CN103461382B - 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
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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 technical field, particularly silver-carrying modified montmorillonite antibacterial agent of one and its preparation method and application.
Background technology
People can inevitably touch the various bacteriums such as mould, Escherichia coli, staphylococcus aureus, because bacterial communicable disease causes the event of human death also again and again to occur in daily life.Therefore, by using antibacterial material to suppress harmful microbe Growth and reproduction, reducing disease, being of great practical significance.Silver system 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 DNA chain, the DNA replication dna of destroy microorganisms cell, play the effect of multiple inhibiting or kill bacteria, successfully overcome sorbic acid, the natural bacteriostatic agent such as chitin are short for 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, bacterium can not be made to produce the advantage of drug resistance, oneself is through becoming one of the most promising bacteriostatic agent.Along with the development of nanometer technology, it is found that because Nano silver grain has minimum particle diameter and high-specific surface area, energy quick adsorption is at the surface of cell membrane of bacterium, the normal osmosis of remarkable change bacterium, cause bacterial death, its effective bacteriocidal concentration can reach nanomole magnitude, makes the use of silver antibacterial agent enter brand-new epoch.
Because Nano Silver surface energy is high, belong to thermodynamic unstable system, between particle, very easily form larger-size aggregate, when causing finally applying, lose the due antibacterial functions of Nano Silver.Although by microwave radiation technology or use protectant to obtain comparatively stable nano silver particles, be separated if directly Nano Silver to be added in polymer often to cause because the compatibility of itself and polymer is poor again as antibacterial agent.Therefore, many scholars attempt carrying out compound with polymer again after silver-colored load is on other materials, 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, year silver-colored imvite that Magana obtains increases 45%(Magana S M to colibacillary antibacterial 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 carrying silver-colored imvite is even better, because adding of imvite contributes to bacterial adsorption and increase antibacterial agent surface area, can significantly improve its antibacterial effect; And, year silver-colored imvite is joined mechanical property and heat endurance (the Roy B of all right reinforcing material while playing antibacterial action in polymer, Bharali P, Konwar B K, Karak N. Silver-embedded modified hyperbranched epoxy/clay nanocomposites as antibacterial materials. Bioresource Technology. 2013,127:175-180).Therefore, carry silver-colored imvite by preparation and obtain the efficacious anti-microbial material with good combination property to have become researcher extensive concern problem at last decade.
But Many researchers finds that the binding ability of montmorillonite layer and silver ion is more weak, the silver ion being loaded to interlayer by ion exchange is easily dissociated out, silver carrying amount can be caused so 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 seriously reduces and carries the safety in utilization of silver-colored imvite and long-lasting, become one of principal element limiting its application at present.Also scholar is had to attempt in ion exchange process, add interaction (the Xu G that PVP(polyvinyl pyrrolidone) (PVP) strengthens montmorillonite layer and silver ion, 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 atom N of mainly mixing in five rings based on the pyrroles in PVP molecule can with Ag coordination.From the HSAB theory of hard and soft acids and bases of Pearson, can infer and have-SH, S
2-soft base Deng group may the easier silver-colored coordination with belonging to soft acid than the pyrroles belonging to boundary alkali.Many researchers also demonstrate that to there is 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 the anti-biotic material for modified montmorillonoid preparation safety.
Summary of the invention
The object of the invention is to the defect existed for prior art, provide a kind of and can be good at loading nano silvery and carry out the silver-carrying modified montmorillonite antibacterial agent of long-acting release.
Another object of the present invention is to the preparation method that described silver-carrying modified montmorillonite antibacterial agent is provided.
Another object of the present invention is the application providing described silver-carrying modified montmorillonite antibacterial agent.
The technical solution used in the present invention is:
Silver-carrying modified montmorillonite antibacterial agent, the carrier that this antibacterial agent is load silver ion with the imvite of sulfur amino acid modification.
