The preparation method of composite nano antibacterial agent and antibiotic NL latex and antibiotic TPI rubber
Technical field
The present invention relates to that the complex precipitation method prepare the ZnO/Ag composite nano antibacterial agent and be the method for additive preparation antimicrobial natural (NL) latex and antibiotic TPI rubber with this antibacterial agent.
Technical background
Antibacterial agent is divided into natural, organic and inorganic antiseptic three major types.Natural antibacterial agent is mainly natural plant extracts, but its antibacterial effect is not so good as organic antibacterial agent, and limited by resource, and application has certain difficulty; Though organic antibacterial agent quick result, sterilizing ability are stronger, toxic side effect, and poor heat resistance, easily decompose, service life is short, and the defective that produces secondary pollution is arranged.By comparison, inorganic antiseptic, the nano inorganic antimicrobial agent that particularly develops rapidly in recent years, nano inorganic complex antimicrobials reach by its anti-biotic material that makes has antibacterial characteristics safe, efficient, wide spectrum, the notion that meets " Green Chemistry ", belong to environmentally friendly material, thereby receive much concern.
In many nano inorganic antimicrobial agents, nano-ZnO is with low cost, and is nontoxic to human body, is a kind of anti-biotic material that application prospect is arranged, but because its anti-microbial property is lower, limited its practical application.(Toshiaki?Ohira,Osamu?Yamamoto,YasuhiroIida,Zenbe-e?Nakagawa.Antibacterial?activity?of?ZnO?powder?with?crystallographic?orientation.JMater?Sci:Mater?Med,2008,19:1407-1412.)。Nanometer Ag has high heat endurance and remarkable antibiotic persistence, but easy to change and price is higher.Noble metal and metal semiconductor oxide are compound to be effective way (the Young Hwan Kim that improves its various physics and chemical property, Don Keun Lee, Hyun Gil Cha, Chang Woo Kim, Young Soo Kang, Synthesis and Characterization of Antibacterial Ag-SiO
2Nanocomposite.J.Phys.Chem.C 2007,111,3629-3635.Haibo Zeng, Peisheng Liu, Weiping Cai, Shikuan Yang, Xiaoxia Xu.ControllablePt/ZnO Porous Nanocages with Improved Photocatalytic Activity.J.Phys.Chem.C 2008,112,19620-19624.TsutomuHirakawa, PrashantV.Kamat.Charge Separation and Catalytic Activity ofAg@TiO
2Core Shell Composite Clusters under UV Irradiation.J AM.CHEM.SOC.2005,127 (11): 3928-3934).Nanometer Ag and ZnO is compound, because the synergy of two kinds of nano materials, not only overcome the high allochroic deficiency of nanometer Ag antibacterial agent cost, can also improve the anti-microbial property of nano-ZnO, thereby obtain the high composite nano antibacterial agent of a kind of antibacterial activity with low cost.
At present, the existing multiple method for preparing composite nano materials.For example: the patented invention of publication number CN101550497 " an one step wet heating legal system is equipped with the method for zinc oxide composite coated with nano-silver particles "; in addition; the main method of the preparation ZnO/Ag composite of bibliographical information also has high-molecular gel method (Shao Zhongbao; Wang Chengyan; old snow ice; Deng. the preparation of nano-ZnO/Ag and photocatalysis performance thereof [J]. the investigation of materials journal; 2005; 190 (1): 59-63.); dipping photolysis method (Chen Shihai; NICKEU.Controllable excition bleaching and recovery observed in ZnO/Ag hybridnanometer-sized particles[J] .Chem.Commun.; 1996; 10 (2): 133-134.); compound heating evaporation technology (the Ronghua Wang of laser; John Haozhong Xin; Yang Yang; Hongfang Liu; Liming Xu; Junhui Hu.Thecharacteristics and photocatalytic activities of silver doped ZnO nanocrystallites[J] .AppliedSurface Science; 2004; 227:312-317.) etc.; but these methods or complex process; or preparation condition harshness; or high to the equipment requirement, be unfavorable for large-scale production.Therefore, the method for preparing the ZnO/Ag composite nano antibacterial agent that development and operation is easy, product is controlled, with low cost has the most important theories meaning and uses using value.
