CN101836660B - Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber - Google Patents
Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber Download PDFInfo
- Publication number
- CN101836660B CN101836660B CN2010101388069A CN201010138806A CN101836660B CN 101836660 B CN101836660 B CN 101836660B CN 2010101388069 A CN2010101388069 A CN 2010101388069A CN 201010138806 A CN201010138806 A CN 201010138806A CN 101836660 B CN101836660 B CN 101836660B
- Authority
- CN
- China
- Prior art keywords
- composite nano
- antibacterial agent
- latex
- zno
- antibiotic
- 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.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000004816 latex Substances 0.000 title claims abstract description 48
- 229920000126 latex Polymers 0.000 title claims abstract description 48
- 229920001971 elastomer Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003242 anti bacterial agent Substances 0.000 claims description 85
- 230000003115 biocidal effect Effects 0.000 claims description 56
- 239000011701 zinc Substances 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 14
- 101710134784 Agnoprotein Proteins 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 10
- 230000000845 anti-microbial effect Effects 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- 239000004166 Lanolin Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000005018 casein Substances 0.000 claims description 4
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 4
- 235000021240 caseins Nutrition 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000000701 coagulant Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 229940039717 lanolin Drugs 0.000 claims description 4
- 235000019388 lanolin Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 abstract 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 abstract 1
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 abstract 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 86
- 239000011787 zinc oxide Substances 0.000 description 45
- 238000002474 experimental method Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000004599 antimicrobial Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- -1 tetraamine compound Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method of a composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber. Zn(NO3)2 or Zn(Ac)2, AgNO3, NH3.H2O, (NH4)2CO3 or Na2CO3 are used as raw materials, hydrolyzed by a coordination compound and then settled to prepare a precursor of a ZnO/Ag composite nano-antibacterial, which takes Zn(OH)2 and Zn5(OH)8(NO3)2.2NH3 as a core and is covered with Zn5(OH)6(CO3)2 and Ag2CO3. The precursor is calcined to obtain the ZnO/Ag composite nano-antibacterial with grain diameter of 10-25 nm and excellent antibacterial property, wherein the MIC (Minimal Inhibitory Concentration) of the ZnO/Ag composite nano-antibacterial is lower than 50mg/L. The method has simple operation, high yield, low cost and easy industrialization. Antibacterial NL latex and antibacterial TPI rubber which have excellent antibacterial property are prepared by taking the obtained antibacterial as functional filling.
Description
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 receives resource limit, application that certain difficulty is arranged; Though organic antibacterial agent quick result, sterilizing ability are stronger, toxic side effect, and poor heat resistance, be prone to 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 " belongs to the environmental friendliness type material, thereby receives much concern.
In many nano inorganic antimicrobial agents, nano-ZnO is with low cost, to human non-toxic, is a kind of anti-biotic material that application prospect is arranged, but because its anti-microbial property is lower, has 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.Controllable Pt/ZnO Porous Nanocages with Improved Photocatalytic Activity.J.Phys.Chem.C 2008; 112,19620-19624.TsutomuHirakawa, PrashantV.Kamat.Charge Separation and Catalytic Activity ofAgTiO
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, etc. 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.), Laser Combined heating evaporation technology (Ronghua Wang, Haozhong Xin; Yang Yang, Hongfang Liu, Liming Xu; Junhui Hu.Thecharacteristics and photocatalytic activities of silver doped ZnO nanocrystallites [J] .Applied Surface; Science, 2004,227:312-317.) etc.; But these methods or complex process; Or preparation condition is harsh, or high to equipment requirements, is 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 applications is worth.
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 that sense organ is uncomfortable.(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 to 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.
