reaction 10-12h in heater, is cooled to room temperature after fully reacting, the solution in reaction kettle is passed through into cloth
Family name's funnel filters removing solvent and obtains gray solid floccule, then is successively distilled using 200mL ethyl acetate and 3000-4000mL
Water washing solid floccule, is subsequently placed in baking oven and is heated to 80-85 DEG C, and dry moisture 8-10h obtains chitin modified poly- carboxylic
Base benzsulfamide.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL is added into 1000mL beaker
Distilled water and 100mL substance withdrawl syndrome are 1.5-2mol/L dilute hydrochloric acid, sequentially add poly- carboxyl made from above-mentioned steps (2)
Benzsulfamide, 3.5-6 part nano silver and 0.5-2 powder stearmide and n-octyl alcohol mixture, place the beaker ultrasonic processor
In, it is heated to 80-85 DEG C, supersonic frequency 28KHz carries out ultrasonic treatment 6-8h, is completely dispersed material uniformly, then will burn
Cup, which is placed in baking oven, is heated to 65-70 DEG C, slowly removes moisture, controls solid-to-liquid ratio 40-48%, obtains nano silver-chitosan and change
The antimicrobial coating of property polyphenyl sulfonamide.
Embodiment 1:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed,
400mL absolute dimethyl sulfoxide is being added, then is successively weighing 30 parts of 2,6-, bis--carboxylphenylsulphonyl chlorides and 32 parts of ammonium nitrate, is stirring
After mixing uniformly, then 3 parts of sodium hydroxides and 0.5 part of catalyst are successively slowly added to, three-necked bottle is placed in water-bath and is heated to 60
DEG C, and in N2It is at the uniform velocity stirred to react in atmosphere for 24 hours, reaction observes reaction result, fully reacting by TLC thin layer chromatography
Afterwards, the solution in three-necked bottle is transferred in 2000mL separatory funnel, 500mL distilled water and the extraction of 800mL ethyl acetate is added,
Ethyl acetate organic layer is taken, and adds 500mL distilled water and is extracted twice, steaming by rotation for ethyl acetate organic layer will be obtained
It sends out instrument vacuum distillation and removes ethyl acetate, mixture then will be concentrated by silica gel column chromatography and carry out TLC separation, elution
Agent is petroleum ether: ethyl acetate=3:1, and the isolated eluant, eluent containing product is enriched with, and is subtracted by Rotary Evaporators
Pressure distillation and oil pump filter, and carry out reduced pressure and remove eluant, eluent, obtain product 2, bis--carboxybenzenesulfonamide of 6- component 1.
(2) it prepares poly- carboxybenzenesulfonamide and is added 200mL distilled water and 300mL ethylene glycol into 1000mL beaker, and according to
2,6-, bis--carboxybenzenesulfonamide component, 1,30 part of chitosan and 0.1 part of initiator sodium peroxydisulfate made from secondary addition, and slowly drip
Add 0.4 part of concentrated sulfuric acid, transferred the material into high temperature hydrothermal reaction kettle after mixing evenly, and reaction kettle is placed in reaction kettle heating
It is heated to 160 DEG C of reaction 10h in device, is cooled to room temperature after fully reacting, the solution in reaction kettle is filtered by Buchner funnel
It removes solvent and obtains gray solid floccule, then is successively cotton-shaped using 200mL ethyl acetate and 3000mL distillation water washing solid
Object, is subsequently placed in baking oven and is heated to 80 DEG C, and dry moisture 8h obtains chitin modified poly- carboxybenzenesulfonamide component 1.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL is added into 1000mL beaker
Distilled water and 100mL substance withdrawl syndrome are 1.5mol/L dilute hydrochloric acid, sequentially add poly- carboxyl benzene made from above-mentioned steps (2)
1,3.5 part of nano silver of sulphonyl amine component and 0.5 powder stearmide and n-octyl alcohol mixture, place the beaker ultrasonic processor
In, 80 DEG C are heated to, supersonic frequency 28KHz carries out ultrasonic treatment 6h, is completely dispersed material uniformly, then sets beaker
It is heated to 65 DEG C in baking oven, slowly removes moisture, controls solid-to-liquid ratio 40%, obtains the chitin modified polyphenyl sulphonyl of nano silver-
The antimicrobial coating material 1 of amine.
Embodiment 2:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed,
400mL absolute dimethyl sulfoxide is being added, then is successively weighing 31 parts of 2,6-, bis--carboxylphenylsulphonyl chlorides and 33 parts of ammonium nitrate, is stirring
After mixing uniformly, then 4 parts of sodium hydroxides and 0.8 part of catalyst are successively slowly added to, three-necked bottle is placed in water-bath and is heated to 60
DEG C, and in N2It is at the uniform velocity stirred to react in atmosphere for 24 hours, reaction observes reaction result, fully reacting by TLC thin layer chromatography
Afterwards, the solution in three-necked bottle is transferred in 2000mL separatory funnel, 500mL distilled water and the extraction of 800mL ethyl acetate is added,
Ethyl acetate organic layer is taken, and adds 500mL distilled water and is extracted twice, steaming by rotation for ethyl acetate organic layer will be obtained
It sends out instrument vacuum distillation and removes ethyl acetate, mixture then will be concentrated by silica gel column chromatography and carry out TLC separation, elution
Agent is petroleum ether: ethyl acetate=3:1, and the isolated eluant, eluent containing product is enriched with, and is subtracted by Rotary Evaporators
Pressure distillation and oil pump filter, and carry out reduced pressure and remove eluant, eluent, obtain product 2, bis--carboxybenzenesulfonamide of 6- component 2.
(2) it prepares poly- carboxybenzenesulfonamide and is added 200mL distilled water and 300mL ethylene glycol into 1000mL beaker, and according to
2,6-, bis--carboxybenzenesulfonamide component, 2,25 parts of chitosans and 0.2 part of initiator sodium peroxydisulfate made from secondary addition, and slowly drip
Add 0.6 part of concentrated sulfuric acid, transferred the material into high temperature hydrothermal reaction kettle after mixing evenly, and reaction kettle is placed in reaction kettle heating
It is heated to 160 DEG C of reaction 12h in device, is cooled to room temperature after fully reacting, the solution in reaction kettle is filtered by Buchner funnel
It removes solvent and obtains gray solid floccule, then is successively cotton-shaped using 200mL ethyl acetate and 3000mL distillation water washing solid
Object, is subsequently placed in baking oven and is heated to 85 DEG C, and dry moisture 8h obtains chitin modified poly- carboxybenzenesulfonamide component 2.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL is added into 1000mL beaker
Distilled water and 100mL substance withdrawl syndrome are 2mol/L dilute hydrochloric acid, sequentially add poly- carboxyl benzene sulphur made from above-mentioned steps (2)
2,4.6 parts of nano silvers of amide component and 0.8 dose of stearmide and n-octyl alcohol mixture, place the beaker in ultrasonic processor, add
For heat to 85 DEG C, supersonic frequency 28KHz carries out ultrasonic treatment 8h, is completely dispersed material uniformly, then places the beaker baking oven
In be heated to 65 DEG C, slowly remove moisture, control solid-to-liquid ratio 42%, obtain the anti-of the chitin modified polyphenyl sulfonamide of nano silver-
Bacterium coating material 2.
Embodiment 3:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed,
400mL absolute dimethyl sulfoxide is being added, then is successively weighing 32 parts of 2,6-, bis--carboxylphenylsulphonyl chlorides and 35 parts of ammonium nitrate, is stirring
After mixing uniformly, then 5 parts of sodium hydroxides and 1 part of catalyst are successively slowly added to, three-necked bottle are placed in water-bath and is heated to 60 DEG C,
And in N228h is at the uniform velocity stirred to react in atmosphere, reaction observes reaction result by TLC thin layer chromatography, after fully reacting,
Solution in three-necked bottle is transferred in 2000mL separatory funnel, 500mL distilled water and the extraction of 800mL ethyl acetate is added, takes
Ethyl acetate organic layer, and add 500mL distilled water and be extracted twice passes through rotary evaporation for obtain ethyl acetate organic layer
Instrument vacuum distillation removes ethyl acetate, and concentration mixture is then passed through silica gel column chromatography progress TLC separation, eluant, eluent
The isolated eluant, eluent containing product is enriched with, and is depressurized by Rotary Evaporators for petroleum ether: ethyl acetate=3:1
Distillation and oil pump filter, and carry out that removing eluant, eluent is concentrated under reduced pressure, obtain product 2, bis--carboxybenzenesulfonamide of 6- component 3.
(2) it prepares poly- carboxybenzenesulfonamide and is added 200mL distilled water and 300mL ethylene glycol into 1000mL beaker, and according to
2,6-, bis--carboxybenzenesulfonamide component, 3,19 parts of chitosans and 0.4 part of initiator sodium peroxydisulfate made from secondary addition, and slowly drip
Add 0.7 part of concentrated sulfuric acid, transferred the material into high temperature hydrothermal reaction kettle after mixing evenly, and reaction kettle is placed in reaction kettle heating
It is heated to 160 DEG C of reaction 12h in device, is cooled to room temperature after fully reacting, the solution in reaction kettle is filtered by Buchner funnel
It removes solvent and obtains gray solid floccule, then is successively cotton-shaped using 200mL ethyl acetate and 4000mL distillation water washing solid
Object, is subsequently placed in baking oven and is heated to 80 DEG C, and dry moisture 8h obtains chitin modified poly- carboxybenzenesulfonamide component 3.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL is added into 1000mL beaker
Distilled water and 100mL substance withdrawl syndrome are 2mol/L dilute hydrochloric acid, sequentially add poly- carboxyl benzene sulphur made from above-mentioned steps (2)
3,5.5 parts of nano silvers of amide component and 1.4 powder stearmides and n-octyl alcohol mixture, place the beaker in ultrasonic processor,
85 DEG C are heated to, supersonic frequency 28KHz carries out ultrasonic treatment 8h, is completely dispersed material uniformly, then places the beaker baking
It is heated to 65 DEG C in case, slowly removes moisture, controls solid-to-liquid ratio 44%, obtains the chitin modified polyphenyl sulfonamide of nano silver-
Antimicrobial coating material 3.
Embodiment 4:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed,
400mL absolute dimethyl sulfoxide is being added, then is successively weighing 34 parts of 2,6-, bis--carboxylphenylsulphonyl chlorides and 36 parts of ammonium nitrate, is stirring
After mixing uniformly, then 5 parts of sodium hydroxides and 1.3 parts of catalyst are successively slowly added to, three-necked bottle is placed in water-bath and is heated to 65
DEG C, and in N2It is at the uniform velocity stirred to react in atmosphere for 24 hours, reaction observes reaction result, fully reacting by TLC thin layer chromatography
Afterwards, the solution in three-necked bottle is transferred in 2000mL separatory funnel, 500mL distilled water and the extraction of 800mL ethyl acetate is added,
Ethyl acetate organic layer is taken, and adds 500mL distilled water and is extracted twice, steaming by rotation for ethyl acetate organic layer will be obtained
It sends out instrument vacuum distillation and removes ethyl acetate, mixture then will be concentrated by silica gel column chromatography and carry out TLC separation, elution
Agent is petroleum ether: ethyl acetate=3:1, and the isolated eluant, eluent containing product is enriched with, and is subtracted by Rotary Evaporators
Pressure distillation and oil pump filter, and carry out reduced pressure and remove eluant, eluent, obtain product 2, bis--carboxybenzenesulfonamide of 6- component 4.
(2) it prepares poly- carboxybenzenesulfonamide and is added 200mL distilled water and 300mL ethylene glycol into 1000mL beaker, and according to
2,6-, bis--carboxybenzenesulfonamide component, 4,16 parts of chitosans and 0.4 initiator sodium peroxydisulfate made from secondary addition, and be slowly added dropwise
0.8 part of concentrated sulfuric acid, transfers the material into after mixing evenly in high temperature hydrothermal reaction kettle, and reaction kettle is placed in reaction kettle heater
In be heated to 165 DEG C of reaction 12h, be cooled to room temperature after fully reacting, by the solution in reaction kettle by Buchner funnel suction filtration remove
It goes solvent to obtain gray solid floccule, then successively distills water washing solid floccule using 200mL ethyl acetate and 4000mL,
It is subsequently placed in baking oven and is heated to 80 DEG C, dry moisture 10h obtains chitin modified poly- carboxybenzenesulfonamide component 4.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL is added into 1000mL beaker
Distilled water and 100mL substance withdrawl syndrome are 2mol/L dilute hydrochloric acid, sequentially add poly- carboxyl benzene sulphur made from above-mentioned steps (2)
4,4.9 parts of nano silvers of amide component and 1.6 powder stearmides and n-octyl alcohol mixture, place the beaker in ultrasonic processor,
85 DEG C are heated to, supersonic frequency 28KHz carries out ultrasonic treatment 8h, is completely dispersed material uniformly, then places the beaker baking
It is heated to 65 DEG C in case, slowly removes moisture, controls solid-to-liquid ratio 46%, obtains the chitin modified polyphenyl sulfonamide of nano silver-
Antimicrobial coating material 4.