Antibiotic NL latex and antibiotic TPI rubber can effectively suppress the harmful microbe breeding, therefore have a wide range of applications in fields such as medical materials.The tradition antibacterial rubber is that organic anti-bacterial additive (tetraamine compound, organoarsenic compound etc.) is mixed in the sizing material, yet these organic antibacterial agents all have the migration precipitation tendency, cause traditional antibacterial rubber to have antibiotic timeliness weak point, poor stability, certain defectives such as toxic and side effect are arranged, also can produce offensive odour, cause the sense organ discomfort.(Zheng Xuqi. be used for the novel antibacterial rubber in food processing, packing, medical treatment and other fields. rubber reference, 2004,34 (2): 11-14).Therefore, substitute organic antibacterial agent such as organoarsenic compound with safety, ZnO/Ag composite nano antibacterial agent efficient, wide spectrum, give excellent more antibacterial characteristics of antibiotic NL latex and antibiotic TPI rubber and more wide application prospect surely as functional additive.
Summary of the invention
Defective at existing ZnO/Ag composite nano antibacterial agent and antibiotic NL latex and antibiotic TPI method for preparing rubber, the present invention proposes the method that the complex precipitation method a kind of simple to operate, with low cost prepare the ZnO/Ag composite nano antibacterial agent and use this preparation of antimicrobial NL latex and antibiotic TPI rubber that proposed.
Technical scheme of the present invention is: adopt the complex precipitation method to prepare the ZnO/Ag composite nano antibacterial agent, and be additive with this antibacterial agent, adopt the antibiotic NL latex of immersion process for preparing, adopt the twin-roll mixing method to prepare antibiotic TPI rubber.It is characterized in that:
(1) with solvable zinc salt [Zn (NO
3)
2Or Zn (Ac)
2] and AgNO
3Be raw material, NH
3H
2O is a complexant, and reaction generates complex solution.Solvable zinc salt, AgNO
3And NH
3H
2The ratio of the amount of substance of O is n (soluble zinc salt): n (AgNO
3): n (NH
3H
2O)=1: 0.02~0.33: 4.10~4.70.
(2) under 50~70 ℃, carry out hydrolysis 35~55min earlier, the generating portion post precipitation is again by solvable zinc salt, AgNO
3, NH
3H
2O and precipitating reagent [(NH
4)
2CO
3Or Na
2CO
3Or (NH
4)
2CO
3And Na
2CO
3Both mixtures] the ratio of amount of substance be n (soluble zinc salt): n (AgNO
3): n (NH
3H
2O): n (precipitating reagent)=1: 0.02~0.33: 4.10~4.70: 1.52~1.75, drip precipitating reagent with the speed of 2~15ml/s, continue reaction 120~150min.
(3) stop to react the back centrifugation, clean and drying, obtain with Zn (OH)
2And Zn
5(OH)
8(NO
3)
2 2NH
3Be nuclear, Zn
5(OH)
6(CO
3)
2And Ag
2CO
3Precursor for external coating.
(4) vessel that will fill body place in the stove, earlier furnace temperature are risen to 200 ℃, insulation 60~120min, and then be warming up to 350~450 ℃, and insulation 240min, cool off with stove, can obtain the about 10~25nm of particle diameter, tool is with the ZnO/Ag composite nano antibacterial agent of good anti-microbial property.
(5) under the prerequisite that does not change immersion process for preparing NL latex common process and prescription substantially, the ZnO/Ag composite nano antibacterial agent that the ratio in 0.29~0.67% adds after disperseing makes antibiotic NL latex.Preparation technology is as follows: at first under mechanical agitation, add casein solution, KOH solution successively in latex, the promoter dispersion after the vulcanizing agent dispersion, adds and disperses back ZnO/Ag composite nano antibacterial agent, presulfurization 30min in 60~70 ℃ of waters bath with thermostatic control, be cooled to room temperature, and then add the promoter dispersion successively, the vulcanizing agent dispersion, the age resistor dispersion, lanolin emulsion makes latex, filters stand-by.Propose after then model being flooded 30s in the starch coagulating agent, dry back is immersed in the good latex of presulfurization in 80 ℃ of hot-airs, proposes behind the stop 30s, in 70 ℃ of drying 1~1.5h, makes antibacterial latex.