Concrete, the invention provides the preparation method of composite nano antibacterial agent and antibiotic NL latex and antibiotic TPI rubber, it is characterized in that: with soluble zinc salt and AgNO
3Be raw material, NH
3H
2O is a complexant, makes complex solution.After making complex hydrolysis generate partly precipitated, the speed with 2～15ml/s drips precipitating reagent again, treats deposition fully, centrifugation, washing, drying, the precursor of ZnO/Ag composite nano antibacterial agent.It is 10～25nm that the calcining precursor obtains particle diameter, has the ZnO/Ag composite nano antibacterial agent of good anti-microbial property.With gained ZnO/Ag composite nano antibacterial agent is additive, adopts infusion process and twin-roll mixing method to make antibiotic NL latex and antibiotic TPI rubber respectively.
In the said method, the preparation method of composite nano antibacterial agent is characterised in that: the raw material soluble zinc salt can be Zn (NO
3)
2Or Zn (Ac)
2, concentration is 1mol/L; Complexant is NH
3H
2O, wherein NH
3The quality percentage composition be 25%～28%, precipitating reagent can be (NH
4)
2CO
3Or Na
2CO
3Or (NH
4)
2CO
3And Na
2CO
3Both mixtures.The ratio of the amount of substance of raw material, complexant and precipitating reagent is 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.
In the said method, the synthesis temperature of the precursor of ZnO/Ag composite nano antibacterial agent is 50～70 ℃, and the single step reaction time is 35～55min, and two reaction time in step were 120～150min.
In the said method, the precursor of ZnO/Ag composite nano antibacterial agent is with Zn (OH)
2And Zn
5(OH)
8(NO
3)
22NH
3Be nuclear, Zn
5(OH)
6(CO
3)
2And Ag
2CO
3Be external coating.
In the said method, the precursor of calcining ZnO/Ag composite nano antibacterial agent carries out in common chamber type electric resistance furnace or vacuum atmosphere oven in two steps, earlier at 200 ℃ of insulation 60～120min down, makes decomposition temperature lower and be positioned at the Zn (OH) of precursor heart portion
2And Zn
5(OH)
8(NO
3)
22NH
3Decompose earlier, and with the Zn of external coating
5(OH)
6(CO
3)
2And Ag
2CO
3Burst apart, help obtaining the small size product.And then be warming up to 350～450 ℃, and insulation 240min, make Zn
5(OH)
6(CO
3)
2And Ag
2CO
3Decompose fully.With the stove cooling, get particle diameter 10～25nm, tool is with the ZnO/Ag composite nano antibacterial agent of good anti-microbial property.The present invention also provides the preparation method of antibiotic NL latex; It is characterized in that: under the prerequisite that does not change immersion process for preparing NL latex common process and prescription basically, the ZnO/Ag composite nano antibacterial agent after latex cooperates the stage in 0.29～0.67% ratio adding dispersion makes antibiotic NL latex.
Antibiotic NL latex preparation technology is following: at first carry out latex and cooperate, under mechanical agitation, in latex, add casein solution, KOH solution successively; The promoter dispersion after the vulcanizing agent dispersion, adds the ZnO/Ag composite nano antibacterial agent again, presulfurization 30min in 60～70 ℃ of waters bath with thermostatic control; Be cooled to room temperature, and then add the promoter dispersion successively, vulcanizing agent dispersion, age resistor dispersion; Lanolin emulsion makes latex, filters for use.Carry out photoplate preparation then, propose model flood 30s in the starch coagulating agent after, 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.
The present invention also provides the preparation method of antibiotic TPI rubber; It is characterized in that: do not changing basically under the prerequisite that the twin-roll mixing legal system is equipped with TPI rubber common process and prescription; In mix stage; ZnO/Ag composite nano antibacterial agent after disperseing is joined in the rubber in 0.74～6.27% ratio, process antibiotic TPI rubber.
Antibiotic TPI rubber preparation technology is following: 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.
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, behind the generation partly precipitated, 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.
The vessel that (4) 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 basically, 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 following: at first under mechanical agitation, in latex, add casein solution, KOH solution, promoter dispersion successively; After the vulcanizing agent dispersion, add and disperse back ZnO/Ag composite nano antibacterial agent, presulfurization 30min in 60～70 ℃ of waters bath with thermostatic control is cooled to room temperature; And then add the promoter dispersion successively, vulcanizing agent dispersion, age resistor dispersion; Lanolin emulsion makes latex, filters for use.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 basically 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, processing antibiotic TPI rubber.