Embodiment 5:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed,
400mL absolute dimethyl sulfoxide is being added, then is successively weighing 35 parts of 2,6-, bis--carboxylphenylsulphonyl chlorides and 38 parts of ammonium nitrate, is stirring
After mixing uniformly, then 6 parts of sodium hydroxides and 1.5 parts of catalyst are successively slowly added to, three-necked bottle is placed in water-bath and is heated to 60
DEG C, and in N228h is at the uniform velocity stirred to react in atmosphere, reaction observes reaction result, fully reacting by TLC thin layer chromatography
Afterwards, the solution in three-necked bottle is transferred in 2000mL separatory funnel, 500mL distilled water and the extraction of 800mL ethyl acetate is added,
Ethyl acetate organic layer is taken, and adds 500mL distilled water and is extracted twice, steaming by rotation for ethyl acetate organic layer will be obtained
It sends out instrument vacuum distillation and removes ethyl acetate, mixture then will be concentrated by silica gel column chromatography and carry out TLC separation, elution
Agent is petroleum ether: ethyl acetate=3:1, and the isolated eluant, eluent containing product is enriched with, and is subtracted by Rotary Evaporators
Pressure distillation and oil pump filter, and carry out reduced pressure and remove eluant, eluent, obtain product 2, bis--carboxybenzenesulfonamide of 6- component 5.
(2) it prepares poly- carboxybenzenesulfonamide and is added 200mL distilled water and 300mL ethylene glycol into 1000mL beaker, and according to
2,6-, bis--carboxybenzenesulfonamide component, 1,30 part of chitosan and 0.5 part of initiator sodium peroxydisulfate made from secondary addition, and slowly drip
Add 1 part of concentrated sulfuric acid, transferred the material into high temperature hydrothermal reaction kettle after mixing evenly, and reaction kettle is placed in reaction kettle heater
In be heated to 165 DEG C of reaction 12h, be cooled to room temperature after fully reacting, by the solution in reaction kettle by Buchner funnel suction filtration remove
It goes solvent to obtain gray solid floccule, then successively distills water washing solid floccule using 200mL ethyl acetate and 4000mL,
It is subsequently placed in baking oven and is heated to 85 DEG C, dry moisture 10h obtains chitin modified poly- carboxybenzenesulfonamide component 5.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL is added into 1000mL beaker
Distilled water and 100mL substance withdrawl syndrome are 2mol/L dilute hydrochloric acid, sequentially add poly- carboxyl benzene sulphur made from above-mentioned steps (2)
5,6 parts of nano silvers of amide component and 2 powder stearmides and n-octyl alcohol mixture, place the beaker in ultrasonic processor, heating
To 85 DEG C, supersonic frequency 28KHz carries out ultrasonic treatment 8h, is completely dispersed material uniformly, then places the beaker in baking oven
70 DEG C are heated to, moisture is slowly removed, solid-to-liquid ratio 48% is controlled, obtains the antibacterial of the chitin modified polyphenyl sulfonamide of nano silver-
Coating material 5.
By the test of anti-microbial property, chemical stability to embodiment 1-5, a kind of nano silver-is chitin modified poly-
Benzsulfamide antimicrobial coating and its preparation method, the matrix by poly- carboxybenzenesulfonamide as coating, sulphonyl imine base therein
Group has very strong reproducibility, so that antimicrobial coating is had good bacteriostasis, while passing through chitin modified poly- carboxyl benzene sulphur
Amide, chitosan have a large amount of activity hydroxy-OH group, are esterified to form chemistry with the carboxyl dehydration in poly- carboxybenzenesulfonamide
The higher electron-withdrawing group ester group of energy, the ester group of electron-withdrawing group reduce the cloud density of sulfonyl by electronic effect,
The chemical energy of sulfonyl is enhanced, to improve the chemical stability and thermal stability of poly- carboxybenzenesulfonamide, applies antibacterial
Layer is not easy by the dioxygen oxidation or light degradation, and the polycation of chitosan in air, is easy and fungal cell's table
The negatively charged group effect in face, changes the mobility and permeability of pathogen cell membrane, to play promotion antimicrobial coating
Antibacterial and sterilization effect.
A kind of chitin modified polyphenyl sulfonamide antimicrobial coating of the nano silver-and its preparation method are connect by the way that nano silver is added
When contacting the albumen oxygen metabolism enzyme in bacterium or fungi, nano silver will in protease have negative electrical charge mercapto-SH and
Amino-NH2Specific binding reaction occurs, the cell wall and cell membrane appearance of pathogen or bacterium have effectively been pierced through, into one
Step makes bacterium or the intracorporal albumen oxygen metabolism enzyme deformation of fungi, loses activity, makes pathogen or bacterium eubolism and breeding, reach
Arrived sterilizing effect, the unique mechanism of action for making thallus be choked to death, can kill the most of bacteriums being in contact with it, fungi,
The microorganisms such as mould, spore, and the chitosan being added has a large amount of amino-NH2With hydroxyl-OH group, it can adsorb and receive
Rice silver forms stable chelate, divides nano silver equably on chitosan surface, avoids nano silver and agglomeration shape occurs
At Argent grain, the phenomenon that reducing the contact area of nano silver and mushroom.
Claims (12)
1. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-and its preparation method, including following parts by weight proportion
Formula material, it is characterised in that: 30-35 part 2, bis--carboxylphenylsulphonyl chloride of 6-, 32-38 part ammonium nitrate, 0.5-1.5 parts of catalyst,
3-6 parts of sodium hydroxides, the 0.4-1 parts of concentrated sulfuric acids, 0.1-0.5 parts of initiators, 10-30 parts of chitosans, 3.5-6 parts of nano silvers, 0.5-2
Dispersing agent.Preparation method includes and following experimental drug: absolute dimethyl sulfoxide, ethyl acetate, distilled water, ethylene glycol, dilute salt
Acid.
2. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: bis--carboxylphenylsulphonyl chloride of 2,6- structural formula isIts mass fraction is >=96.5%.
3. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: NH in the ammonium nitrate4NO3Mass fraction be >=94.2%.
4. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: the catalyst is palladium acetate (COO-)2Pd2+。
5. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: mass fraction >=95.8% of the sodium hydroxide in NaOH.
6. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: the chitosan is β-(1-4) -2-amino-2-deoxy-D-Glucose, and monomer molecule formula is (C6H11NO4) N, molecule
Amount is 350000-380000, deacetylation 70-80%.
7. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: H in the concentrated sulfuric acid2SO4Mass fraction is >=92.5%.
8. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: Ag in the nano silver2CO3Mass fraction >=98.2%.
9. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method, special
Sign is: the dispersing agent is the mixture of stearmide and n-octyl alcohol, mass ratio 1-1.5:2-3.
10. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method,
Be characterized in that: the substance withdrawl syndrome of the dilute hydrochloric acid is 1.5-2mol/L.
11. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method,
It is characterized in that: absolute dimethyl sulfoxide water content≤0.05%.
12. a kind of chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-according to claim 1 and its preparation method,
Be characterized in that: the chitin modified polyphenyl sulfonamide antimicrobial coating of nano silver-, preparation method the following steps are included:
(1) it prepares bis--carboxybenzenesulfonamide of 2,6-: being passed through N in the 1000mL three-necked bottle dry to one2Air is removed, is being added
400mL absolute dimethyl sulfoxide, then 30-35 part 2 is successively weighed, bis--carboxylphenylsulphonyl chloride of 6- and 32-38 parts of ammonium nitrate stir
After mixing uniformly, then 3-6 parts of sodium hydroxides and 0.5-1.5 parts of catalyst are successively slowly added to, three-necked bottle is placed in water-bath and is added
Heat is to 60-65 DEG C, and in N224-28h is at the uniform velocity stirred to react in atmosphere, reaction passes through the observation reaction of TLC thin layer chromatography
As a result, the solution in three-necked bottle is transferred in 2000mL separatory funnel after fully reacting, 500mL distilled water and 800mL is added
Ethyl acetate extraction, takes ethyl acetate organic layer, and add 500mL distilled water and be extracted twice, organic by ethyl acetate is obtained
Being evaporated under reduced pressure by Rotary Evaporators for layer removes ethyl acetate, and concentration mixture is then carried out thin layer by silica gel column chromatography
Chromatographic isolation, eluant, eluent are petroleum ether: ethyl acetate=3:1, and the isolated eluant, eluent containing product is enriched with, and passes through
Rotary Evaporators vacuum distillation and oil pump filter, and carry out that removing eluant, eluent is concentrated under reduced pressure, obtain product 2,6- bis--carboxyl benzene sulfonyl
Amine.
(2) it prepares poly- carboxybenzenesulfonamide and 200mL distilled water and 300mL ethylene glycol is added into 1000mL beaker, and successively add
Enter 2,6- obtained, bis--carboxybenzenesulfonamide, 10-30 parts of chitosans and 0.1-0.5 parts of initiator sodium peroxydisulfates, and is slowly added dropwise
The 0.4-1 parts of concentrated sulfuric acids, transfer the material into after mixing evenly in high temperature hydrothermal reaction kettle, and reaction kettle is placed in reaction kettle heating
It is heated to 160-165 DEG C of reaction 10-12h in device, is cooled to room temperature after fully reacting, the solution in reaction kettle is leaked by Bu Shi
Bucket filters removing solvent and obtains gray solid floccule, then successively using 200mL ethyl acetate and 3000-4000mL distillation washing
Solid floccule is washed, is subsequently placed in baking oven and is heated to 80-85 DEG C, dry moisture 8-10h obtains chitin modified poly- carboxyl benzene
Sulfonamide.
(3) it prepares the antimicrobial coating of the chitin modified polyphenyl sulfonamide of nano silver-: 400mL distillation being added into 1000mL beaker
Water and 100mL substance withdrawl syndrome are 1.5-2mol/L dilute hydrochloric acid, sequentially add poly- carboxyl benzene sulphur made from above-mentioned steps (2)
Amide, 3.5-6 part nano silver and 0.5-2 powder stearmide and n-octyl alcohol mixture, place the beaker in ultrasonic processor, add
For heat to 80-85 DEG C, supersonic frequency 28KHz carries out ultrasonic treatment 6-8h, is completely dispersed material uniformly, then sets beaker
It is heated to 65-70 DEG C in baking oven, slowly removes moisture, controls solid-to-liquid ratio 40-48%, it is chitin modified poly- to obtain nano silver-
The antimicrobial coating of benzsulfamide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980531A (en) * | 2021-11-16 | 2022-01-28 | 山东晶承净化科技有限公司 | Antibacterial coating liquid and preparation method and application thereof |
| CN114849501A (en) * | 2022-05-30 | 2022-08-05 | 沃顿科技股份有限公司 | Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893484A (en) * | 2015-06-18 | 2015-09-09 | 广东美的厨房电器制造有限公司 | Amphiphobic, antibacterial and easy-to-clean coating as well as preparation method and application thereof |
| CN106146358A (en) * | 2015-04-15 | 2016-11-23 | 南京理工大学 | A kind of method of synthesizing amino-(N-alkyl) benzsulfamide |
| CN107057486A (en) * | 2017-03-22 | 2017-08-18 | 广西浩昌敏再生资源利用有限公司 | A kind of mould proof antibacterial paint and preparation method thereof |
| US20180134682A1 (en) * | 2014-09-19 | 2018-05-17 | Forma Therapeutics, Inc. | Quinolinone pyrimidines compositions as mutant-isocitrate dehydrogenase inhibitors |
| CN108715729A (en) * | 2018-06-26 | 2018-10-30 | 段小宁 | Fire-retardant, antibiotic property aqueous polyurethane coating and adhesive preparation method |
-
2019
- 2019-08-16 CN CN201910760606.8A patent/CN110499091B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180134682A1 (en) * | 2014-09-19 | 2018-05-17 | Forma Therapeutics, Inc. | Quinolinone pyrimidines compositions as mutant-isocitrate dehydrogenase inhibitors |
| CN106146358A (en) * | 2015-04-15 | 2016-11-23 | 南京理工大学 | A kind of method of synthesizing amino-(N-alkyl) benzsulfamide |
| CN104893484A (en) * | 2015-06-18 | 2015-09-09 | 广东美的厨房电器制造有限公司 | Amphiphobic, antibacterial and easy-to-clean coating as well as preparation method and application thereof |
| CN107057486A (en) * | 2017-03-22 | 2017-08-18 | 广西浩昌敏再生资源利用有限公司 | A kind of mould proof antibacterial paint and preparation method thereof |
| CN108715729A (en) * | 2018-06-26 | 2018-10-30 | 段小宁 | Fire-retardant, antibiotic property aqueous polyurethane coating and adhesive preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980531A (en) * | 2021-11-16 | 2022-01-28 | 山东晶承净化科技有限公司 | Antibacterial coating liquid and preparation method and application thereof |
| CN113980531B (en) * | 2021-11-16 | 2022-08-23 | 山东晶承净化科技有限公司 | Antibacterial coating liquid and preparation method and application thereof |
| CN114849501A (en) * | 2022-05-30 | 2022-08-05 | 沃顿科技股份有限公司 | Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same |
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