(6) do not changing substantially under the prerequisite that the twin-roll mixing legal system is equipped with TPI rubber common process and prescription, the ZnO/Ag composite nano antibacterial agent after disperseing is being joined in the rubber, making antibiotic TPI rubber.
Preparation technology is as follows: earlier mill is warming up to 50~70 ℃, adds rubber size, the 3~7min that plasticates is to sizing material bag roller.Carry out mixingly subsequently, and in mixing process, add stearic acid, age resistor, promoter, reinforcing agent at first successively, and then add composite nano antibacterial agent, add sulphur at last.Continued mixing 20~30 minutes, treat that the rubber integral color evenly after, roll spacing is transferred to about 1mm, play the triangle bag six times, under 143~150 ℃ and 15MPa pressure, vulcanize 27~32min and prepare antibiotic TIP rubber.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 prepares the process chart of ZnO/Ag composite nano antibacterial agent and antibiotic NL latex and antibiotic TPI rubber for the complex precipitation method.
Fig. 2 is the X-Ray diffracting spectrum of embodiment 1 gained ZnO/Ag composite nano antibacterial agent.
Fig. 3 is the transmission electron microscope photo of embodiment 1 gained ZnO/Ag composite nano antibacterial agent.
Fig. 4 is that embodiment 1 gained ZnO/Ag composite nano antibacterial agent is to colibacillary antibacterial experiment photo.Wherein scheme (a) no antibacterial agent; (b) antibacterial agent concentration is 20mg/L; (c) antibacterial agent concentration is 50mg/L.
Fig. 5 is the X-Ray diffracting spectrum of embodiment 2 gained ZnO/Ag composite nano antibacterial agents.
Fig. 6 is the transmission electron microscope photo of embodiment 2 gained ZnO/Ag composite nano antibacterial agents.
Fig. 7 is the antibacterial experiment photos of embodiment 2 gained ZnO/Ag composite nano antibacterial agents to the Escherichia coli bacterium.(a) no antibacterial agent wherein; (b) antibacterial agent concentration is 20mg/L; (c) antibacterial agent concentration is 40mg/L.
Fig. 8 is the antibacterial experiment photo to staphylococcus aureus of antibiotic NL latex.(a) no antibacterial agent wherein; (b) 0.1g antibacterial agent; (c) 0.5g antibacterial agent.
Fig. 9 is the antibacterial experiment photo of antibiotic TPI rubber to the Escherichia coli bacterium.(a) no antibacterial agent wherein; (b) 1g antibacterial agent; (c) 5g antibacterial agent.
Embodiment
Fig. 1 is seen in the technological process of preparation ZnO/Ag composite nano antibacterial agent and antibiotic NL latex and antibiotic TPI rubber.
Embodiment 1. is with Zn (NO
3)
2And AgNO
3Be raw material, NH
3H
2O is a complexant, (NH
4)
2CO
3Be precipitating reagent, adopt the complex precipitation method to prepare the ZnO/Ag composite nano antibacterial agent.
(1) gets the Zn (NO that 30ml concentration is 1mol/L
3)
2Solution is in there-necked flask, and adding 10ml quality percentage composition is 25%~28% dense NH under stirring
3H
2O, the ratio by the amount of substance of raw material is n[Zn (NO again
3)
2]: n[AgNO
3It is the AgNO of 0.168mol/L that]=1: 0.083 adds 15ml concentration
3Solution, make its fully react the clear complex solution.
(2) complex solution is behind the reaction 45min that is hydrolyzed under 60 ℃, and the speed dropping 45ml concentration with 3ml/s is the (NH of lmol/L again
4)
2CO
3Continue to react to 120min under the solution, equality of temperature and stop.Centrifugation is cleaned with distilled water and ethanol, and drying precipitated in drying box, obtains with Zn (OH)
2And Zn
5(OH)
8(NO
3)
2 2NH
3Be nuclear, coat Zn
5(OH)
6(CO
3)
2And Ag
2CO
3The precursor of ZnO/Ag composite nano antibacterial agent.