Preparation technology is following: 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
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
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 1mol/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.
The crucible that (3) will fill precursor places in the stove; Earlier furnace temperature is warming up to 200 ℃, insulation 90min continues 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 superior to the required standard of HG/T 3794-2005 " inorganic antiseptic-performance and evaluation ".
Embodiment 3. antibiotic NL latex preparations.
Under mechanical agitation, in the 100g Heveatex, add the casein solution of 5g 10% successively, 1g 10%KOH solution; 2g 50% 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, add the promoter ZDC dispersion of 1g 50% more successively, the S dispersion of 0.4g50%; The antioxidant 264 dispersion of 1g 50%; 2.5g 20% lanolin emulsion makes latex, filters for use.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 superior to 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 superior to 2002 disinfection technology standard standards.
Claims (5)
1. the preparation method of antibiotic NL latex and antibiotic TPI rubber is characterized in that: with soluble zinc salt and AgNO
3Be raw material, NH
3H
2O is a complexant, makes complex solution, make complex hydrolysis generate partly precipitated after; Speed with 2～15ml/s drips precipitating reagent again, treats deposition fully, centrifugation, washing, drying; Get the precursor of ZnO/Ag composite nano antibacterial agent; It is 10～25nm that the calcining precursor obtains particle diameter, has the ZnO/Ag composite nano antibacterial agent of good anti-microbial property, is additive with gained ZnO/Ag composite nano antibacterial agent; Adopt infusion process and twin-roll mixing method to make antibiotic NL latex and antibiotic TPI rubber respectively
In the preparation method of antibiotic NL latex, under the prerequisite that does not change immersion process for preparing NL latex common process and prescription basically, the ZnO/Ag composite nano antibacterial agent after latex cooperates the stage in 0.29～0.67% ratio adding dispersion makes antibiotic NL latex,
Antibiotic NL latex preparation technology is following: at first carry out latex and cooperate, under mechanical agitation, in latex, add casein solution, KOH solution successively; The promoter dispersion after the vulcanizing agent dispersion, adds the ZnO/Ag composite nano antibacterial agent again, presulfurization 30min in 60～70 ℃ of waters bath with thermostatic control; Be cooled to room temperature, and then add the promoter dispersion successively, vulcanizing agent dispersion, age resistor dispersion; Lanolin emulsion makes latex, filters for use; Carry out photoplate preparation then, propose model flood 30s in the starch coagulating agent after, in the latex that the immersion presulfurization of dry back is good in 80 ℃ of hot-airs; Propose after stopping 30s,, make antibiotic NL latex in 70 ℃ of drying 1～1.5h;
In the preparation method of antibiotic TPI rubber; Not changing basically 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 joined in the rubber in 0.74～6.27% ratio in mix stage; Process antibiotic TPI rubber
Antibiotic TPI rubber preparation technology is following: earlier mill is warming up to 50～70 ℃, adds rubber size, 3～7min plasticates; To sizing material bag roller, carry out subsequently mixing, 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, sulfuration 27～32min prepares antibiotic TIP rubber.
2. preparation method according to claim 1 is characterized in that: the raw material soluble zinc salt can be Zn (NO
3)
2Or Zn (Ac)
2, concentration is 1mol/L; Complexant is NH
3H
2O, wherein NH
3The quality percentage composition be 25%～28%, precipitating reagent can be (NH
4)
2CO
3Or Na
2CO
3Or (NH
4)
2CO
3And Na
2CO
3Both mixtures, the ratio of the amount of substance of raw material, complexant and precipitating reagent is soluble zinc salt: AgNO
3: NH
3H
2O: precipitating reagent=1: 0.02～0.33: 4.10～4.70: 1.52～1.75.
