CN103461382A - Silver-loading modified montmorillonite antibacterial agent, preparation method and application thereof - Google Patents
Silver-loading modified montmorillonite antibacterial agent, preparation method and application thereof Download PDFInfo
- Publication number
- CN103461382A CN103461382A CN2013103445816A CN201310344581A CN103461382A CN 103461382 A CN103461382 A CN 103461382A CN 2013103445816 A CN2013103445816 A CN 2013103445816A CN 201310344581 A CN201310344581 A CN 201310344581A CN 103461382 A CN103461382 A CN 103461382A
- Authority
- CN
- China
- Prior art keywords
- silver
- antibacterial agent
- imvite
- preparation
- carrying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The present invention discloses a silver-loading modified montmorillonite antibacterial agent, a preparation method and an application thereof. According to the antibacterial agent, sulfur-containing amino acid modified montmorillonite is adopted as a silver-loading carrier, a sulfur-containing amino acid is adopted to modify montmorillonite, ion exchange is performed to load silver ions between the modified montmorillonite interlayers, and the sliver ions are converted into nanometer sliver with ultraviolet irradiation to obtain the silver-loading modified montmorillonite antibacterial agent. The silver-loading modified montmorillonite antibacterial agent has a good antibacterial performance, and can be doped into plastics, coating materials, adhesives, ceramic materials and products thereof so as to provide excellent antibacterial functions.
Description
Technical field
The invention belongs to antibacterial material technology field, particularly a kind of silver-carrying modified montmorillonite antibacterial agent and its preparation method and application.
Background technology
People can inevitably touch the various bacteriums such as mould, Escherichia coli, staphylococcus aureus in daily life, because bacterial communicable disease causes the event of mankind's death, also again and again occur.Therefore, by with antibacterial material, suppressing the harmful microbe Growth and reproduction, reduce disease, be of great practical significance.Silver be bacteriostatic agent based on its on the one hand can with protein, enzyme equimolecular chelating or absorption, hinder the eubolism of bacterium, trace silver can activate the oxygen in air or water on the other hand, produce active oxygen ion, with bacterium and gas chromatography generation oxidation reaction, cause the di-phosphate ester bond fission between the base in the DNA chain, the DNA replication dna of destroy microorganisms cell, play the effect of multiple inhibition or kill bacteria, successfully overcome sorbic acid, the natural bacteriostatic agent such as chitin are short service life, poor heat resistance, organic bacteriostatic agent poor stability such as the narrower and thiazoles of range of application, the shortcoming that chemical stability is poor, collection is stable, wide spectrum, efficiently, can not make the advantage of bacterium generation drug resistance, oneself is through becoming one of the most promising bacteriostatic agent.Development along with nanometer technology, it is found that because Nano silver grain has minimum particle diameter and high-specific surface area, the energy quick adsorption is at the surface of cell membrane of bacterium, significantly change the normal permeability of bacterium, cause bacterium death, its effective bacteriocidal concentration can reach the nanomole magnitude, makes the use of silver antibacterial agent enter brand-new epoch.
Because the Nano Silver surface can be high, belong to thermodynamic unstable system, very easily form larger-size aggregate between particle, lose the due antibacterial functions of Nano Silver while causing finally applying.Although, by the microwave comparatively stable nano silver particles of having assisted or used protectant to obtain, if often directly add Nano Silver as antibacterial agent in polymer again because the compatibility of itself and polymer is poor, cause and be separated.Therefore, many scholars carry out compoundly with polymer after attempting loading on other materials by silver again, and wherein imvite becomes one of excellent carrier owing to having unique layer structure, huge specific surface area, good absorption property and ion-exchange capacity.
By ion exchange, silver ion is loaded in the imvite of calcination, the silver-colored imvite of carrying that Magana obtains has increased 45%(Magana S M to colibacillary antibiotic loop diameter than common imvite, Quintana P, Aguilar D H, Toledo J A, A ' ngeles-Cha ' ve C, Cort ' es M A, Le ' on L, Freile-Pelegr ' in Y, L ' opez T, S ' anchez R M T. Antibacterial activity of montmorillonites modified with silver. Journal of Molecular Catalysis A:Chemical. 2008, 281:192 – 199).With Ag
+compare, the antibacterial effect that carries silver-colored imvite is even better, because adding of imvite contributes to bacterial adsorption and increased the antibacterial agent surface area, can obviously improve its antibacterial effect; And, by carry silver-colored imvite join in polymer when playing antibacterial action can also reinforcing material mechanical property and heat endurance (Roy B, Bharali P, Konwar B K, Karak N. Silver-embedded modified hyperbranched epoxy/clay nanocomposites as antibacterial materials. Bioresource Technology. 2013,127:175-180).Therefore, carrying silver-colored imvite by preparation obtains the high-efficiency antimicrobial material with good combination property and has become the problem of researcher extensive concern at last decade.
But the binding ability that Many researchers is found montmorillonite layer and silver ion a little less than, the silver ion that loads to interlayer by ion exchange easily dissociates out, can cause like this silver carrying amount not high, and easily cause quick release (Ohashi F at the use initial stage, Ueda S, Taguri T, Kawachi S, Abe H. Antimicrobial activity and thermostability of silver 6-benzylaminopurine montmorillonite. Applied Clay Science. 2009, 46:296-299, Pablo L, Ch á vez M L, Abatal M. Adsorption of heavy metals in acid to alkaline environments by montmorillonite and Ca-montmorillonite. Chemical Engineering Journal. 2011, 171:1276-1286), this has seriously reduced the safety in utilization of year silver-colored imvite and long-lasting, become one of principal element that limits at present its application.Also there is the scholar to attempt adding PVP(polyvinyl pyrrolidone) (PVP) to strengthen interaction (the Xu G of montmorillonite layer and silver ion in ion exchange process, Qiao X, Qiu X, Chen J. Preparation and characterization of nano-silver loaded montmorillonite with strong antibacterial activity and slow release property. Journal of Material Science and Technology. 2011, 27:685-690), this mainly be based on N atom in the assorted five rings of pyrroles in the PVP molecule can with the Ag coordination.From the HSAB theory of hard and soft acids and bases of Pearson, can infer have-SH, S
2-soft base Deng group may be than the easier silver-colored coordination with belonging to soft acid of the pyrroles who belongs to boundary alkali.Many researchers have also confirmed to have strong interaction between the soft base of the sulfur-bearings such as mercaptan and silver ion or Nano Silver, and contribute to the stable of Nano Silver, avoid its (Yang G that reunites, Li H. Sonochemical synthesis of highly monodispersed and size controllable Ag nanoparticles in ethanol solution. Materials Letters. 2008,62:2189-2191).But in view of the toxicity of mercaptan, and be not suitable for preparing safe anti-biotic material for modified montmorillonoid.
Summary of the invention
The object of the invention is to the defect existed for prior art, a kind of silver-carrying modified montmorillonite antibacterial agent that can be good at loading nano silvery and carry out long-acting release is provided.
Another object of the present invention is to provide the preparation method of described silver-carrying modified montmorillonite antibacterial agent.
A further object of the present invention is to provide the application of described silver-carrying modified montmorillonite antibacterial agent.
The technical solution used in the present invention is:
Silver-carrying modified montmorillonite antibacterial agent, this antibacterial agent be take the carrier that the imvite of sulfur amino acid modification is load silver ion.
Silver-carrying modified montmorillonite antibacterial agent, its raw material by weight, comprises following component: 1～5 part of imvite, 0.5～3 part of sulfur amino acid, containing the water soluble silver salt of 0.1～0.6 part of silver ion.
The preparation method of above-mentioned silver-carrying modified montmorillonite antibacterial agent comprises the following steps:
(1) adopt sulfur amino acid to carry out modification to imvite, obtain modified montmorillonoid;
(2) the preparation silver salt solution, add modified montmorillonoid, is uniformly dispersed;
(3) the microwave assisted reaction, after 2～10 minutes, washs, and drying is ground, and obtains presoma;
(4) presoma, through UV-irradiation 4～48 hours, obtains silver-carrying modified montmorillonite antibacterial agent.
Preferably, in silver salt solution, concentration of silver ions is 0.15～0.3mol/L.
Preferably, microwave power is 400～800W.
Preferably, the preparation of modified montmorillonoid comprises the following steps: (1) is scattered in imvite in deionized water, obtains the imvite suspension; (2) aqueous solution of preparation sulfur amino acid, and adjust pH to 1.2～2.5; (3) aqueous solution of sulfur amino acid is added in the imvite suspension, be warming up to 40～70 ℃, stirring reaction 1～2 hour, washing, drying, grind, and obtains modified montmorillonoid.
The application of above-mentioned silver-carrying modified montmorillonite antibacterial agent in plastics, coating, adhesive, ceramic material and goods thereof.
Antibiotic plastic, the above-mentioned silver-carrying modified montmorillonite antibacterial agent that its raw material contains 1～3wt%.
The invention has the beneficial effects as follows:
(1) the present invention first carries out modification with sulfur amino acid to imvite, makes itself and the silver ion that loads to the modified montmorillonoid interlayer that good combination be arranged, and has improved silver carrying amount.Directly with imvite, carry out that ion exchange obtains to carry a silver-colored imvite silver carrying amount be only 1.22%, and the silver-carrying modified imvite silver carrying amount obtained with the cystine modified montmorillonoid can reach 10.93%.
(2) silver ion that will load on the modified montmorillonoid interlayer by the ultraviolet irradiation method changes Nano Silver into, and by sulfur-containing group and silver directly strong the interaction strengthened montmorillonite layer and silver-colored binding ability, improve the release performance of year silver-colored imvite.With irradiated sample not, compare, 48 hours silver-colored release rates of the silver-carrying modified imvite obtained in 48 hours through ultraviolet irradiation have dropped to 22.096% by 33.076%.
(3) silver-carrying modified montmorillonite antibacterial agent of the present invention has good bacteriostasis property, adds the polypropylene plastics that carries silver-colored methionine modified montmorillonoid antibacterial agent of 3wt%, and its antibacterial circle diameter can increase to 10.4mm by 6.0mm.
(4) preparation process of silver-carrying modified montmorillonite antibacterial agent of the present invention is without " three wastes " discharge, and the antibacterial material of preparation can not develop immunity to drugs to bacterium etc., belongs to " green " antibacterial material of environment-friendly type.
(5) silver-carrying modified montmorillonite antibacterial agent of the present invention overcome common nano-Ag particles easy agglomeration, poor with the compatibility of polymer, directly add in polymer and easily cause the shortcoming such as be separated, very easy to use, by common plastics melt blending processing method, can be dispersed in the plastic basis materials such as polypropylene, ABS, processing technology is simple, easily control, there is good application and promotion prospect.