(3) crucible that will fill precursor places in the stove, earlier furnace temperature is warming up to 200 ℃, insulation 90min, continue to be warming up to 350 ℃ again, insulation 240min, then with stove cooling, obtain having the ZnO/Ag composite nano antibacterial agent of the Ag of hexagonal wurtzite structure ZnO crystal and cubic structure, its X-Ray diffracting spectrum is seen Fig. 2; About 10~the 20nm of the particle diameter of complex antimicrobials, its transmission electron microscope photo is seen Fig. 3; This antibacterial agent of different amounts is seen Fig. 4 to colibacillary antibacterial experiment photo.The minimal inhibitory concentration of antibacterial agent is 50mg/L, is better than the required standard of HG/T 3794-2005 " inorganic antiseptic-performance and evaluation ".
Embodiment 2. operating procedures are with embodiment 1, but precipitating reagent is Na
2CO
3, control raw material ratio n[Zn (NO
3)
2)]: n[AgNO
3]: n[NH
3H
2O]: n[Na
2CO
3] be 1: 0.09: 4.31: 1.67, single step reaction time 55min, two step reaction time 150min during the calcining presoma, are incubated 120min down at 200 ℃ earlier, continue to be warming up to 450 ℃ again, insulation 240min, with stove cooling, the gained antibacterial agent is with to execute example 1 the same, be the complex of the Ag of hexagonal wurtzite structure ZnO crystal and cubic structure, its X-Ray diffracting spectrum is seen Fig. 5; About 10~the 25nm of particle diameter, its transmission electron microscope photo is seen Fig. 6; This antibacterial agent of different amounts is seen Fig. 7 to colibacillary antibacterial experiment photo.The minimal inhibitory concentration of antibacterial agent is 40mg/L, is better than the required standard of HG/T 3794-2005 " inorganic antiseptic-performance and evaluation ".
Embodiment 3. antibiotic NL latex preparations.
Under mechanical agitation, the casein solution that in the 100g Heveatex, adds 5g 10% successively, 1g 10%KOH solution, 2g50% TM monex TD dispersion, 0.6g 50%S dispersion, 1g 50%ZnO/Ag composite nano antibacterial agent dispersion, in 70 ℃ of waters bath with thermostatic control, be cooled to room temperature behind the presulfurization 30min, the promoter ZDC dispersion that adds 1g 50% more successively, the S dispersion of 0.4g50%, the antioxidant 264 dispersion of 1g 50%, the lanolin emulsion of 2.5g 20%, make latex, filter stand-by.Model is flooded 30s propose in the starch coagulating agent, dry back is immersed in the good latex of presulfurization in 80 ℃ of hot-airs, and 30s proposes, and 70 ℃ of dry 1h make antibiotic NL latex.Add the prepared antibiotic NL latex of different amount antibacterial agents the antibacterial experiment photo of staphylococcus aureus is seen Fig. 8.When the antibacterial agent consumption was 0.5g, antibiotic rate was 99.62%, was better than 2002 disinfection technology standard standards.
The preparation of embodiment 4. antibiotic TPI rubber.
Earlier mill is warming up to 70 ℃, adds 100g TPI, the 5min that plasticates, treat sizing material bag roller after, add 1g (C successively
17H
35COO)
2AlOH, 3g C
18H
22O
2, 30g CaCO
3ZnO/Ag composite nano antibacterial agent with after the 5g dispersion adds 0.5g S at last.Mixing evenly after, roll spacing is transferred to about 1mm, play the triangle bag six times ,] under 45 ℃, 15MPa, vulcanize 30min and prepare antibiotic TPI rubber.Add the prepared antibiotic TPI rubber of different amount antibacterial agents colibacillary antibacterial experiment photo is seen Fig. 9.When the antibacterial agent consumption was 5g, antibiotic rate was 99.67%, was better than 2002 disinfection technology standard standards.