3. the preparation method of composite nano antibacterial agent according to claim 1, it is characterized in that: the synthesis temperature of the precursor of ZnO/Ag composite nano antibacterial agent is 50～70 ℃, and the single step reaction time is 35～55min, and two reaction time in step were 120～150min.
4. the preparation method of composite nano antibacterial agent according to claim 1 is characterized in that: the precursor of ZnO/Ag composite nano antibacterial agent is for Zn (OH)
2And Zn
5(OH)
8(NO
3)
22NH
3Be nuclear, Zn
5(OH)
6(CO
3)
2And Ag
2CO
3Be external coating.
5. the preparation method of composite nano antibacterial agent according to claim 1; It is characterized in that: the precursor of calcining ZnO/Ag composite nano antibacterial agent carries out in common chamber type electric resistance furnace or vacuum atmosphere oven in two steps; Earlier at 200 ℃ of insulation 60～120min down, make decomposition temperature lower and be positioned at the Zn (OH) of precursor heart portion
2And Zn
5(OH)
8(NO
3)
22NH
3Decompose earlier, and with the Zn of external coating
5(OH)
6(CO
3)
2And Ag
2CO
3Burst apart, help obtaining the small size product, and then be warming up to 350～450 ℃, and insulation 240min, make Zn
5(OH)
6(CO
3)
2And Ag
2CO
3Decompose fully, with the stove cooling, get particle diameter 10～25nm, tool is with the ZnO/Ag composite nano antibacterial agent of good anti-microbial property.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101388069A CN101836660B (en) | 2010-04-06 | 2010-04-06 | Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101388069A CN101836660B (en) | 2010-04-06 | 2010-04-06 | Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101836660A CN101836660A (en) | 2010-09-22 |
| CN101836660B true CN101836660B (en) | 2012-11-28 |
Family
ID=42740542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101388069A Expired - Fee Related CN101836660B (en) | 2010-04-06 | 2010-04-06 | Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101836660B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898921B (en) * | 2012-10-25 | 2015-02-11 | 陕西科技大学 | Preparation method of antibacterial leather coating material |
| CN108867036B (en) * | 2018-08-09 | 2021-06-01 | 杭州闻涛锦纶有限公司 | Modification treatment method for enhancing antibacterial property of polyester fiber |
| CN109161065A (en) * | 2018-09-19 | 2019-01-08 | 淄博正邦知识产权企划有限公司 | A kind of rubber material and preparation method thereof that medical antibacterial is wear-resisting |
| CN109233122A (en) * | 2018-11-16 | 2019-01-18 | 杨帆 | A kind of antimicrobial form composite Nano ag material water storage tank |
| CN113321865A (en) * | 2021-06-08 | 2021-08-31 | 诚德科技股份有限公司 | PE (polyethylene) antibacterial film and preparation method thereof |
| CN115322390B (en) * | 2022-08-26 | 2023-06-13 | 厦门稀土材料研究所 | Antibacterial silver complex crystal, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1140977A (en) * | 1993-11-18 | 1997-01-22 | 韦斯泰姆技术有限公司 | Anti-microbial material |
| CN1211210A (en) * | 1996-05-04 | 1999-03-17 | 巴斯福股份公司 | Process for producing dip-coated articles |
| CN1341358A (en) * | 2000-09-07 | 2002-03-27 | 刘建忠 | Silver zinc combined antimicrobial agent |
| CN1364056A (en) * | 1999-06-25 | 2002-08-14 | 阿奇化工公司 | Pyrithione biocides enhanced by silver, copper, or zinc ions |
| CN1387763A (en) * | 2002-06-12 | 2003-01-01 | 骆天荣 | Composite nano germicide and its prepn |
| CN101541312A (en) * | 2006-08-24 | 2009-09-23 | 马拉德克里科聚合物公司 | Anionic latex as a carrier for bioactive ingredients |
-
2010
- 2010-04-06 CN CN2010101388069A patent/CN101836660B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1140977A (en) * | 1993-11-18 | 1997-01-22 | 韦斯泰姆技术有限公司 | Anti-microbial material |
| CN1211210A (en) * | 1996-05-04 | 1999-03-17 | 巴斯福股份公司 | Process for producing dip-coated articles |
| CN1364056A (en) * | 1999-06-25 | 2002-08-14 | 阿奇化工公司 | Pyrithione biocides enhanced by silver, copper, or zinc ions |
