CN104163933A - Polymer film prepared based on freeze drying technology and method and application thereof - Google Patents
Polymer film prepared based on freeze drying technology and method and application thereof Download PDFInfo
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Abstract
The invention relates to application of a biofouling protection film, in particular to a polymer film prepared based on a freeze drying technology and a method and application thereof. The method comprises the following steps: combining an anti-fouling agent or a two-dimensional nanomaterial of an antibacterial material under the cross-linking action of a polymer; and performing freeze drying to obtain the polymer film. The prepared polymer film can be used for resisting the adhesion of harmful microorganisms (escherichia coli, staphylococcus aureus, Edwardsiella tarda, blue-green algae and the like). The polymer film is a porous antifouling film based on nanomaterials (graphene, hydrotalcite, kaolin and aluminum oxide nanosheets) and prepared by using the freeze drying technology, and can be applied to the interfaces of biomedical materials and oceanographic engineering materials. The prepared biofouling protection material has the remarkable advantages of low preparation cost, low price, short preparation time, environmental friendliness, avoidance of the production of harmful reagents, and the like.
Description
Technical field
The present invention relates to the application of biodeterioration protection film, a kind of polymer thin film of preparing based on Freeze Drying Technique and methods and applications thereof specifically.
Background technology
Microorganism is stained has material impact in fields such as medical supply, medical applications, water treatment and environmental safeties.This is to be very complicated field because harmful microbe infects.Research finds that many methods can reduce the stained propagation of microorganism.
Much biodeterioration mechanism, comprises microbiotic, phagotherapy, host defense peptide and antibiotic paint etc.Microbiotic is conventional kill bacteria method, but it is often effective to specific bacterium and pathogenic agent, is not all useful (R.Nagarajan, et al., J.Am.Chem.Soc., 1971,93,2308-2310.) of bacterium; Phagotherapy can be selected indirectly harmless host organisms and other useful bacteriums, reduce infection chance, obtain high efficiency method, the phage of a mixing often, as combination (W.C.Summers, Annu.Rev.Microbiol., 2001,55,437-451.).Defense peptides is the congenital immunity albumen of a conservative integral part, but, can make the generation of bacterial drug resistance more frequent and rapid.Worse, in some cases, antibacterial peptide can cause anti-human body Autoimmune Disorders (K.A.Brogden, Nat.Rev.Micro., 2005,3,238-250.).Antimicrobial coating is interested especially.Antimicrobial surface is desirable, is not only aerospace, national defence, and the industries such as public transportation are also biomedical devices industry simultaneously, individual's health industry, food safety (T.Shalev, J.Mater.Chem., 2012,22,2026-2032.).
In many cases, the nanometer sheet material of antibacterial is the structured material of the most useful structure shallow layer.Desirable antimicrobial coating should meet following requirement: antibacterial widely, and environmentally friendly, long-term anti-microbial property, synthetic convenient and with low cost.Layer assembly nano composite material (P.Podsiadlo, Langmuir, 2005,21,11915-11921.), hydrophilic polymer brush (G.Gao, Biomaterials, 2011,32,3899-3909.), plasma polymer (K.Malzahn, PlasmaProcess.Polym., 2012, DOI:10.1002/ppap.201200106.) and self-assembled monolayer (W.Soliman, J.Phys.Chem.B, 2010,114,11292-11302.) etc. technology be all applied to biodeterioration protection field.Film prepared by laminated assembling technology presents stronger anti-microbial activity, by the self-supporting layer replacing, and stable silver nano-grain, the carbon nanotube of N,O-Diacetylmuramidase coating or other antimicrobial nano materials.
Summary of the invention
The object of the invention is to provide a kind of polymer thin film of preparing based on Freeze Drying Technique and methods and applications thereof.
For achieving the above object, the present invention adopts technical scheme to be:
A polymer thin film of preparing based on Freeze Drying Technique, under the effect of crosslinked polymer, in conjunction with the two-dimensional nano material of stain control agent or anti-biotic material, then through lyophilize, obtains polymer thin film.
Described two-dimensional nano material Graphene, graphite oxide nanometer sheet, hydrotalcite, kaolin or aluminium oxide nano sheet.
Described stain control agent is antibiotic molecule, N,O-Diacetylmuramidase, nanometer silver, antifouling enzyme, titanium dioxide, Vanadium Pentoxide in FLAKES.
Described polymkeric substance is hexamethylene diisocyanate, polyvinyl alcohol, polyaniline, glutaraldehyde or boric acid.
The method of the polymer thin film of preparing based on Freeze Drying Technique, under the effect of crosslinked polymer, in conjunction with the two-dimensional nano material of stain control agent or anti-biotic material, then through lyophilize, obtains polymer thin film.
Further, the anti-biotic material of the 1%-5% of the stain control agent of the 1%-5% of the two-dimensional nano material of the 1%-10% of the linking agent of the 1%-10% of polymer thin film quality, polymer thin film quality, polymer thin film quality or polymer thin film quality, under the effect of crosslinked polymer, is obtained to the two-dimensional nano material in conjunction with stain control agent or anti-biotic material; Then freezing under subzero 50-80 degree cold condition, drier in vacuum dehydrating at lower temperature device, obtain polymer thin film.Described linking agent is glutaraldehyde, boric acid or isocyanic ester.
The application of the polymer thin film of preparing based on Freeze Drying Technique, described polymer thin film can be used as bioantifouling film for bio-medical material or oceanographic engineering material interface.
The present invention has advantages of: polymer thin film prepared by the present invention can be used for resisting adhering to of harmful microorganism (intestinal bacteria, streptococcus aureus, tarda, blue-green algae etc.).It is to utilize Freeze Drying Technique to prepare the antifouling film based on nano material (Graphene, hydrotalcite, kaolin and aluminium oxide nano sheet) of porous, can be for bio-medical material and oceanographic engineering material interface.The biodeterioration protective material of preparation has and has that preparation cost is low, low price, preparation time are fast, environmental protection and without significant advantages such as harmful reagent generations.Gained polymer thin film of the present invention can be used as bioantifouling film for bio-medical material or oceanographic engineering material interface, wherein bio-medical material comprises Medical Instruments interface, hospital facility interface, oceanographic engineering material facility comprises Transbay Bridge, marine ships, ocean harbour etc.
Brief description of the drawings
The schematic diagram based on graphene nanometer sheet that Fig. 1 a is prepared for the Freeze Drying Technique that the embodiment of the present invention provides, wherein, polyvinyl alcohol (PVC), graphite oxide nanometer sheet (GO), silver-graphite oxide nanometer sheet mixture (Ag GO) and N,O-Diacetylmuramidase-silver-colored-graphite oxide nanometer sheet (LYZ-Ag GO).
The Raman spectrum of N,O-Diacetylmuramidase-Yin-graphite oxide nanometer sheet (LYZ-Ag GO) that Fig. 1 b provides for the embodiment of the present invention.
The uv-vis spectra of N,O-Diacetylmuramidase-Yin-graphite oxide nanometer sheet (LYZ-Ag GO) that Fig. 1 c provides for the embodiment of the present invention.
N,O-Diacetylmuramidase-Yin-graphite oxide nanometer sheet (LYZ-Ag GO) that Fig. 1 d provides for the embodiment of the present invention is for the titre experiment of micrococcus lysodeikticus.
The antibacterial kinetic curve of N,O-Diacetylmuramidase-Yin-graphite oxide nanometer sheet (LYZ-Ag GO) that Fig. 1 e provides for the embodiment of the present invention.
The seasoning technology that Fig. 2 a provides for the embodiment of the present invention obtains the scanning electronic microscope phenogram of antimicrobial coating based on graphite oxide nanometer sheet.
The Freeze Drying Technique that Fig. 2 b provides for the embodiment of the present invention obtains the vertical view of the scanning electronic microscope sign of antimicrobial coating based on graphite oxide nanometer sheet.
The seasoning technology that Fig. 2 c, Fig. 2 e provide for the embodiment of the present invention obtains the sectional view of the scanning electronic microscope sign of antimicrobial coating based on graphite oxide nanometer sheet.
The Freeze Drying Technique that Fig. 2 d, Fig. 2 f provide for the embodiment of the present invention obtains the sectional view of the scanning electronic microscope sign of antimicrobial coating based on graphite oxide nanometer sheet.
The XRD spectra of the different coating that Fig. 3 a provides for the embodiment of the present invention.
The antibacterial kinetic curve to micrococcus lysodeikticus that Fig. 3 b provides for the embodiment of the present invention.
Fig. 4. the seasoning technology (a) and the antibacterial schematic diagram comparison of Freeze Drying Technique (b) that provide for the embodiment of the present invention, for micrococcus lysodeikticus (c) and the comparison of intestinal bacteria (d) anti-microbial effect.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1: seasoning technology and Freeze Drying Technique are prepared based on Graphene antibiosis film:
(1) seasoning technology, LYZ-Ag@GO (50mL, 2.0mg mL
-1) mixed uniformly by polyvinyl alcohol (50mL2.0%).After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, 100mg graphite oxide (GO, 1.0mg mL
-1) at 15000rpm, centrifugal 20min, removes supernatant liquor.Add again 50mL silver enhancement solution (pH5.2), reaction 2h.With ultrapure water cleaning three times, and then add 100m L N,O-Diacetylmuramidase (LYZ, 0.1mg mL
-1), reaction is spent the night.Mixture is at 15000rpm, and centrifugal 20min, removes supernatant liquor, obtains LYZ-Ag@GO.
LYZ-Ag@GO (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition (referring to Fig. 4 c-d).Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 2: seasoning technology and Freeze Drying Technique are prepared based on kaolin antibacterial film:
(1) seasoning technology, kaolin-nanometer silver (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, 100mg kaolin (GO, 1.0mg mL
-1) at 15000rpm, centrifugal 20min, removes supernatant liquor.Add 50mL silver enhancement solution (pH5.2), reaction is spent the night again.Mixture is at 15000rpm, and centrifugal 20min, removes supernatant liquor.Obtain kaolin-nanometer silver.
Kaolin-nanometer silver (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition (referring to Fig. 4 e-f).Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 3: seasoning technology and Freeze Drying Technique are prepared based on kaolin antibacterial film:
(1) seasoning technology, graphite oxide nanometer sheet-N,O-Diacetylmuramidase (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, the preparation of graphite oxide nanometer sheet-N,O-Diacetylmuramidase is: 100mg graphite oxide (GO, 1.0mg mL
-1) at 15000rpm, centrifugal 20min, removes supernatant liquor.Add again 100m L N,O-Diacetylmuramidase (LYZ, 0.1mg mL
-1), reaction is spent the night.Mixture is at 15000rpm, and centrifugal 20min, removes supernatant liquor.
Graphite oxide nanometer sheet-N,O-Diacetylmuramidase (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition.Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and antibacterial efficiency reaches 98%, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 4: seasoning technology and Freeze Drying Technique are prepared based on Graphene antibiosis film:
(1) seasoning technology, LYZ-Ag@GO (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with hexamethylene diisocyanate (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, LYZ-Ag@GO (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with hexamethylene diisocyanate (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition.Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and antibacterial efficiency reaches 95%, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 5: seasoning technology and Freeze Drying Technique are prepared based on kaolin antibacterial film:
(1) seasoning technology, kaolin-nanometer silver (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with hexamethylene diisocyanate (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, kaolin-nanometer silver (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with hexamethylene diisocyanate (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition.Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and antibacterial efficiency reaches 92%, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 6: seasoning technology and Freeze Drying Technique are prepared based on kaolin antibacterial film:
(1) seasoning technology, graphite oxide nanometer sheet-N,O-Diacetylmuramidase (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with hexamethylene diisocyanate (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, graphite oxide nanometer sheet-N,O-Diacetylmuramidase (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with hexamethylene diisocyanate (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition.Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and antibacterial efficiency reaches 99%, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 7: seasoning technology and Freeze Drying Technique are prepared based on Graphene antibiosis film:
(1) seasoning technology, hydrotalcite-N,O-Diacetylmuramidase (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, the preparation of hydrotalcite-N,O-Diacetylmuramidase is: 100mg hydrotalcite (1.0mgmL
-1) at 15000rpm, centrifugal 20min, removes supernatant liquor.Add again 100m L N,O-Diacetylmuramidase (LYZ, 0.1mg mL
-1), reaction is spent the night.Mixture is at 15000rpm, and centrifugal 20min, removes supernatant liquor.
Hydrotalcite-N,O-Diacetylmuramidase (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition.Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and antibacterial efficiency reaches 95%, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 8: seasoning technology and Freeze Drying Technique are prepared based on kaolin antibacterial film:
(1) seasoning technology, hydrotalcite-N,O-Diacetylmuramidase (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, hydrotalcite-N,O-Diacetylmuramidase (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition.Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and antibacterial efficiency reaches 96%, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Embodiment 9: seasoning technology and Freeze Drying Technique are prepared based on kaolin antibacterial film:
(1) seasoning technology, hydrotalcite-N,O-Diacetylmuramidase (50mL, 2.0mg mL
-1) be 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, then prepare antifouling film at 40 ° of C evaporation 48h.
(2) Freeze Drying Technique, hydrotalcite-N,O-Diacetylmuramidase (50mL, 2.0mg mL-1) is 200 to turn under condition and mix uniformly with polyvinyl alcohol (50mL2.0%) stirring speed of rotation.After mixing, get 1m L and drip and be coated onto polyfluortetraethylene plate surface, at-80 ° of freezing 6h of C, at the dry 12h of vacuum dehydrating at lower temperature case-50 ° C, prepare antifouling film.
The antifouling film of preparing for two kinds of methods, has compared antifouling film short period of time and long-time antibacterial experiment.Short period of time experiment: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 5mL microbial inoculum, and the concentration of bacterium liquid is tested with ultraviolet spectrophotometer.Long period of experiments: antibacterial film (1cm × 1cm) is immersed in (micrococcus lysodeikticus and intestinal bacteria) in 10mL microbial inoculum, successive soaking 5 days, with scanning electron microscope test surface microorganism adhesion condition.Under long-time soaking conditions, film prepared by Freeze Drying Technique has superpower antifouling property, and microorganism is all had to stronger germ resistance, and antibacterial efficiency reaches 92%, and the antifouling film of preparing under natural condition can lose efficacy under long-time condition.
Claims (7)
1. a polymer thin film of preparing based on Freeze Drying Technique, is characterized in that: under the effect of crosslinked polymer, in conjunction with the two-dimensional nano material of stain control agent or anti-biotic material, then through lyophilize, obtain polymer thin film.
2. by the polymer thin film of preparing based on Freeze Drying Technique claimed in claim 1, it is characterized in that: described two-dimensional nano material Graphene, graphite oxide nanometer sheet, hydrotalcite, kaolin or aluminium oxide nano sheet.
3. by the polymer thin film of preparing based on Freeze Drying Technique claimed in claim 1, it is characterized in that: described stain control agent is antibiotic molecule, N,O-Diacetylmuramidase, nanometer silver, antifouling enzyme, titanium dioxide, Vanadium Pentoxide in FLAKES.
4. by the polymer thin film of preparing based on Freeze Drying Technique claimed in claim 1, it is characterized in that: described polymkeric substance is hexamethylene diisocyanate, polyvinyl alcohol, polyaniline, glutaraldehyde or boric acid.
5. a method for the polymer thin film of preparing based on Freeze Drying Technique claimed in claim 1, is characterized in that: under the effect of crosslinked polymer, in conjunction with the two-dimensional nano material of stain control agent or anti-biotic material, then through lyophilize, obtain polymer thin film.
6. by the method for the polymer thin film of preparing based on Freeze Drying Technique claimed in claim 5, it is characterized in that:
The anti-biotic material of the 1%-5% of the stain control agent of the 1%-5% of the two-dimensional nano material of the 1%-10% of the linking agent of the 1%-10% of polymer thin film quality, polymer thin film quality, polymer thin film quality or polymer thin film quality, under the effect of crosslinked polymer, is obtained to the two-dimensional nano material in conjunction with stain control agent or anti-biotic material; Then freezing under subzero 50-80 degree cold condition, drier in vacuum dehydrating at lower temperature device, obtain polymer thin film.
7. an application for the polymer thin film of preparing based on Freeze Drying Technique claimed in claim 1, is characterized in that: described polymer thin film can be used as bioantifouling film for bio-medical material or oceanographic engineering material interface.
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| CN107083045A (en) * | 2017-05-25 | 2017-08-22 | 句容市兴武包装有限公司 | A kind of method that degradable film for package is prepared by base-material of blue-green algae |
| CN107083045B (en) * | 2017-05-25 | 2020-01-17 | 句容市兴武包装有限公司 | Method for preparing degradable packaging film by using blue algae as base material |
| CN107293765A (en) * | 2017-07-28 | 2017-10-24 | 韦德永 | A kind of fuel battery gas diffusion layer structure |
| CN107494539A (en) * | 2017-08-28 | 2017-12-22 | 北京化工大学 | A kind of lysozyme/hydrotalcite composite antibacterial material and preparation method thereof and antibacterial applications |
| CN107936630A (en) * | 2017-12-01 | 2018-04-20 | 河南省健琪医疗器械有限公司 | A kind of medical instrument special surface antimicrobial coating and its preparation process |
| CN109735154A (en) * | 2018-12-21 | 2019-05-10 | 天津西敦粉漆科技有限公司 | A kind of long-acting antibiotic agent, long-acting antibiotic agent with prompt effect and preparation method thereof |
| CN109735154B (en) * | 2018-12-21 | 2021-08-27 | 天津西敦粉漆科技有限公司 | Long-acting antibacterial agent, long-acting antibacterial agent with immediate effect and preparation method thereof |
| CN112640914A (en) * | 2020-12-22 | 2021-04-13 | 江苏瞪羚科技有限公司 | Novel disinfectant special for pets and preparation method thereof |
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| CN104163933B (en) | 2017-10-20 |
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