Silver-carrying modified montmorillonite antibacterial agent, its raw material by weight, comprises following component: imvite 1 ~ 5 part, and sulfur amino acid 0.5 ~ 3 part, 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) prepare silver salt solution, add modified montmorillonoid, be uniformly dispersed;
(3) microwave radiation technology reaction is after 2 ~ 10 minutes, and washing is dry, and grinding, obtains presoma;
(4) presoma was through UV-irradiation 4 ~ 48 hours, obtained 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: imvite is scattered in deionized water by (1), obtains imvite suspension; (2) prepare the aqueous solution of sulfur amino acid, and adjust pH to 1.2 ~ 2.5; (3) added in imvite suspension by the aqueous solution of sulfur amino acid, be warming up to 40 ~ 70 DEG C, stirring reaction 1 ~ 2 hour, washing, dry, grinding, 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, its raw material contains the above-mentioned silver-carrying modified montmorillonite antibacterial agent of 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 it have good combination with the silver ion loading to modified montmorillonoid interlayer, improves silver carrying amount.Direct imvite is carried out the silver-colored imvite silver carrying amount that carries that ion exchange obtains and is only 1.22%, and can reach 10.93% with the silver-carrying modified imvite silver carrying amount that cystine modified montmorillonoid obtains.
(2) change load into Nano Silver at the silver ion of modified montmorillonoid interlayer by ultraviolet irradiation method, and directly strongly interact by sulfur-containing group and silver and strengthen montmorillonite layer and the binding ability of silver, improve and carry the release performance of silver-colored imvite.Compared with non-irradiated sample, 48 hours silver-colored release rates of the silver-carrying modified imvite obtained for 48 hours through ultraviolet irradiation have decreased to 22.096% by 33.076%.
(3) silver-carrying modified montmorillonite antibacterial agent of the present invention has good bacteriostasis property, and add the polypropylene plastics carrying silver-colored methionine modified montmorillonoid antibacterial agent of 3wt%, its antibacterial circle diameter can be increased 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 shortcomings such as being separated, very easy to use, by common plastics melt blending processing method, can be dispersed in the plastic basis material such as polypropylene, ABS, processing technology is simple, easy control, has 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.The notch impact strength of carrying the polypropylene plastics of silver-colored methionine modified montmorillonoid antibacterial agent as added 3wt% reaches 5.28KJ/m
2, than impact strength 3.00 KJ/m of virgin pp plastics
2be significantly improved.
Accompanying drawing explanation
Fig. 1 is sodium-based montmorillonite, carries 2 ~ 12 ° of X-ray diffractograms of silver-colored methionine modified montmorillonoid presoma, year silver-colored cysteine-modifying imvite presoma and year silver-colored cystine modified montmorillonoid presoma.
Fig. 2 is sodium-based montmorillonite, carries silver-colored cystine modified montmorillonoid presoma and the X-ray diffractogram of 30 ° ~ 70 ° carrying silver-colored cystine modified montmorillonoid antibacterial agent through ultraviolet irradiation.
Fig. 3 is the transmission electron microscope photo carrying silver-colored cystine modified montmorillonoid antibacterial agent through ultraviolet irradiation acquisition in 48 hours.
Embodiment
Silver-carrying modified montmorillonite antibacterial agent, the carrier that this antibacterial agent is load silver ion with the imvite of sulfur amino acid modification.
Silver-carrying modified montmorillonite antibacterial agent, its raw material by weight, comprises following component: imvite 1 ~ 5 part, and sulfur amino acid 0.5 ~ 3 part, 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 the imvite of other classifications as required.
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: adopt sulfur amino acid to carry out modification to imvite in acid condition and obtain modified montmorillonoid, then by ion exchange, silver ion is loaded on modified montmorillonoid with silver salt solution under microwave irradiation, 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) prepare silver salt solution, add modified montmorillonoid, be uniformly dispersed;
(3) microwave radiation technology reaction is after 2 ~ 10 minutes, and washing is dry, and grinding, obtains presoma;
(4) presoma was through UV-irradiation 4 ~ 48 hours, obtained 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, microwave radiation technology reaction 2.5 ~ 5 minutes.
Preferably, the preparation of modified montmorillonoid comprises the following steps: imvite is scattered in deionized water by (1), obtains imvite suspension; (2) prepare the aqueous solution of sulfur amino acid, and adjust pH to 1.2 ~ 2.5; (3) added in imvite suspension by the aqueous solution of sulfur amino acid, be warming up to 40 ~ 70 DEG C, stirring reaction 1 ~ 2 hour, washing, dry, grinding, 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 material such as polypropylene, ABS, can prepare the plastic products with excellent bacteriostasis property.
Antibiotic plastic, its raw material contains the above-mentioned silver-carrying modified montmorillonite antibacterial agent of 1 ~ 3wt%.
The preparation method of antibiotic plastic, comprises the following steps:
(1) at 160 ~ 170 DEG C of temperature, make polypropylene or ABS melting bag roller, then add antioxidant and silver-carrying modified montmorillonite antibacterial agent;
(2) mixing evenly rear compressing tablet, obtained 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, set forth content of the present invention further.
embodiment 1
(1) preparation of modified montmorillonoid
Getting 1g sodium-based montmorillonite (Na-MMT) is dispersed in 100ml deionized water, within 1 hour, obtains imvite suspension in 60 DEG C of stirrings; In another beaker, add the sulfur amino acid of 1.9g and the deionized water of 100ml, the HCl adjust ph added at 60 DEG C containing 0.1mol/L is 1.8, obtains the sulfur amino acid aqueous solution; The sulfur amino acid aqueous solution is joined in imvite suspension, stirs 1 hour at 60 DEG C, be cooled to room temperature, washing and filtering, until the AgNO of filtrate 0.1mol/L
3detect without white precipitate; Finally product is put in baking oven, in 70 DEG C 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 DEG C of stirring 30min are uniformly dispersed, be placed in microwave generator, react 4 minutes under 750W power, cooling, washing and filtering, (does not namely contain Ag to through hydrochloric acid inspection filtrate without white precipitate material
+), dry to constant weight, grinding refinement, obtains silver-carrying modified montmorillonite antibacterial agent presoma, is designated as Ag@AA-MMT; Under Ag@AA-MMT is placed in the ultraviolet lamp of 365nm wavelength, irradiation is after 48 hours, obtains the silver-carrying modified montmorillonite antibacterial agent of product, is designated as Ag@AA-MMT-UV.
As stated above, methionine, cysteine, cystine is used to prepare three kinds of different silver-carrying modified montmorillonite antibacterial agents respectively.Performance characterization is as follows:
Fig. 1 is sodium-based montmorillonite (Na-MMT), carries 2 ° ~ 12 ° X-ray diffractograms of silver-colored methionine modified montmorillonoid presoma (Ag@AA-MMT-1), year silver-colored cysteine-modifying imvite presoma (Ag@AA-MMT-2) and year 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, d is Ag@AA-MMT-3.Can find out does not have that the MMT interlamellar spacing of modification is 1.21nm, Ag@AA-MMT-1, the interlamellar spacing of Ag@AA-MMT-2 and Ag@AA-MMT-3 is increased to 1.28nm, 1.35nm and 1.34nm respectively.
Fig. 2 is Na-MMT, Ag@AA-MMT-3 and carries the X-ray diffractogram of 30 ° ~ 70 ° of silver-colored cystine modified montmorillonoid (Ag@AA-MMT-3-UV) through ultraviolet irradiation, and wherein, a is Na-MMT, b be Ag@AA-MMT-3, c is Ag@AA-MMT-3-UV.Can see that three kinds of silver-carrying modified imvites have all occurred 38.4 °, 44.4 ° and 64.3 ° the diffraction maximum corresponding to nanocrystalline silver structure.
Fig. 3 is the transmission electron microscope photo of the Ag@AA-MMT-3-UV through ultraviolet irradiation acquisition in 48 hours, can see the Nano Silver of black particle shape, its size uniform, good dispersion.
Carry silver-colored imvite to compare with the silver carrying amount of silver-carrying modified imvite presoma:
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 that prepare by method of the present invention silver-carrying modified imvite presomas and bacteriostasis property all carry silver-colored imvite than routine and are improved largely.
Silver carrying amount and the bacteriostasis property of table 1 year silver-colored imvite and silver-carrying modified imvite presoma compare
| 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 |
embodiment 2
(1) preparation of modified montmorillonoid
Get 2g calcium-base montmorillonite to be dispersed in 100ml deionized water, obtain imvite suspension; In another beaker, add the cystine of 0.5g and the deionized water of 100ml, and adjust ph is 1.2, obtains the cystine aqueous solution; The cystine aqueous solution is joined in imvite suspension, is warming up to 70 DEG C, stirring reaction 1 hour, is then cooled to room temperature, washing and filtering, until filtrate AgNO
3detect 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 DEG C, stirring makes to be uniformly dispersed, and is then placed in microwave generator, reacts 10 minutes under 400W power, cooling, washing and filtering, checks filtrate without after white precipitate material to through hydrochloric acid, dries to constant weight, grinding refinement, must carry silver-colored cystine modified montmorillonoid antibacterial agent presoma; Presoma to be placed under ultraviolet lamp irradiation 24 hours, silver-colored cystine modified montmorillonoid antibacterial agent must be carried.
embodiment 3
(1) preparation of modified montmorillonoid
Get 5g sodium-based montmorillonite to be dispersed in 100ml deionized water, obtain imvite suspension; In another beaker, add the cystine of 3 g and the deionized water of 100ml, and adjust ph is 2.5, obtains the cystine aqueous solution; The cystine aqueous solution is joined in imvite suspension, is warming up to 40 DEG C, stirring reaction 2 hours, is then cooled to room temperature, washing and filtering, until filtrate AgNO
3detect 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 DEG C, stirring makes to be uniformly dispersed, and is then placed in microwave generator, reacts 2 minutes under 800W power, cooling, washing and filtering, checks filtrate without after white precipitate material to through hydrochloric acid, dries to constant weight, grinding refinement, must carry silver-colored cystine modified montmorillonoid antibacterial agent presoma; Presoma to be placed under ultraviolet lamp irradiation 4 hours, silver-colored cystine modified montmorillonoid antibacterial agent must be carried.
embodiment 4
The preparation method of the present embodiment and reaction condition, as embodiment 1, change liquor argenti nitratis ophthalmicus concentration time prepared by silver-carrying modified imvite, and the silver carrying amount data of gained silver-carrying modified imvite presoma are as shown in table 2.
Under the different silver nitrate concentration of table 2, the silver carrying amount of the silver-carrying modified imvite presoma of gained compares
| 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, this is because the concentration improving liquor argenti nitratis ophthalmicus is equivalent to the concentration increasing reactant, the chemical balance forward being 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 Ag in the silver nitrate because of excessive concentrations
+can not ionize completely, cause the actual Ag increasing participation ion exchange in solution
+number and concentration value added can not be completely reciprocity, and thus the growth trend of the silver carrying amount of silver-carrying modified imvite presoma slows down.Consider the factors such as cost, the concentration selecting liquor argenti nitratis ophthalmicus is that 0.2mol/L is proper.
embodiment 5
The preparation method of the present embodiment and reaction condition are as embodiment 1, and keep liquor argenti nitratis ophthalmicus concentration to be 0.2mol/L, change microwave reaction time time prepared by silver-carrying modified imvite, the silver carrying amount data of gained silver-carrying modified imvite presoma are as shown in table 3.
Under the table 3 different microwave reaction time, the silver carrying amount of the silver-carrying modified imvite presoma of gained compares
| 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 |
Significantly can see that silver carrying amount reaches peak when the microwave reaction time is 4min, after continuing prolongation when reacted, the silver carrying amount of silver-carrying modified imvite presoma declines on the contrary.This is because after reaching optimum value when reacted, continue to increase radiation, modified montmorillonoid can be caused dry rapidly, and temperature rises rapidly, and the chemical balance of ion exchange is destroyed, and thus silver carrying amount reduces.
embodiment 6
The preparation method of the present embodiment and reaction condition, as embodiment 1, take 0.1g sample, put into the triangular flask that 100ml distilled water is housed, be fixed on 25 DEG C 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 carry silver-colored imvite release silver-colored rate, result data is as shown in table 4.
The silver-colored rate of releasing of the different silver-carrying modified imvite of table 4 compares
Can see, the silver-colored rate of releasing of Ag@AA-MMT-3 and Ag@AA-MMT-3-UV all declines to some extent than Ag@MMT, mainly because the sulfur-containing group on cystine modified montmorillonoid strengthens 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 significantly carries silver-colored imvite lower than other two kinds, this is mainly because the Nano Silver of its load can interact with the sulfur-containing group on modified montmorillonoid surface, this combination hinders silver and proceeds to rapidly free ion state by chemical bound state, thus the release of impact silver.
embodiment 7
That embodiment 1 is prepared carries silver-colored methionine modified montmorillonoid antibacterial agent (Ag@AA-MMT-1-UV) as bacteriostatic agent for the preparation of bacteriostatic PP, and preparation method is as follows:
(1) at 160 DEG C of temperature, make polypropylene fusion bag roller, then add antioxidant 1010 and Ag@AA-MMT-1-UV;
(2) mixing evenly rear compressing tablet, obtained Antibacterial polypropylene plastic;
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 impact of the mechanical property of consumption on bacteriostatic PP of Ag@AA-MMT-1-UV and the bacteriostasis property on staphylococcus aureus is as shown in table 4.
The table 4 different Ag@mechanical property of AA-MMT-1-UV consumption on 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, adding of Ag@AA-MMT-1-UV improves rapidly polyacrylic bacteriostasis, and when addition is only 1wt%, namely antibacterial circle diameter increases 56.6%; Also increase to the mechanical property of bacteriostatic PP adding of Ag AA-MMT-1-UV, when addition is 3wt%, the impact strength of bacteriostatic PP and tensile strength distribution, than improve 76% and 14% before adding, obtain good combination property simultaneously.
Claims (6)
1. silver-carrying modified montmorillonite antibacterial agent, the carrier that this antibacterial agent is load silver ion with the imvite of cystine modification; The preparation method of described silver-carrying modified montmorillonite antibacterial agent, comprises the following steps:
(1) adopt cystine to carry out modification to imvite, obtain modified montmorillonoid;
(2) prepare silver salt solution, add modified montmorillonoid, be uniformly dispersed;
(3) microwave radiation technology reaction is after 2 ~ 10 minutes, and washing is dry, and grinding, obtains presoma;
(4) presoma was through UV-irradiation 4 ~ 48 hours, obtained silver-carrying modified montmorillonite antibacterial agent;
Wherein, imvite 1 ~ 5 part, cystine 0.5 ~ 3 part, containing the water soluble silver salt of 0.1 ~ 0.6 part of silver ion.
2. silver-carrying modified montmorillonite antibacterial agent according to claim 1, is characterized in that: in silver salt solution, concentration of silver ions is 0.15 ~ 0.3mol/L.
3. silver-carrying modified montmorillonite antibacterial agent according to claim 1, is characterized in that: microwave power is 400 ~ 800W.
4. silver-carrying modified montmorillonite antibacterial agent according to claim 1, is characterized in that: the preparation of modified montmorillonoid comprises the following steps:
(1) imvite is scattered in deionized water, obtains imvite suspension;
(2) prepare the aqueous solution of cystine, and adjust pH to 1.2 ~ 2.5;
(3) added in imvite suspension by the aqueous solution of cystine, be warming up to 40 ~ 70 DEG C, stirring reaction 1 ~ 2 hour, washing, dry, grinding, obtains modified montmorillonoid.
5. the application of silver-carrying modified montmorillonite antibacterial agent according to claim 1 in plastics, coating, adhesive, ceramic material and goods thereof.
6. antibiotic plastic, its raw material contains the according to claim 1 silver-carrying modified montmorillonite antibacterial agent of 1 ~ 3wt%.
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