| CN1341358A (en) * | 2000-09-07 | 2002-03-27 | 刘建忠 | Silver zinc combined antimicrobial agent |
| CN1387763A (en) * | 2002-06-12 | 2003-01-01 | 骆天荣 | Composite nano germicide and its prepn |
| CN101541312A (en) * | 2006-08-24 | 2009-09-23 | 马拉德克里科聚合物公司 | Anionic latex as a carrier for bioactive ingredients |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101836660A (en) | 2010-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101836660B (en) | Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber | |
| CN103015166B (en) | Nano-silver antibacterial fabric and preparation method thereof | |
| CN102233269B (en) | Integral nano material with high-efficiency removing formaldehyde at room temperature and broad-spectrum long-acting antibacterial property at same time | |
| CN101245211A (en) | Coating composition with antimicrobial and air purification function | |
| CN109432507B (en) | Antibacterial hydroxyapatite composite material containing metal oxide and preparation method thereof | |
| CN103754953B (en) | Preparation method of multi-morphologynano-sized zinc ferrite | |
| CN101347124A (en) | Method for preparing silver-carrying ion and copper ion kaolin anti-bacteria agent | |
| CN101508863B (en) | Nano-hydroxyapatite antimicrobial paint and method for producing the same | |
| CN108991013A (en) | Spraying nano mildew-proof antibacterial agent and preparation method thereof | |
| CN110200013A (en) | A kind of antibacterial mildew inhibitor and the preparation method and application thereof | |
| CN106270479A (en) | A kind of attapulgite-nanometer silver composite inorganic powder and preparation method | |
| TWI640565B (en) | Polymer latex particle composition containing nano silver particles | |
| CN101927030A (en) | Preparation method of biological dressing containing nano silver, zinc and bismuth | |
| JP7298067B2 (en) | Method for producing plate-shaped zinc oxide while controlling size and morphology | |
| CN103570072A (en) | Trimanganese tetroxide preparation method and trimanganese tetroxide prepared therethrough | |
| Li et al. | Crystal-facet-controllable synthesis of Cu 2 O microcrystals, shape evolution and their comparative photocatalytic activity | |
| US20170217840A1 (en) | Method for coating metal nanoparticles on oxide ceramic powder surface | |
| CN106633829B (en) | A kind of anti-bacteria nylon and preparation method thereof | |
| CN104558993A (en) | Modified polyvinyl alcohol membrane and preparing method thereof | |
| CN102197825B (en) | Nanosilver antibacterial agent and preparation method thereof | |
| CN115501897A (en) | Nano composite material, preparation method and application thereof in hydrogen production by visible light catalysis | |
| Balamurugan et al. | Comparison of the synthesis of s, p, d, and f block simple oxides of MgO, SnO2, NiO, and CeO2 nanostructured materials | |
| CN103651569A (en) | Technology for preparing surface-coated modified Ag/ZnO nano composite antibacterial agent | |
| CN108432831A (en) | A kind of leaf of bamboo nanometer air conditioner sterilizing powder and preparation method thereof of static magnetic field control | |
| KR102207088B1 (en) | Method for producing copper-tin nanoparticles with antibacterial activity, Copper-tin nanoparticles with antibacterial activity and Antibacterial fiber comprising copper-tin nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 266061 Shandong Province, Qingdao city Laoshan District Songling Road No. 99, Qingdao University of Science & Technology, College of chemistry and Molecular Engineering Applicant after: Qingdao University of Science & Technology Address before: 266042 School of chemistry and molecular engineering, Qingdao University of Science & Technology, 53 Zhengzhou Road, Qingdao, Shandong Applicant before: Qingdao University of Science & Technology |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121128 Termination date: 20130406 |