(6) silver-carrying modified montmorillonite antibacterial agent decapacitation of the present invention significantly improves outside the bacteriostasis property of the plastics such as polypropylene, ABS, and less to the comprehensive mechanical property infringement of plastics, even some performance can also improve.As the notched Izod impact strength of adding the polypropylene plastics that carries silver-colored methionine modified montmorillonoid antibacterial agent of 3wt% reaches 5.28KJ/m
2, than the impact strength of virgin pp plastics 3.00 KJ/m
2be significantly improved.
The accompanying drawing explanation
Fig. 1 is sodium-based montmorillonite, year silver-colored methionine modified montmorillonoid presoma, year silver-colored cysteine modified montmorillonoid presoma and 2～12 ° of X-ray diffractograms that carry silver-colored cystine modified montmorillonoid presoma.
Fig. 2 is sodium-based montmorillonite, carry silver-colored cystine modified montmorillonoid presoma and through the X-ray diffractogram of 30 °～70 ° that carries silver-colored cystine modified montmorillonoid antibacterial agent of ultraviolet irradiation.
Fig. 3 is the transmission electron microscope photo that carries silver-colored cystine modified montmorillonoid antibacterial agent through ultraviolet irradiation acquisition in 48 hours.
Embodiment
Silver-carrying modified montmorillonite antibacterial agent, this antibacterial agent be take the carrier that the imvite of sulfur amino acid modification is load silver ion.
Silver-carrying modified montmorillonite antibacterial agent, its raw material by weight, comprises following component: 1～5 part of imvite, 0.5～3 part of sulfur amino acid, containing the water soluble silver salt of 0.1～0.6 part of silver ion.
Described sulfur amino acid is at least one in methionine, cystine, cysteine.
Conventional sodium-based montmorillonite or calcium-base montmorillonite are selected in imvite, certainly, also can use as required the imvite of other classifications.
Preferably, silver salt is silver ammino solution or liquor argenti nitratis ophthalmicus.
The preparation method of the silver-carrying modified montmorillonite antibacterial agent of the present invention is: under acid condition, adopt sulfur amino acid to carry out modification to imvite and obtain modified montmorillonoid, then with silver salt solution, under microwave irradiation, by ion exchange, silver ion is loaded on modified montmorillonoid, and change silver ion into Nano Silver through ultraviolet irradiation, obtain silver-carrying modified montmorillonite antibacterial agent.Specifically comprise the following steps:
(1) adopt sulfur amino acid to carry out modification to imvite, obtain modified montmorillonoid;
(2) the preparation silver salt solution, add modified montmorillonoid, is uniformly dispersed;
(3) the microwave assisted reaction, after 2～10 minutes, washs, and drying is ground, and obtains presoma;
(4) presoma, through UV-irradiation 4～48 hours, obtains silver-carrying modified montmorillonite antibacterial agent.
Preferably, in silver salt solution, concentration of silver ions is 0.15～0.3mol/L.Preferred, in silver salt solution, concentration of silver ions is 0.2mol/L.
Preferably, microwave power is 400～800W.Preferably, the microwave assisted reaction is 2.5～5 minutes.
Preferably, the preparation of modified montmorillonoid comprises the following steps: (1) is scattered in imvite in deionized water, obtains the imvite suspension; (2) aqueous solution of preparation sulfur amino acid, and adjust pH to 1.2～2.5; (3) aqueous solution of sulfur amino acid is added in the imvite suspension, be warming up to 40～70 ℃, stirring reaction 1～2 hour, washing, drying, grind, and obtains modified montmorillonoid.Preferred, adjust pH to 1.8 in step (2).
The application of above-mentioned silver-carrying modified montmorillonite antibacterial agent in plastics, coating, adhesive, ceramic material and goods thereof.
The silver-carrying modified montmorillonite antibacterial agent of the present invention joins in the plastic basis materials such as polypropylene, ABS, can prepare the plastic products with good bacteriostasis property.
Antibiotic plastic, the above-mentioned silver-carrying modified montmorillonite antibacterial agent that its raw material contains 1～3wt%.
The preparation method of antibiotic plastic comprises the following steps:
(1) make polypropylene or ABS melting bag roller at 160～170 ℃ of temperature, then add antioxidant and silver-carrying modified montmorillonite antibacterial agent;
(2) mixing evenly rear compressing tablet, make antibacterial plastics;
Wherein, the consumption of silver-carrying modified montmorillonite antibacterial agent, antioxidant, polypropylene or ABS is respectively 1～3 weight portion, 0.001～0.01 weight portion and 97～99 weight portions, amounts to 100 weight portions; Described antioxidant is the general antioxidant in this area, comprises antioxidant 1010, B215, but is not limited to this.
Below in conjunction with specific embodiment, further set forth content of the present invention.
embodiment 1
(1) preparation of modified montmorillonoid
Get 1g sodium-based montmorillonite (Na-MMT) and be dispersed in the 100ml deionized water, in 60 ℃, stir and within 1 hour, obtain the imvite suspension; In another beaker, add the deionized water of sulfur amino acid and the 100ml of 1.9g, adding the HCl adjusting pH value containing 0.1mol/L under 60 ℃ is 1.8, obtains the sulfur amino acid aqueous solution; The sulfur amino acid aqueous solution is joined in the imvite suspension, stir 1 hour under 60 ℃, be cooled to room temperature, washing and filtering, until filtrate is used the AgNO of 0.1mol/L
3detection is without white precipitate; Finally product is put in baking oven, in 70 ℃ of heating, dryings to constant weight, the solid abrasive obtained becomes fine powder, obtains modified montmorillonoid (AA-MMT).
(2) preparation of silver-carrying modified montmorillonite antibacterial agent
AA-MMT is joined in the silver nitrate aqueous solution of 10ml 0.2 mol/L, after 60 ℃ of stirring 30min are uniformly dispersed, be placed in microwave generator, under 750W power, reaction is 4 minutes, cooling, washing and filtering, to through hydrochloric acid check filtrate, without the white precipitate material, (not containing Ag
+), dry to constant weight, grind refinement, obtain silver-carrying modified montmorillonite antibacterial agent presoma, be designated as Ag@AA-MMT; Ag@AA-MMT is placed in to irradiation under the ultraviolet lamp of 365nm wavelength and, after 48 hours, obtains the silver-carrying modified montmorillonite antibacterial agent of product, be designated as Ag@AA-MMT-UV.
As stated above, use respectively methionine, cysteine, cystine to prepare three kinds of different silver-carrying modified montmorillonite antibacterial agents.Performance characterization is as follows:
Fig. 1 is sodium-based montmorillonite (Na-MMT), year silver-colored methionine modified montmorillonoid presoma (Ag@AA-MMT-1), year silver-colored cysteine modified montmorillonoid presoma (Ag@AA-MMT-2) and 2 °～12 ° X-ray diffractograms that carry silver-colored cystine modified montmorillonoid presoma (Ag@AA-MMT-3), wherein, a is Na-MMT, b is Ag@AA-MMT-1, c is Ag@AA-MMT-2, and d is [email protected] find out that there is no the MMT of modification interlamellar spacing is 1.21nm, the interlamellar spacing of Ag@AA-MMT-1, Ag@AA-MMT-2 and Ag@AA-MMT-3 is increased to respectively 1.28nm, 1.35nm and 1.34nm.
Fig. 2 is Na-MMT, Ag@AA-MMT-3 and through the X-ray diffractogram of 30 °～70 ° that carries silver-colored cystine modified montmorillonoid (Ag@AA-MMT-3-UV) of ultraviolet irradiation, and wherein, a is Na-MMT, and b is Ag@AA-MMT-3, and c is [email protected] see that three kinds of silver-carrying modified imvites are all 38.4 °, 44.4 ° and 64.3 ° of diffraction maximums that occurred corresponding to the nanocrystalline silver structure.
Fig. 3 is the transmission electron microscope photo through the Ag@AA-MMT-3-UV of ultraviolet irradiation acquisition in 48 hours, can see the Nano Silver of black particle shape, its size uniform, good dispersion.
Carry the silver carrying amount of silver-colored imvite and silver-carrying modified imvite presoma relatively:
Carry the silver carrying amount of silver-colored imvite and silver-carrying modified imvite presoma and as shown in table 1 to the inhibition zone method test data of staphylococcus aureus.Can see, the silver carrying amount of three kinds of silver-carrying modified imvite presomas that prepare by method of the present invention and bacteriostasis property all carry silver-colored imvite than routine and are improved largely.
The silver carrying amount of table 1 year silver-colored imvite and silver-carrying modified imvite presoma and bacteriostasis property are relatively
| Sample | Silver carrying amount (%) | Antibacterial circle diameter (mm) |
| Carry silver-colored imvite (Ag@MMT) | 1.22 | 9.4 |
| Ag@AA-MMT-1 | 5.58 | 9.9 |
| Ag@AA-MMT-2 | 5.45 | 10.1 |
| Ag@AA-MMT-3 | 10.93 | 11.2 |
(1) preparation of modified montmorillonoid
Get the 2g calcium-base montmorillonite and be dispersed in the 100ml deionized water, obtain the imvite suspension; In another beaker, add the deionized water of cystine and the 100ml of 0.5g, and to regulate the pH value be 1.2, obtain the cystine aqueous solution; The cystine aqueous solution is joined in the imvite suspension, be warming up to 70 ℃, stirring reaction 1 hour, then be cooled to room temperature, and washing and filtering, until filtrate is used AgNO
3detection is without white precipitate; Finally product is dried to constant weight, grind to form fine powder, obtain modified montmorillonoid.
(2) preparation of silver-carrying modified montmorillonite antibacterial agent
Modified montmorillonoid is joined in the silver nitrate aqueous solution of 20ml 0.2 mol/L, be warming up to 60 ℃, stirring makes to be uniformly dispersed, and then is placed in microwave generator, and under 400W power, reaction is 10 minutes, cooling, washing and filtering, to after hydrochloric acid check filtrate is without the white precipitate material, dry to constant weight, grind refinement, must carry silver-colored cystine modified montmorillonoid antibacterial agent presoma; Presoma is placed under ultraviolet lamp to irradiation 24 hours, must carries silver-colored cystine modified montmorillonoid antibacterial agent.
embodiment 3
(1) preparation of modified montmorillonoid
Get the 5g sodium-based montmorillonite and be dispersed in the 100ml deionized water, obtain the imvite suspension; In another beaker, add the deionized water of cystine and the 100ml of 3 g, and to regulate the pH value be 2.5, obtain the cystine aqueous solution; The cystine aqueous solution is joined in the imvite suspension, be warming up to 40 ℃, stirring reaction 2 hours, then be cooled to room temperature, and washing and filtering, until filtrate is used AgNO
3detection is without white precipitate; Finally product is dried to constant weight, grind to form fine powder, obtain modified montmorillonoid.
(2) preparation of silver-carrying modified montmorillonite antibacterial agent
Modified montmorillonoid is joined in the silver nitrate aqueous solution of 20ml 0.3 mol/L, be warming up to 60 ℃, stirring makes to be uniformly dispersed, and then is placed in microwave generator, and under 800W power, reaction is 2 minutes, cooling, washing and filtering, to after hydrochloric acid check filtrate is without the white precipitate material, dry to constant weight, grind refinement, must carry silver-colored cystine modified montmorillonoid antibacterial agent presoma; Presoma is placed under ultraviolet lamp to irradiation 4 hours, must carries silver-colored cystine modified montmorillonoid antibacterial agent.
The preparation method of the present embodiment and reaction condition be as embodiment 1, the liquor argenti nitratis ophthalmicus concentration when changing silver-carrying modified imvite and preparing, and the silver carrying amount data of the silver-carrying modified imvite presoma of gained are as shown in table 2.
Under the different silver nitrate concentrations of table 2, the silver carrying amount of the silver-carrying modified imvite presoma of gained relatively
| Liquor argenti nitratis ophthalmicus concentration (mol/L) | Ag@AA-MMT-1 silver carrying amount (wt%) | Ag@AA-MMT-2 silver carrying amount (wt%) | Ag@AA-MMT-3 silver carrying amount (wt%) |
| 0.1 | 4.21 | 4.16 | 8.56 |
| 0.15 | 5.00 | 5.04 | 9.93 |
| 0.2 | 5.58 | 5.45 | 10.93 |
| 0.25 | 5.96 | 5.86 | 11.71 |
| 0.3 | 6.22 | 6.03 | 12.34 |
Can see, along with the increase of silver nitrate concentration, the silver carrying amount of three kinds of silver-carrying modified imvite presomas also improves constantly, and this is because improve the concentration that the concentration of liquor argenti nitratis ophthalmicus is equivalent to increase reactant, the chemical balance forward that is conducive to ion exchange moves, and the concentration of product is also corresponding higher.But the increase trend of silver carrying amount starts obviously to slow down after silver nitrate concentration reaches 0.2 mol/L, this may be because of Ag in the silver nitrate of excessive concentrations
+can not ionize fully, cause the actual Ag that participates in ion exchange that increases in solution
+number and concentration value added be equity fully, thereby the growth trend of the silver carrying amount of silver-carrying modified imvite presoma slows down.Consider the factors such as cost, selecting the concentration of liquor argenti nitratis ophthalmicus is that 0.2mol/L is proper.
embodiment 5
The preparation method of the present embodiment and reaction condition be as embodiment 1, and keeping liquor argenti nitratis ophthalmicus concentration is 0.2mol/L, and the microwave reaction time when changing silver-carrying modified imvite and preparing, the silver carrying amount data of the silver-carrying modified imvite presoma of gained are as shown in table 3.
The silver carrying amount of the different microwave reactions of table 3 silver-carrying modified imvite presoma of gained under the time relatively
| The microwave reaction time (min) | Ag@AA-MMT-1 silver carrying amount (wt%) | Ag@AA-MMT-2 silver carrying amount (wt%) | Ag@AA-MMT-3 silver carrying amount (wt%) |
| 2.0 | 4.21 | 4.16 | 8.56 |
| 2.5 | 4.60 | 4.44 | 9.23 |
| 3.0 | 5.01 | 4.75 | 9.98 |
| 3.5 | 5.23 | 4.96 | 10.11 |
| 4.0 | 5.58 | 5.45 | 10.93 |
| 4.5 | 5.34 | 5.37 | 10.21 |
| 5.0 | 4.87 | 5.08 | 9.11 |
Can significantly see that silver carrying amount reaches peak when the microwave reaction time is 4min, after the reaction time continues to extend, the silver carrying amount of silver-carrying modified imvite presoma descends on the contrary.This is because after the reaction time reaches optimum value, and continuing increases radiation, can cause modified montmorillonoid dry rapidly, and temperature rises rapidly, and the chemical balance of ion exchange is destroyed, thereby silver carrying amount reduces.
The preparation method of the present embodiment and reaction condition, as embodiment 1, take the 0.1g sample, put into the triangular flask that 100ml distilled water is housed, be fixed on 25 ℃ of constant temperature oscillators, with 72 r/min lucifuge joltings, get the solution after appropriate jolting, measure Ag in different time solution with ultraviolet specrophotometer
+concentration, analyze to carry the silver-colored rate of releasing of silver-colored imvite, result data is as shown in table 4.
The silver-colored rate of releasing of the different silver-carrying modified imvites of table 4 compares
Can see, the silver-colored rate of releasing of Ag@AA-MMT-3 and Ag@AA-MMT-3-UV all descends to some extent than Ag@MMT, be mainly because the sulfur-containing group on the cystine modified montmorillonoid has been strengthened the interaction between montmorillonite layer and silver, avoid the quick release at silver.Particularly the silver-colored rate of releasing of Ag@AA-MMT-3-UV is significantly carried silver-colored imvite lower than other two kinds, this is mainly that Nano Silver due to its load can interact with the sulfur-containing group on modified montmorillonoid surface, this combination has hindered silver and has proceeded to rapidly the free ion state by chemical bound state, thereby affects silver-colored release.
embodiment 7
Year silver-colored methionine modified montmorillonoid antibacterial agent (Ag@AA-MMT-1-UV) prepared by embodiment 1 is as bacteriostatic agent for the preparation of bacteriostatic PP, and the preparation method is as follows:
(1) make polypropylene fusion bag roller at 160 ℃ of temperature, then add antioxidant 1010 and Ag@AA-MMT-1-UV;
(2) mixing evenly rear compressing tablet, make the bacteriostatic PP plastics;
Wherein, the consumption of polypropylene, antioxidant 1010 and Ag@AA-MMT-1-UV is respectively 97～100 weight portions, 0.002 weight portion and 0～3 weight portion, amounts to 100 weight portions.
The consumption of Ag@AA-MMT-1-UV is on the mechanical property of bacteriostatic PP and as shown in table 4 on the impact of the bacteriostasis property of staphylococcus aureus.
The different Ag@of table 4 AA-MMT-1-UV consumption is on the mechanical property of polypropylene plastics and the impact of bacteriostasis property
| Ag@AA-MMT-1-UV consumption (weight portion) | Antibacterial circle diameter (mm) | Impact strength (KJ/m 2） | Tensile strength (MPa) |
| 0 | 6.0 | 3.00 | 35.25 |
| 1 | 9.4 | 3.25 | 37.56 |
| 2 | 10.1 | 5.17 | 38.68 |
| 3 | 10.4 | 5.28 | 40.09 |
Can find out, Ag@AA-MMT-1-UV adds the rapid polyacrylic bacteriostasis that improved, and when addition only is 1wt%, antibacterial circle diameter has increased 56.6%; The mechanical property to bacteriostatic PP that adds of Ag AA-MMT-1-UV also increases simultaneously, and when addition is 3wt%, the impact strength of bacteriostatic PP and tensile strength distribute than for having improved 76% and 14% before adding, and have obtained good combination property.
Claims (8)
1. silver-carrying modified montmorillonite antibacterial agent, this antibacterial agent be take the carrier that the imvite of sulfur amino acid modification is load silver ion.
2. silver-carrying modified montmorillonite antibacterial agent according to claim 1, it is characterized in that: its raw material by weight, comprises following component: 1～5 part of imvite, 0.5～3 part of sulfur amino acid, containing the water soluble silver salt of 0.1～0.6 part of silver ion.
3. the preparation method of claim 1 or 2 described silver-carrying modified montmorillonite antibacterial agent comprises the following steps:
(1) adopt sulfur amino acid to carry out modification to imvite, obtain modified montmorillonoid;
(2) the preparation silver salt solution, add modified montmorillonoid, is uniformly dispersed;
(3) the microwave assisted reaction, after 2～10 minutes, washs, and drying is ground, and obtains presoma;
(4) presoma, through UV-irradiation 4～48 hours, obtains silver-carrying modified montmorillonite antibacterial agent.
4. preparation method according to claim 3, it is characterized in that: in silver salt solution, concentration of silver ions is 0.15～0.3mol/L.
5. preparation method according to claim 3, it is characterized in that: microwave power is 400～800W.
6. preparation method according to claim 3, it is characterized in that: the preparation of modified montmorillonoid comprises the following steps: (1) is scattered in imvite in deionized water, obtains the imvite suspension; (2) aqueous solution of preparation sulfur amino acid, and adjust pH to 1.2～2.5; (3) aqueous solution of sulfur amino acid is added in the imvite suspension, be warming up to 40～70 ℃, stirring reaction 1～2 hour, washing, drying, grind, and obtains modified montmorillonoid.
7. the application of the described silver-carrying modified montmorillonite antibacterial agent of claim 1 or 2 in plastics, coating, adhesive, ceramic material and goods thereof.
8. antibiotic plastic, the described silver-carrying modified montmorillonite antibacterial agent of the claim 1 or 2 that its raw material contains 1～3wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310344581.6A CN103461382B (en) | 2013-08-08 | 2013-08-08 | Silver-loading modified montmorillonite antibacterial agent, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310344581.6A CN103461382B (en) | 2013-08-08 | 2013-08-08 | Silver-loading modified montmorillonite antibacterial agent, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103461382A true CN103461382A (en) | 2013-12-25 |
| CN103461382B CN103461382B (en) | 2015-07-01 |
Family
ID=49786624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310344581.6A Expired - Fee Related CN103461382B (en) | 2013-08-08 | 2013-08-08 | Silver-loading modified montmorillonite antibacterial agent, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103461382B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104585235A (en) * | 2014-12-31 | 2015-05-06 | 芜湖恒杰膨润土科技有限公司 | Silver-loaded bentonite and preparation method thereof |
| CN104604937A (en) * | 2014-12-31 | 2015-05-13 | 芜湖恒杰膨润土科技有限公司 | Silver-loaded bentonite and preparation method thereof |
| CN105462221A (en) * | 2015-12-17 | 2016-04-06 | 广东药学院 | Polycarbonate and silver-loaded montmorillonite composite functional hydrophobic material and preparation method thereof |
| CN106234355A (en) * | 2016-07-28 | 2016-12-21 | 东莞市雄林新材料科技股份有限公司 | A kind of organic-inorganic nano antibacterial and preparation method thereof |
| CN106582622A (en) * | 2016-11-10 | 2017-04-26 | 广东药科大学 | Easy-recycling palladium-supporting modified montmorillonite catalyst preparation method and applications of easy-recycling palladium-supporting modified montmorillonite catalyst in Suzuki reaction |
| CN106633190A (en) * | 2016-10-21 | 2017-05-10 | 安徽江淮汽车集团股份有限公司 | Preparation method and application of antibacterial agent |
| CN107159166A (en) * | 2017-07-13 | 2017-09-15 | 长春工业大学 | A kind of modified illite loading nano silvery antibacterial material and preparation method thereof |
| CN109077053A (en) * | 2018-07-14 | 2018-12-25 | 泉州师范学院 | A kind of preparation method of carrying silver antimicrobials |
| CN110254014A (en) * | 2019-03-19 | 2019-09-20 | 三菱电机(中国)有限公司 | A kind of high-efficiency antimicrobial ABS plastic and preparation method thereof |
| CN110586956A (en) * | 2019-09-29 | 2019-12-20 | 同济大学 | Method for in-situ synthesis of montmorillonite/gold nanorod composite material |
| CN111657033A (en) * | 2020-05-06 | 2020-09-15 | 六安市裕安区伊甸园油茶种植专业合作社 | Method for preventing and treating diseases and pests of camellia oleifera forest |
| CN112538217A (en) * | 2020-12-09 | 2021-03-23 | 武汉金发科技有限公司 | Polypropylene composite material and preparation method thereof |
| CN113605105A (en) * | 2021-07-21 | 2021-11-05 | 苏州金多利纺织新材料有限公司 | Novel antiviral PU protective clothing |
| CN113875501A (en) * | 2021-10-28 | 2022-01-04 | 桂东森宜食用菌发展有限公司 | High-pressure steam sterilization method for mushroom sticks for mushroom planting in greenhouse |
| CN114680133A (en) * | 2022-03-18 | 2022-07-01 | 湖南工业大学 | Metal organic framework/montmorillonite composite material and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369011A (en) * | 2018-12-24 | 2019-02-22 | 广东宝丰陶瓷科技发展股份有限公司 | A kind of synthesis technology of the domestic ceramics glaze containing inorganic antiseptic |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101589727A (en) * | 2009-06-30 | 2009-12-02 | 中南林业科技大学 | A kind of preparation method of silver-carrying nano-antimicrobial organic montmorillonite |
| CN102125055A (en) * | 2010-12-02 | 2011-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Sliver-carried nano-montmorillonite antibacterial agent and preparation method thereof |
| JP4982837B2 (en) * | 2003-11-19 | 2012-07-25 | 独立行政法人産業技術総合研究所 | Antibacterial agent for marine adherents |
| CN102860325A (en) * | 2012-09-12 | 2013-01-09 | 江南大学 | Bactericidal nano-silver water gel and preparation method thereof |
-
2013
- 2013-08-08 CN CN201310344581.6A patent/CN103461382B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4982837B2 (en) * | 2003-11-19 | 2012-07-25 | 独立行政法人産業技術総合研究所 | Antibacterial agent for marine adherents |
| CN101589727A (en) * | 2009-06-30 | 2009-12-02 | 中南林业科技大学 | A kind of preparation method of silver-carrying nano-antimicrobial organic montmorillonite |
| CN102125055A (en) * | 2010-12-02 | 2011-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Sliver-carried nano-montmorillonite antibacterial agent and preparation method thereof |
| CN102860325A (en) * | 2012-09-12 | 2013-01-09 | 江南大学 | Bactericidal nano-silver water gel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 丁峰等: "硫改性硅酸盐吸附剂脱汞性能的实验研究", 《华中科技大学学报(自然科学版)》, vol. 39, no. 11, 23 November 2011 (2011-11-23), pages 116 - 119 * |
| 宫雪: "载纳米银抗菌复合材料的研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》, 15 May 2011 (2011-05-15), pages 020 - 95 * |
| 段淑娥等: "银-组氨酸配合物-蒙脱石抗菌剂的制备及抗菌活性", 《高等学校化学学报》, vol. 33, no. 12, 10 December 2012 (2012-12-10), pages 2617 - 2622 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104604937A (en) * | 2014-12-31 | 2015-05-13 | 芜湖恒杰膨润土科技有限公司 | Silver-loaded bentonite and preparation method thereof |
| CN104604937B (en) * | 2014-12-31 | 2017-09-01 | 芜湖恒杰膨润土科技有限公司 | Carry silver-colored bentonite and preparation method thereof |
| CN104585235B (en) * | 2014-12-31 | 2017-09-01 | 芜湖恒杰膨润土科技有限公司 | Carry silver-colored bentonite and preparation method thereof |
| CN104585235A (en) * | 2014-12-31 | 2015-05-06 | 芜湖恒杰膨润土科技有限公司 | Silver-loaded bentonite and preparation method thereof |
| CN105462221A (en) * | 2015-12-17 | 2016-04-06 | 广东药学院 | Polycarbonate and silver-loaded montmorillonite composite functional hydrophobic material and preparation method thereof |
| CN106234355A (en) * | 2016-07-28 | 2016-12-21 | 东莞市雄林新材料科技股份有限公司 | A kind of organic-inorganic nano antibacterial and preparation method thereof |
| CN106633190A (en) * | 2016-10-21 | 2017-05-10 | 安徽江淮汽车集团股份有限公司 | Preparation method and application of antibacterial agent |
| CN106582622A (en) * | 2016-11-10 | 2017-04-26 | 广东药科大学 | Easy-recycling palladium-supporting modified montmorillonite catalyst preparation method and applications of easy-recycling palladium-supporting modified montmorillonite catalyst in Suzuki reaction |
| CN107159166A (en) * | 2017-07-13 | 2017-09-15 | 长春工业大学 | A kind of modified illite loading nano silvery antibacterial material and preparation method thereof |
| CN109077053B (en) * | 2018-07-14 | 2021-02-02 | 泉州师范学院 | Preparation method of silver-loaded antibacterial agent |
| CN109077053A (en) * | 2018-07-14 | 2018-12-25 | 泉州师范学院 | A kind of preparation method of carrying silver antimicrobials |
| CN110254014A (en) * | 2019-03-19 | 2019-09-20 | 三菱电机(中国)有限公司 | A kind of high-efficiency antimicrobial ABS plastic and preparation method thereof |
| CN110254014B (en) * | 2019-03-19 | 2021-07-30 | 三菱电机(中国)有限公司 | Efficient antibacterial ABS plastic and preparation method thereof |
| CN110586956A (en) * | 2019-09-29 | 2019-12-20 | 同济大学 | Method for in-situ synthesis of montmorillonite/gold nanorod composite material |
| CN111657033A (en) * | 2020-05-06 | 2020-09-15 | 六安市裕安区伊甸园油茶种植专业合作社 | Method for preventing and treating diseases and pests of camellia oleifera forest |
| CN112538217A (en) * | 2020-12-09 | 2021-03-23 | 武汉金发科技有限公司 | Polypropylene composite material and preparation method thereof |
| CN113605105A (en) * | 2021-07-21 | 2021-11-05 | 苏州金多利纺织新材料有限公司 | Novel antiviral PU protective clothing |
| CN113875501A (en) * | 2021-10-28 | 2022-01-04 | 桂东森宜食用菌发展有限公司 | High-pressure steam sterilization method for mushroom sticks for mushroom planting in greenhouse |
| CN114680133A (en) * | 2022-03-18 | 2022-07-01 | 湖南工业大学 | Metal organic framework/montmorillonite composite material and preparation method and application thereof |
| CN114680133B (en) * | 2022-03-18 | 2023-11-03 | 湖南工业大学 | Metal organic framework/montmorillonite composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103461382B (en) | 2015-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103461382B (en) | Silver-loading modified montmorillonite antibacterial agent, preparation method and application thereof | |
| Lu et al. | Improved recyclability and selectivity of environment-friendly MFA-based heterojunction imprinted photocatalyst for secondary pollution free tetracycline orientation degradation | |
| Lan et al. | Application of polyoxometalates in photocatalytic degradation of organic pollutants | |
| Sahiner et al. | Utilization of smart hydrogel–metal composites as catalysis media | |
| CN107086313B (en) | A kind of iron, cobalt, nitrogen co-doped Pd/carbon catalyst and its preparation method and application | |
| CN102153103B (en) | Preparation method and application of modified attapulgite clay | |
| Zhou et al. | The preparation, and applications of gC 3 N 4/TiO 2 heterojunction catalysts—a review | |
| Motshekga et al. | Preparation and antibacterial activity of chitosan-based nanocomposites containing bentonite-supported silver and zinc oxide nanoparticles for water disinfection | |
| Murthy et al. | First successful design of semi-IPN hydrogel–silver nanocomposites: a facile approach for antibacterial application | |
| Yuan et al. | Research progress on photocatalytic reduction of Cr (VI) in polluted water | |
| Huang et al. | Optical properties of biomass-derived nanomaterials for sensing, catalytic, biomedical and environmental applications | |
| Liu et al. | Magnetic nanocomposite adsorbents | |
| CN104667945A (en) | Preparation of supported palladium catalyst Fe3O4/SiO2/Pd and application of supported palladium catalyst Fe3O4/SiO2/Pd in Suzuki reaction | |
| CN104472538A (en) | Functional graphene oxide loaded nano-silver antibacterial material as well as preparation method and application thereof | |
| CN103194030A (en) | Preparation method for temperature-sensitive hydrogel/silver nanocomposite | |
| CN109225242A (en) | A kind of composite nano attapulgite haydite ozone catalyst and its preparation method and application | |
| CN107570191B (en) | Preparation method and application of visible light catalyst | |
| Wang et al. | The study of titanium dioxide modification by glutaraldehyde and its application of immobilized penicillin acylase | |
| Kokilavani et al. | Integrating Ag2WO4 on VS4 nanoplates with synergy of plasmonic photocatalysis and boosted visible-light harvesting and its antibacterial applications | |
| Huang et al. | Facile pyrolysis preparation of rosin-derived biochar for supporting silver nanoparticles with antibacterial activity | |
| CN111450806B (en) | Preparation method of porous adsorption antibacterial composite material based on waste corncobs | |
| CN111978565A (en) | Preparation method and application of cellulose hydrogel-based nano silver/silver chloride | |
| CN108160991A (en) | Antibacterial composite granule, antibacterial functionalized composite material and preparation method | |
| CN105112453A (en) | Preparation method of nano-particle material | |
| CN112795098A (en) | Antibacterial plastic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 510240 40 Haizhuqu District, Guangdong, Guangzhou. Patentee after: Guangdong Pharmaceutical University Address before: 510006 No. 280 East Ring Road, Guangzhou City University, Guangdong Patentee before: Guangdong Pharmaceutical University |
|
| CP03 | Change of name, title or address | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150701 Termination date: 20180808 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |