CN104059344B - A kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method - Google Patents
A kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method Download PDFInfo
- Publication number
- CN104059344B CN104059344B CN201410310299.0A CN201410310299A CN104059344B CN 104059344 B CN104059344 B CN 104059344B CN 201410310299 A CN201410310299 A CN 201410310299A CN 104059344 B CN104059344 B CN 104059344B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- poly
- lactic acid
- antibiotic plastic
- modified graphene
- 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.)
- Active
Links
Abstract
The invention discloses a kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method.This antibiotic plastic is made up of polylactic acid based resin, complex antimicrobials.Described complex antimicrobials is the graphene oxide sheet of area load Zinc oxide nanoparticle.Described antibiotic plastic adopts the method for solution blending to carry out blended by the trichloromethane dispersion liquid of the chloroform soln of poly(lactic acid) and above-mentioned complex antimicrobials according to certain proportioning, utilize automatic film applicator by mixed solution film on clean sheet glass, room temperature solvent of ordering naturally volatilizees and obtains.This poly-lactic acid material antibacterial effect is obvious, and antibacterial range is wide, and product is biodegradable, safe and reliable, free from extraneous odour, to the harm of human body and environment and pollution level low.
Description
Technical field
The present invention relates to the antimicrobial technology field of poly-lactic acid material, be specifically related to a kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method.
Background technology
In recent years, along with the enhancing of people's environmental consciousness, biodegradable plastic is subject to the extensive concern of investigators day by day.Poly(lactic acid) (PLA) has good biocompatibility and biodegradable performance, and degraded product is in vivo carbonic acid gas and water, to biological and environment without any detrimentally affect.At present, poly(lactic acid) has a wide range of applications in fields such as packaging, automotive industry, drug conveying and organizational projects.But because poly(lactic acid) decomposes the oligopolymer of generation easily by various bacterial contamination, under suitable temperature humidity condition, bacterium very easily breeds, and affects human health.Therefore, the anti-microbial property of people to some poly-lactic acid products is had higher requirement.
Preparing antimicrobial form poly(lactic acid) is generally add antiseptic-germicide in poly(lactic acid).Graphene oxide is as the important derivative of graphene-based material one class, and have the physics and chemistry character of some uniquenesses, be therefore the focus of field of nanometer material technology research always.Except character such as good chemical stability and mechanical properties, Recent study person find that graphene oxide also has good biocompatibility and anti-microbial property.(the IsisE.Mej í asCarpio such as Carpio, CatherineM.Santos, XinWei, DeboraF.Rodrigues.Nanoscale, 2012,4:4746-4756) report in polyvinyl carbazole matrix, the graphene oxide adding 3wt% matrix material can be made to have germ resistance and this material to mammalian cell without overt toxicity.But the addition of graphene oxide is relatively many.Nano zine oxide is a kind of conventional inorganic antiseptic, and it has good biocompatibility, environmental safety and long-term antimicrobial efficiency.But, directly this nano antibacterial agent is added the agglomeration easily causing nano antibacterial agent in plastic substrate, its original anti-microbial property will be affected to a certain extent.(the JongchulSeo such as Seo, GwonyoungJeon, EUiSungJang, SherBahadarKhan, HaksooHan.JournalofAppliedPolymerScience, 2011,112:1101-1108) report and directly nano zine oxide and polypropylene carbonate are made composite membrane by solution blending, when the anti-bacterial result display nano zine oxide is added into 10wt%, the antibiotic rate of composite membrane to intestinal bacteria and lactobacillus could reach 100% and 87.5% respectively, and in material, zinc oxide exists obvious agglomeration.
Summary of the invention
The object of this invention is to provide a kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method.Be intended to overcome the deficiencies in the prior art, can not only material be made to have significant anti-microbial property under the condition of adding less antiseptic-germicide, and antibacterial range is wide, product be biodegradable, safe and reliable, free from extraneous odour, to the harm of human body and environment and pollution level low.
Realizing technical scheme of the present invention is:
In poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic, described poly(lactic acid)/modified graphene oxide antibiotic plastic is made up of polylactic acid based resin, complex antimicrobials, complex antimicrobials is the graphene oxide of area load Zinc oxide nanoparticle, described polylactic acid based resin, the mass ratio of complex antimicrobials are 100:(0.2 ~ 1.0), preferred 100:(0.2 ~ 0.7).
The graphene oxide of described area load Zinc oxide nanoparticle is the laminate structure that individual layer sheet or a small amount of lamella are piled up, and the Zinc oxide nanoparticle particle diameter of load is 15 ~ 30nm, and actual negative carrying capacity is about 80wt%.
The preparation of described complex antimicrobials is dried by graphene oxide obtained for Hummers method and is ultrasonicly dispersed in ethanol, add zinc acetate in a heated condition and constantly stir and make it abundant mixed dissolution, slowly sodium hydroxide solution is added after solution boiling, after completion of the reaction product centrifugal water is washed till neutrality, vacuum-drying gained.
The preparation method of poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic, comprises the following steps:
(1) preparation of complex antimicrobials: graphene oxide obtained for Hummers method is dried and is ultrasonicly dispersed in ethanol, add zinc acetate in a heated condition and constantly stir and make it abundant mixed dissolution, slowly sodium hydroxide solution is added after solution boiling, after completion of the reaction product centrifugal water is washed till neutrality, vacuum-drying;
(2) utilize low boiling point solvent trichloromethane that poly(lactic acid) and complex antimicrobials are carried out solution blending in proportion, with automatic film applicator by mixed solution film on clean sheet glass, room temperature solvent of ordering volatilizees naturally, finally in warm water, demoulding is placed in baking oven dry, obtains described poly(lactic acid)/modified graphene oxide antibiotic plastic.
In step (1), the concentration of graphene oxide in ethanolic soln is 0.5mg/mL, and the concentration of sodium hydroxide solution is 0.5mol/mL, and the mol ratio of sodium hydroxide and zinc acetate is 2:1.04, and the reaction times is 1h.
In step (2), the mass ratio of polylactic acid based resin, complex antimicrobials is 100:(0.2 ~ 1.0).
The concentration of step (2) poly(lactic acid) in blended liquid is 0.13 ~ 0.16g/mL, and the blended time is 3 ~ 6h.
Controlling its thickness during film in step (2) is 1.5mm.
In step (2), under trichloromethane solvent room temperature, natural volatilizes is 12h, and oven drying temperature is 60 DEG C, and time of drying is 48h.
Poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic compared with prior art, has the following advantages:
(1) Zinc oxide nanoparticle is carried on the surface of graphene oxide sheet, utilize the effect of chemical bond between zinc oxide and graphene oxide, effectively hinder the reunion of Zinc oxide nanoparticle in poly(lactic acid) matrix, improve the anti-microbial activity of zinc oxide in this system;
(2) graphene oxide has large specific surface area, and the oxygen-containing functional group on surface can form strong interface interaction power with polylactic acid based body, and Miscibility is good;
(3) due to the mutual synergy of graphene oxide in complex antimicrobials and nano zine oxide, only need to add a small amount of (< 1.0wt%) this complex antimicrobials and can reach significant antibacterial effect;
(4) antibiotic plastic that obtains of the present invention is recyclable, reusable, and antibacterial range is wide, and product is biodegradable, safe and reliable, to the harm of human body and environment and pollution level low.
Below in conjunction with accompanying drawing, the invention will be further described.
Accompanying drawing explanation
Fig. 1 is the graphene oxide transmission electron microscope picture of area load Zinc oxide nanoparticle in the present invention.
Fig. 2 is anti-bacteria test result figure in comparative example and embodiment 2.
Embodiment
A kind of poly(lactic acid)/modified graphene oxide antibiotic plastic, described poly(lactic acid)/modified graphene oxide antibiotic plastic is made up of polylactic acid based resin, complex antimicrobials, complex antimicrobials is the graphene oxide of area load Zinc oxide nanoparticle, described polylactic acid based resin, the mass ratio of complex antimicrobials are 100:(0.2 ~ 1.0), preferred 100:(0.2 ~ 0.7).
A preparation method for poly(lactic acid)/modified graphene oxide antibiotic plastic, comprises the following steps:
(1) preparation of complex antimicrobials: graphene oxide obtained for Hummers method is dried and is ultrasonicly dispersed in ethanol, add zinc acetate in a heated condition and constantly stir and make it abundant mixed dissolution, slowly sodium hydroxide solution is added after solution boiling, after completion of the reaction product centrifugal water is washed till neutrality, vacuum-drying;
(2) utilize low boiling point solvent trichloromethane that poly(lactic acid) and complex antimicrobials are carried out solution blending in proportion, with automatic film applicator by mixed solution film on clean sheet glass, room temperature solvent of ordering volatilizees naturally, finally in warm water, demoulding is placed in baking oven dry, obtains described poly(lactic acid)/modified graphene oxide antibiotic plastic.
In order to Comprehension and Implementation better, below in conjunction with comparative example and embodiment, the present invention is further described.
Anti-microbial property test in following comparative example and embodiment: anti-microbial property detects with reference to People's Republic of China (PRC) light industry standard QB/T2591-2003, adopts film applicator coating, investigates the antibiotic rate of sample 24h, and total number of bacterial colony measures and counts according to GB/T4789.2-2003.The antibiotic plastic film prepared is cut into the antimicrobial sample of 50mm × 50mm.The calculation formula of antibiotic rate is as follows:
R(％)＝(B－C)/B×100
In formula, R is antibacterium rate (%), B is the average bacterial count recovered of blank control sample (cfu/ sheet), and C is antibiotic plastic sample average bacterial count recovered (cfu/ sheet).
Detect with bacterium: streptococcus aureus (Staphylococcusaureus) ATCC6538; Colon bacillus (Escherichiacoli) ATCC25922
The preparation of different ingredients poly(lactic acid)/modified graphene oxide antibiotic plastic:
Comparative example: take 10g poly(lactic acid) and be dissolved in 60mL trichloromethane, magnetic agitation 6h makes it fully dissolve.With automatic film applicator, solution is painted on sheet glass the film of 1.5mm, at room temperature makes trichloromethane naturally volatilize 24h subsequently, with after the warm water demoulding at 60 DEG C vacuum-drying 48h, obtained poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic.Antibiotic rate test result: streptococcus aureus 0; Colon bacillus 0.
Embodiment 1: take 10g poly(lactic acid) and be dissolved in 40mL trichloromethane, magnetic agitation 2h makes it fully dissolve.Taking 0.02g complex antimicrobials is scattered in 20mL trichloromethane, and ultrasonic 1.5h makes it to be uniformly dispersed.Subsequently by two dispersion liquid mix and blends, blended 4h.With automatic film applicator, mixing solutions is painted on sheet glass the film of 1.5mm, at room temperature makes trichloromethane naturally volatilize 24h subsequently, with after the warm water demoulding at 60 DEG C vacuum-drying 48h, obtained poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic.Antibiotic rate test result: streptococcus aureus 99.2%; Colon bacillus 97.6%.
Embodiment 2: take 10g poly(lactic acid) and be dissolved in 40mL trichloromethane, magnetic agitation 2h makes it fully dissolve.Taking 0.05g complex antimicrobials is scattered in 20mL trichloromethane, and ultrasonic 1.5h makes it to be uniformly dispersed.Subsequently by two dispersion liquid mix and blends, blended 4h.With automatic film applicator, mixing solutions is painted on sheet glass the film of 1.5mm, at room temperature makes trichloromethane naturally volatilize 24h subsequently, with after the warm water demoulding at 60 DEG C vacuum-drying 48h, obtained poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic.Antibiotic rate test result: streptococcus aureus 99.9%; Colon bacillus 98.5%.
Embodiment 3: take 10g poly(lactic acid) and be dissolved in 40mL trichloromethane, magnetic agitation 2h makes it fully dissolve.Taking 0.07g complex antimicrobials is scattered in 20mL trichloromethane, and ultrasonic 1.5h makes it to be uniformly dispersed.Subsequently by two dispersion liquid mix and blends, blended 4h.With automatic film applicator, mixing solutions is painted on sheet glass the film of 1.5mm, at room temperature makes trichloromethane naturally volatilize 24h subsequently, with after the warm water demoulding at 60 DEG C vacuum-drying 48h, obtained poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic.Antibiotic rate test result: streptococcus aureus 99.6%; Colon bacillus 98.7%.
Embodiment 4: take 10g poly(lactic acid) and be dissolved in 40mL trichloromethane, magnetic agitation 2h makes it fully dissolve.Taking 0.10g complex antimicrobials is scattered in 20mL trichloromethane, and ultrasonic 1.5h makes it to be uniformly dispersed.Subsequently by two dispersion liquid mix and blends, blended 4h.With automatic film applicator, mixing solutions is painted on sheet glass the film of 1.5mm, at room temperature makes trichloromethane naturally volatilize 24h subsequently, with after the warm water demoulding at 60 DEG C vacuum-drying 48h, obtained poly(lactic acid) of the present invention/modified graphene oxide antibiotic plastic.Antibiotic rate test result: streptococcus aureus 98.9%; Colon bacillus 97.8%.
As shown in Figure 1, in the present invention, the pattern of the graphene oxide of area load Zinc oxide nanoparticle is the laminate structure that individual layer sheet or a small amount of lamella are piled up, and the Zinc oxide nanoparticle particle diameter of load is 15 ~ 30nm.
As shown in Figure 2, (a) (b) is for the polylactic acid plastic film adding complex antimicrobials in polylactic acid film pure in comparative example and embodiment 2 is respectively to effects on surface enumeration result after the antibacterial test of gram-positive microorganism streptococcus aureus and Gram-negative bacteria colon bacillus 24h.Add the polylactic acid plastic film of complex antimicrobials described in the present invention in embodiment 2 compared to pure polylactic acid film, fungistatic effect is remarkable, can reach 99.9% and 98.5% respectively to the antibiotic rate of streptococcus aureus and colon bacillus.
Claims (8)
1. poly(lactic acid)/modified graphene oxide antibiotic plastic, it is characterized in that, described poly(lactic acid)/modified graphene oxide antibiotic plastic is by polylactic acid based resin, complex antimicrobials forms, complex antimicrobials is the graphene oxide of area load Zinc oxide nanoparticle, described polylactic acid based resin, the mass ratio of complex antimicrobials is 100:(0.2 ~ 1.0), the preparation of described complex antimicrobials is dried by graphene oxide obtained for Hummers method and is ultrasonicly dispersed in ethanol, add zinc acetate in a heated condition and constantly stir and make it abundant mixed dissolution, slowly sodium hydroxide solution is added after solution boiling, after completion of the reaction product centrifugal water is washed till neutrality, vacuum-drying gained, wherein, the concentration of graphene oxide in ethanolic soln is 0.5mg/mL, the concentration of sodium hydroxide solution is 0.5mol/mL, the mol ratio of sodium hydroxide and zinc acetate is 2:1.04.
2. poly(lactic acid) according to claim 1/modified graphene oxide antibiotic plastic, is characterized in that, described polylactic acid based resin, the mass ratio of complex antimicrobials are 100:(0.2 ~ 0.7).
3. poly(lactic acid) according to claim 1/modified graphene oxide antibiotic plastic, it is characterized in that, the graphene oxide of described area load Zinc oxide nanoparticle is the laminate structure that individual layer sheet or a small amount of lamella are piled up, the Zinc oxide nanoparticle particle diameter of load is 15 ~ 30nm, and actual negative carrying capacity is 80wt%.
4. a preparation method for poly(lactic acid)/modified graphene oxide antibiotic plastic, is characterized in that, comprise the following steps:
(1) preparation of complex antimicrobials: graphene oxide obtained for Hummers method is dried and is ultrasonicly dispersed in ethanol, add zinc acetate in a heated condition and constantly stir and make it abundant mixed dissolution, slowly sodium hydroxide solution is added after solution boiling, after completion of the reaction product centrifugal water is washed till neutrality, vacuum-drying, wherein, the concentration of graphene oxide in ethanolic soln is 0.5mg/mL, the concentration of sodium hydroxide solution is 0.5mol/mL, and the mol ratio of sodium hydroxide and zinc acetate is 2:1.04;
(2) utilize low boiling point solvent trichloromethane that poly(lactic acid) and complex antimicrobials are carried out solution blending in proportion, with automatic film applicator by mixed solution film on clean sheet glass, room temperature solvent of ordering volatilizees naturally, finally in warm water, demoulding is placed in baking oven dry, obtain described poly(lactic acid)/modified graphene oxide antibiotic plastic, wherein, the mass ratio of polylactic acid based resin, complex antimicrobials is 100:(0.2 ~ 1.0).
5. the preparation method of poly(lactic acid) according to claim 4/modified graphene oxide antibiotic plastic, is characterized in that, in step (1), the reaction times is 1h.
6. the preparation method of poly(lactic acid) according to claim 4/modified graphene oxide antibiotic plastic, is characterized in that, the concentration of step (2) poly(lactic acid) in blended liquid is 0.13 ~ 0.16g/mL, and the blended time is 3 ~ 6h.
7. the preparation method of poly(lactic acid) according to claim 4/modified graphene oxide antibiotic plastic, is characterized in that, controlling its thickness during film in step (2) is 1.5mm.
8. the preparation method of poly(lactic acid) according to claim 4/modified graphene oxide antibiotic plastic, is characterized in that, in step (2), under trichloromethane solvent room temperature, natural volatilizes is 12h, and oven drying temperature is 60 DEG C, and time of drying is 48h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410310299.0A CN104059344B (en) | 2014-07-01 | 2014-07-01 | A kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410310299.0A CN104059344B (en) | 2014-07-01 | 2014-07-01 | A kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104059344A CN104059344A (en) | 2014-09-24 |
| CN104059344B true CN104059344B (en) | 2015-12-30 |
Family
ID=51547286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410310299.0A Active CN104059344B (en) | 2014-07-01 | 2014-07-01 | A kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104059344B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710733B (en) * | 2015-04-07 | 2016-09-07 | 嘉兴学院 | A kind of heat-resistance antibacterial poly-lactic acid material and preparation method thereof |
| CN105380067A (en) * | 2015-10-19 | 2016-03-09 | 南京财经大学 | Coating inhibiting listeria monocytogenes and preparation method and application |
| CN105778140A (en) * | 2016-04-28 | 2016-07-20 | 南京凤源新材料科技有限公司 | Preparation method of high-barrier-property polylactic acid multilayer composite film |
| CN106893301B (en) * | 2017-03-27 | 2019-06-04 | 广东乔艺塑胶有限公司 | A kind of antibiotic plastic and preparation method thereof |
| CN108690263A (en) * | 2017-04-12 | 2018-10-23 | 合肥杰事杰新材料股份有限公司 | A kind of antibacterial polyolefin and preparation method thereof |
| CN109553939B (en) * | 2017-09-27 | 2022-08-19 | 江南大学 | Non-migration type efficient antibacterial composite material and preparation method thereof |
| CN109265752A (en) * | 2018-09-11 | 2019-01-25 | 广西中医药大学 | A kind of antibacterial and biodegradable food package box and preparation method thereof |
| CN109280194A (en) * | 2018-09-20 | 2019-01-29 | 黄旭东 | A kind of preparation method of antibacterial polylactic acid film |
| CN110999947A (en) * | 2019-11-20 | 2020-04-14 | 浙江工商大学 | Preservative and fresh-keeping coating film for aquatic products |
| CN111893754A (en) * | 2020-08-19 | 2020-11-06 | 广东极客亮技术有限公司 | Graphene nanosheet antibacterial and antiviral fabric with special-shaped structure edge |
| CN112852206B (en) * | 2021-02-23 | 2022-03-11 | 广东施彩新材料科技有限公司 | Polylactic acid modified acrylic resin slow-release antibacterial agent and preparation method and application thereof |
| CN113308016B (en) * | 2021-05-26 | 2022-03-22 | 无锡德立柯特纳米新材料科技有限公司 | Foaming film based on composite antibacterial nano material and preparation method thereof |
| CN113121869B (en) * | 2021-05-26 | 2022-03-22 | 无锡德立柯特纳米新材料科技有限公司 | Foaming film based on copper oxide/graphene oxide composite antibacterial nano material and preparation method thereof |
| CN113696569A (en) * | 2021-08-27 | 2021-11-26 | 苏州金多利纺织新材料有限公司 | PU (polyurethane) antiviral protective fabric and application thereof |
| CN113637232B (en) * | 2021-09-11 | 2022-04-15 | 深圳环能石墨烯科技有限公司 | Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof |
| CN113829689A (en) * | 2021-10-19 | 2021-12-24 | 深圳市石能纸业有限公司 | Antibacterial modified stone paper and production and preparation method thereof |
| CN113861645B (en) * | 2021-10-25 | 2023-03-21 | 杭州神彩包装印业有限公司 | Rapidly degradable antibacterial plastic film and preparation method thereof |
| CN115651300A (en) * | 2022-11-07 | 2023-01-31 | 安徽昊源化工集团有限公司 | Production process of degradable plastic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215411A (en) * | 2008-01-21 | 2008-07-09 | 南京大学 | Light degradation antibiotic polylactic acid material and preparation method thereof |
| CN103283781A (en) * | 2013-06-21 | 2013-09-11 | 中山大学 | Graphene oxide loaded nanometer zinc oxide antibacterial agent, preparation method and applications thereof |
-
2014
- 2014-07-01 CN CN201410310299.0A patent/CN104059344B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215411A (en) * | 2008-01-21 | 2008-07-09 | 南京大学 | Light degradation antibiotic polylactic acid material and preparation method thereof |
| CN103283781A (en) * | 2013-06-21 | 2013-09-11 | 中山大学 | Graphene oxide loaded nanometer zinc oxide antibacterial agent, preparation method and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104059344A (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104059344B (en) | A kind of poly(lactic acid)/modified graphene oxide antibiotic plastic and preparation method | |
| Li et al. | Poly (vinyl alcohol)/sodium alginate/layered silicate based nanofibrous mats for bacterial inhibition | |
| Liu et al. | Characterization and antibacterial properties of genipin-crosslinked chitosan/poly (ethylene glycol)/ZnO/Ag nanocomposites | |
| CN103283781B (en) | Graphene oxide loaded nanometer zinc oxide antibacterial agent, preparation method and applications thereof | |
| Zhao et al. | Electrospun chitosan/sericin composite nanofibers with antibacterial property as potential wound dressings | |
| Amna et al. | Antibacterial activity and interaction mechanism of electrospun zinc-doped titania nanofibers | |
| CN101731272B (en) | Method for preparing antibacterial nanometer silver colloid | |
| CN103947675B (en) | Magnetic oxygenated graphene nanometer composite and its preparation method and application | |
| TW201919477A (en) | Antibacterial/antiviral composition | |
| CN107951902B (en) | Graphene antibacterial composition and sanitary material using same | |
| CN104389245B (en) | A kind of preparation technology of nano Ag antibacterial fiber tableware | |
| CN103467828A (en) | Antibacterial plastic and preparation method thereof | |
| CN108690263A (en) | A kind of antibacterial polyolefin and preparation method thereof | |
| Amna et al. | Characterization and potent bactericidal effect of cobalt doped titanium dioxide nanofibers | |
| CN108102152A (en) | A kind of food packaging hectorite immobilization nano silver/chitosan anti-bacteria composite membrane and preparation method and application | |
| CN104145993A (en) | Method for preparing complex antimicrobial agent by blending chitosan and silver copper | |
| Machovsky et al. | Antibacterial performance of ZnO-based fillers with mesoscale structured morphology in model medical PVC composites | |
| KR20140118294A (en) | Graphene-based antibacterial composite and method for production thereof | |
| CN102191681A (en) | Antibacterial non-woven fabric and method for producing non-woven fabric product | |
| CN102391573A (en) | Modified polypropylene plastic and preparation method and use thereof | |
| TWI640565B (en) | Polymer latex particle composition containing nano silver particles | |
| CN104383820A (en) | Visible-light-response antibacterial and antifouling polyvinylidene fluoride film and preparation method thereof | |
| CN102326585B (en) | Slowly-released silver oxide (AgO) microcapsule antimicrobial and preparation method thereof | |
| CN102885087A (en) | Nanometer magnesium oxide inorganic antibacterial agent, preparation method and applications of nanometer magnesium oxide inorganic antibacterial agent | |
| CN101347127A (en) | Novel surrounding purifying material as well as preparation and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |