CN109952026A - The polymer comprising CaO nano particle for food packaging - Google Patents
The polymer comprising CaO nano particle for food packaging Download PDFInfo
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- CN109952026A CN109952026A CN201780051744.8A CN201780051744A CN109952026A CN 109952026 A CN109952026 A CN 109952026A CN 201780051744 A CN201780051744 A CN 201780051744A CN 109952026 A CN109952026 A CN 109952026A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
Abstract
The present invention relates to Biocidal polymers films, it includes less than 55nm calcium oxide (CaO) nano particle as biocide and be selected from polyethylene (PE), polypropylene (PP), polystyrene (PS), poly- (lactic acid) (PLA), poly(hydrobutyl ester) (PHB), poly- (glycolic) (PGA) or both or more person mixture thermoplastic polymer, and optionally comprising the CaO nano particle modified through oleic acid, wherein relative to the total weight of film, CaO nano particle exists with the concentration of 3 weight % to 10 weight %.
Description
Technical field
Biocidal polymers film the present invention relates to the nano particle comprising calcium oxide (CaO) as biocide.
Background technique
The sector needs to save the food of external factor (such as hot, light, moisture, smell and undesirable microorganism).These meetings
Lead to the loss of quality or accelerates rotten.Therefore, polymer film or polylactic acid poly ethylene are found to allow to manufacture protecting and
It is very concerned from the packaging of microbiological attack to save food.
On the other hand, in the field of medicine, seeking to obtain has the material of antimicrobial property to reduce bio-medical material
The pollution of material.High density polyethylene (HDPE) and polylactic acid (PLA) are usually used in medical domain due to its physics and chemical characteristic
[Ziabka M.,Mertas A.,Krol W.,Bobrowski A.,Chl/opek J.,High Density
Polyethylene Containing Antibacterial Silver Nanoparticles for Medical
Applications Macromolecu.Sym,315(2013)218-225].In the field of medicine, these polymer are not only used
In production Medical Devices, but also for implantation material such as conduit, face reparation etc..One problem is the bacterium sense of medical device
Dye, this is because leading to dead reason to the resistance of antibiotic.Infection is prevented to be important in the field of medicine, one
Effective strategy is the neoformation medical apparatus that exploitation has antibacterial ability.In this respect, it is mixed with using the two and resists micro- life
The composite material of agent is the growth for preventing, controlling or prevent and controlling microorganism and therefore prevents the excellent of infection from replacing
For scheme [Cao H., Liu X., Silver nanoparticles-modified films versus biomedical
device-associated infections,Wiley Interdisciplinary Rev.Nanomed
Nanobiotechnol.(2010)670-684].Currently, with mix silver nano-grain obtain medical device [Hoon S,
Hwang Hwan Yun,Sung Chul Y.Antibacterial properties of padded PP/PE nonwovens
incorporating nano-sized silver colloids J.Mater Sci 40(2005)5413-8]。
The alternative solution of these problems is to prepare the polymer nanocomposites being made of organic matrix and nano particle.
Being based primarily upon using the advantages of reinforcement (nano particle) in nanometer range, which improves polymer-particle, interacts, because it
With big surface area [Zenteno A., Guerrero S., Ulloa M.T., Palza H., Zapata P.A.,
Effect of hydrothermally synthesized titanium nanotubes on the behavior of
polypropylene for antimicrobial applications,Polymer International 64(2015)
1442-1450].According to the property of nano particle, the mechanical property of polymer, barrier property (de can be improved by mixing them
Barrera), anti-flammability and antibacterial characteristics [Svagan A.J., Akesson A., Cardenas M., Bulut S., Knudsen
J.C.,Rlsbo J.,Plackett D.Transparent films based on PLAand montmorillonite
with tunable oxygen barrier properties.Biomacromolecules 13(2012)397-405].Most
The most commonly used is silver nano particle [P.A.Zapata, L.Tamayo, M.P á ez, E.Cerda, I.Azocar,
F.M.Rabagliati,Nanocomposites based on polyethylene and nanosilver particles
produced by metallocenic“in situ”polymerization:synthesis characterization,
And antimicrobial behavior.European polymer Journal 47 (2011) 1541-1549], copper receives
Rice grain [L.Tamayo, P.A.Zapata, N.D.Vejar, M.I.Azocar, M.A.Gulppi, X.Zhou,
G.E.Thompson,F.M.Rabagliati,M.A.Paez.Release of silver and copper
nanoparticles from polyethylene nanocomposites and their penetration into
Listeria mopnocytogenes.Master Sci Eng C.40(2014)24-31；Palza H,Gutierrez S,
Salazar O, Fuenzalida V, Avila J waits Toward tailor-made biocide materials based
on Poly(propylene)copper nanoparticles.Macromol Rapid Commun 31(2010)563-7]、
Titanium oxide (TiO2) nano particle [D,F.M.Rabagliati,S.Guerrero,I.Lieberwirth,
M.T.Ulloa,T.Gómez P.A.Zapata*,Photocatalytic inhibition of bacteria by
TiO2nanotubes-doped polyethylene composites,Applied Catalysis A:General,489
(2015)255-261]。
It has been reported that it is applied to the research of the polyvinyl nanocomposite of food packaging and medical domain, preparation
Polyethylene is mixed with TiO2Or the nano particle of silver.In the case where the nanocomposite of polyethylene and 2% silver nano-grain,
Show 99% efficiency as biocide to Escherichia coli (Escherichia coli).When the load capacity of nano particle increases
When adding 5%, the high release of Ag ion is obtained, 99.99% efficiency [the Zenteno A., Guerrero to Escherichia coli are reflected in
S.,Ulloa M.T.,Palza H.,Zapata P.A.,Effect of hydrothermally synthesized
titanium nanotubes on the behavior of polypropylene for antimicrobial
applications,Polymer International 64(2015)1442-1450]。
In addition, we have studied nanocomposite polyethylene titanium oxide (TiO2) nanosphere and nanotube preparation
[Zenteno A.,Guerrero S.,Ulloa M.T.,Palza H.,Zapata P.A.,Effect of
hydrothermally synthesized titanium nanotubes on the behavior of
polypropylene for antimicrobial appllcations,Polymer International 64(2015)
1442-1450.,L.Tamayo,P.A.Zapata,N.D.Vejar,M.I.Azocar,M.A.Gulppi,X.Zhou,
G.E.Thompson,F.M.Rabagliati,M.A.Paez.Release of silver and copper
nanoparticles from polyethylene nanocomposites and their penetration into
Listeria monocytogenes.Mater Sci Eng C.40(2014)24-31].After the load of addition 8%, institute
The film of acquisition shows the strong biocide effect to Escherichia coli (E.coli).This matrix for showing biocidal activity and using
It is related with the type of nano particle.TiO2Major defect be film obtained need UV light with discharge determine its biocidal capability
Substance, this makes, and it is not very attractive under industrial level [P.A.Zapata, H.Palza, F.M.Rabagliati,
Novel antimicrobial polyethylene composites prepared by metallocenic"in-situ"
polymerization with TiO2based nanoparticles.Journal of Polymer Science Part
A:Journal of Polymer Science Part A:Polymer Chemistry.50(2012)4055-4062].It will
TiO2Nano particle incorporation polylactic acid matrix in obtain to Escherichia coli have Biocidal properties and to for medical treatment dress
The material to have a great attraction is set, but uses TiO2When the shortcomings that be need irradiate with to bacterium be it is active [Fonseca C.,
Ochoa A.,Ulloa M.T.,Alvarez E.,Canales C.,Zapata P.A.,Poly(lactic acid)/
TiO2nanocomposites as alternative biocidal and antifungal materials,Material
Science an Engineering57(2015)314-320]。
It it is not immediately clear nano particle (such as copper or silver) to the toxicity of the mankind further, it is important to refer to.
In this background, need to find the polymer composition with antimicrobial acivity to mankind's edible safety,
Wherein CaO nano particle occurs as promising substitute.CaO nano particle is noticeable as biocide, but
Seldom report its application [Dizaj S., Lotfipour F., Barzegar-Jalali M., Hossein in the polymer
M.,Adibkia K.,Antimicrobial activity of the metals and metal oxide
nanoparticles,Materials Science and Engineering C44(2014)278-284；Lyndon J.A.,
Boyd B.J.,Birbilis N.,Metallic implant drug/device combinations for
controlled drug release in orthopedic applications.Journal of Controlled
Release 179(2014)63-75].CaO nano particle has the advantages that cheap, bio-compatible, obtainable, this make they at
For promising antimicrobial [Jin T., He Y., Antibacterial activities of magnesium oxide
(MgO)nanoparticles against foodborne pathogens,Journal ofNanoparticle
Research13(2011)6877-6885].It has been reported that nano particle is to Escherichia coli and staphylococcus aureus
(Staphy í ococcus aureus) bacterium excellent antimicrobial acivity [Boubeta C., M.Bacelis L.,
Cristofol R.,Sanfeliu C.,RodriguezΕ.,Weissleder R.,Piedrafita S.,Simeonidis
K.,Gelakeris M.,Andiumenge F.,Calleja A.,Casas L.,Monty C.,Martinez B.,Self-
assembled multifunctional Fe/MgO nanospheres for magnetic resonance imaging
and hyperthermia.Nanomedicine 6(2010)362-370].Different authors explain the excellent properties of CaO with
Other are oxide-based seemingly.CaO toxicity, which is attributed to generate reactive species on the surface of these nano particles and be attributed to pH, to be increased
[Yamamoto O.,Ohira T.,Alvarez K.,Fukuda M.,Antibacterial characteristics of
CaCO3-MgO composites,Materials Science and Engineering B 173(2010)208-212]。
As described above, seldom report mixes CaO in polymeric matrix.
KR20010083418, which is taught, to be filled in antimicrobial ceramic composition in polymer film to prepare film, and
Pears are stored using the film to keep the quality and the method that stores under the state of cooling for a long time of pears.The film is by comprising low
The masterbatch of density polyethylene (LDPE) and antimicrobial compositions squeeze out single layer, or by upper layer LDPE and lower layer LDPE with
And three layers of the film that the middle layer filled with ceramic antimicrobial is constituted.Antimicrobial ceramic composition is with 2 weight % to 30
Weight % is used, and includes oxide (including the Fe of at least transition elements of 70 weight %2O3、MnO2、Ag2O、Cr2O3).It is main
The oxide of race's element includes Al2O3, BaO or CaO.
KR100741514 discloses a kind of inorganic nano composite material composition for construction material, with excellent
Anti-flammability and moisture resistance, microbial resistance, antibiotic property and deodorization, improve residential housing health in terms of be advantageous.
Inorganic nano composite material composition include three-decker 100 weight % biological function light material, by hydrated mica,
The moisture and water formation of absorption are constituted, and 150 parts to 200 parts of granularity is the biological function mineral of 150nm to 25nm
(minera！Biofuncionai) belong to amphibole group (grupo am í iboio): the inorganic bond of 50 weight % to 150 weight %
The water of agent such as dimethyl silicone polymer or octyltri-ethoxysilane and 50 weight % to 250 weight %.The light material of biological function
Material is made up of: the SiO of 36 weight % to 46 weight %2；The AI of 6 weight % to 16 weight %2G3；16 weight % to 35 weights
Measure the MgO of %；The Fe of 6 weight % to 13 weight %2O3；The CaO of 1 weight % to 5 weight %；1 weight % is to 6 weight %'s
K2O；The TiO of 1 weight % to 3 weight %2；With 8 weight % to the H of 16 weight %2O。
JPH03227340 discloses a kind of composition, it includes high density polyethylene (HDPE), is based on polyacrylic polymer, cunning
Stone, CaO etc. and with excellent mouldability and be capable of providing tensile strength and excellent waterproofness, rigidity etc. surface it is living
Property agent.The composition includes the high density polyethylene (HDPE) of 35 parts by weight to 87 parts by weight, with 0.01g/10 points at 190 DEG C
The melt flow rate (MFR) (MFR) of clock to 0.1g/10 minutes, density is 0.938g/cc to 0.965g/cc, and it is big to melt tension
In equal to 10g；A kind of polymer based on propylene, the MFR at 230 DEG C are 0.3g/10 minutes to 10g/10 minutes；10 weights
Measure the talcum of part to 45 parts by weight；The total amount of first three said components based on 100 parts by weight is measured as 1 parts by weight to 10 weight
The CaO or MgO of part；The first three component listed above (content of above-mentioned second component and third component based on 100 parts by weight
Ratio be 2 to 4) total amount, measure the surfactant for 0.05 parts by weight to 1 parts by weight.In addition, the composition is used to form
Film.
JPH0493360 discloses a kind of antifungal composition, by selected from can heat cure organic siliconresin and thermoplasticity
The resin of resin (for example, polyvinyl resin) is constituted with selected from least one of ZnO, MgO and propionate compound, furthermore may be used
To be added to it CaO, NaHCO3, citrate, sorbate, dehydroacetate salts and phosphoric acid to be to improve fungal resistance.It is described
Composition can be used for kitchen, toothbrush, clothes etc..
KR20000032538 discloses a kind of bioceramic film, and it includes ceramic powders, paraffin and silicone oil, and for a long time
Vegetables or fruit are saved with fresh form.The film pass through following procedure obtain: by FeO, MnO of 5 parts by weight to 15 parts by weight,
AlO, TiO, ZrO, MgO, ZnO, SiO, CaO and Ag are mixed with the polyethylene ethylene base of 100 parts by weight, at 800 DEG C to 1250 DEG C
Lower sintered mixture is to obtain ceramic powders.By the ceramic powders of 0.001 parts by weight to 10 parts by weight and 25 parts by weight to 35 weights
The silicone oil of the paraffin and 35 parts by weight to 45 parts by weight of measuring part mixes at 100 DEG C.The film protection plant and fruit are than conventional
Film long twice of the period.
M ü nchow Elisen etc., Clin Oral Invest., on November 27th, 2015 (" Synthesis and
characterization of CaO-loaded electrospaun matrices for bone tissue
Engineering ") it discloses synthesis and characterizes the nano particle for having CaO for treating the load of osteomyelitis and bone tissue engineer
Based on the biodegradable matrix (poly- (6-caprolactone), PCL) based on polymer.In order to prepare, PCL/ gelatin ratio is used
Example is the solution comprising CaO nano particle of 1:1 (by weight), is Electrospun in fibrous matrix.Publication religion
Although it is inconsistent to have led antibacterial activity, CaO nano particle is actually supported in PCL or PCL fiber/gelatin and does not have to matrix
There is negative effect.
Therefore, although prior art discloses the polymer films for being mixed with CaO, incorporation as in the present invention is not referred to
There are the low density polyethylene (LDPE) of the nano particle of CaO and the polymer film with fungicidal properties and biocide of polylactic acid.
The film is that the film applied in medicine and food packaging applications has started chance.
Summary of the invention
Biocidal polymers film the present invention relates to the nano particle comprising calcium oxide (CaO) as biocide.
CaO nano particle is less than or equal to 55nm, preferably lower than or equal to 20nm, and can also be and change through oleic acid surface
The CaO nano particle of property is to improve its adhesiveness with polymer.
Polymer is selected from polyethylene (PE), polypropylene (PP), polystyrene (PS), polylactic acid (PLA), poly(hydrobutyl ester)
(PHB), polyglycolic acid (PGA) or both or more the mixture of person thermoplastic polymer and nano particle be CaO,
Wherein the polymer forms nanocomposite, wherein the total weight based on film, CaO is with 3 weight % to the amount of 10 weight %
In the presence of.
The film shows antimicrobial (especially for Escherichia coli) characteristic.
Detailed description of the invention
Fig. 1 analyzes the transmission electron microscopy (TEM) of the calcium oxide nano particle of 55nm.
Tem analysis of Fig. 2 to the calcium oxide nano particle of 20nm.
XRD analysis of Fig. 3 to CaO nano particle, in which: P portlandite, C calcite or calcium oxide.
Fig. 4 e. coli concentration 10-1The bacterium colony of CFU/mL: a) original PE；B) the modified CaO 10%w/w of PE/, diameter are
20nm。
Specific embodiment
Biocidal polymers film the present invention relates to the nano particle comprising calcium oxide (CaO) as biocide.
CaO nano particle is less than or equal to 55nm, preferably lower than or equal to 20nm, and including through the modification of oleic acid surface
CaO nano particle is to improve its adhesiveness to polymer.
Polymer is the thermoplasticity polymerization selected from PE, PP, PS, PLA, PHB, PGA or its two or more mixture
Object and nano particle are CaO, and the polymer forms nanocomposite, wherein the total weight based on film, CaO is with 3
The amount of weight % to 10 weight % exists.
The film shows antimicrobial (especially for Escherichia coli) characteristic.
The film, which is shown, kills microbiologic properties and other characteristics (such as mechanical property).Therefore, it was demonstrated that calcium oxide nanometer
Particle is to confer to a variety of improved multi-purpose materials of polymeric matrix.Particularly, the Biocidal properties of nano particle and nanometer
The diameter of grain is related, and smaller size increases the biocidal activity of nanocomposite.
In addition, the film is produced by method comprising the following steps:
A) by Ca (NO at 60 DEG C3)2·4H2The mixture synthesis 20nm of the solution of the solution and citric acid of O is to 55nm's
Then temperature is risen to 100 DEG C to form gel by nano-sized particles, calcine gel at 600 DEG C then to obtain CaCO3's
Nano particle, and the nano particle is calcined at 900 DEG C to obtain CaO nano particle；
B) optionally, CaO nano particle is dissolved in hexane and oleic acid to modified, then ultrasonic treatment and mistake under vacuum
Filter, it is then dry at 90 DEG C, obtain the CaO nano particle with improved adhesion characteristic；And
C) polyethylene (PE) or poly- cream are prepared by the CaO nano particle that melt mixed mixes CaO nano particle or modification
Then the nanocomposite of sour (PLA) is added wherein PE or PLA is premixed at 190 DEG C with the amount in the range of 1% to 5%
Add CaO nano particle, then mixes；And
D) film is obtained and the nanocomposite melt obtained in previous step is blended.
Embodiment
The synthesis of nano particle
The synthesis of CaO nano particle having a size of 55nm
Firstly, preparing two kinds of solution at room temperature.Solution 1 includes Ca (NO3)2·4H2O(1M).At room temperature by the solution
It is kept for 5 minutes under stiring.Second solution includes citric acid (2.5M), its hand operated mixing is homogenized until realizing.
Once obtaining two kinds of solution, solution 2 is added in solution 1 at 60 DEG C.Then, by sample at 100 DEG C
Stirring is lower to be kept for 20 hours.It waits until forming gel and it being made to cool down a night at a suitable temperature.Finally forged at 600 DEG C
It burns 5 hours, obtains CaCO3Nano particle.In order to generate CaO nano particle, sample is calcined 5 hours at 900 DEG C respectively.
CaO nano particle having a size of 20nm
1g NaOH is added to ethylene glycol and Ca (NO3)2·4H2In the mixture of O, by solution be ultrasonically treated 10 minutes with
Gel is formed, and gel is stood 5 hours.Then it using water washing and is dried under vacuum.By nano particle at 500 DEG C
5 hours [Safaei-Ghoml J., Ghasemzadeh M.A., Mehrabi M., Calcium oxide of lower calcining
nanopartlcles catalyzed one-step multicomponent synthesis of highly
substituted pyrines in aqueous ethanol media,Scientia Iranica C 20(2013)549-
554]。
The modification (CaO mod) of CaO nano particle
Modified by nano particles is carried out after synthesizing by the above method.Use 0.5g 50ml hexane and 400 microlitres of oil
The CaO of acid dissolution.The operation is carried out, solution is ultrasonically treated about 20 minutes.Then by suspension in nitrogen environment
It is stirred 5 hours in 60 DEG C of baths of the magnetic stirring apparatus with 250rpm.Then, nano particle is filtered under vacuum, finally
It is 24 hours dry in 90 DEG C of baking oven.It is modified to improve the adhesiveness of nano particle and polymer.
Mix the nanocomposite of CaO and modified CaO particle preparation PE
Using computer Brabender Plasticorder by melt-mixing processes prepare composite material PE/CaO and
PLA/CaO。
In the first scenario, polymer is premixed at 150 DEG C to 190 DEG C according to matrix, mixing velocity 10rpm.
Nano particle (calcium oxide) then is added by changing the amount of quality between 1%, 3% and 5%, especially at 5 minutes
In time.Then it is carried out mixing step 5 minutes at 110rpm.
The nano particle of CaO and PE/CaO nanocomposite characterizes
Scanning electron microscopy (TEM)
In order to study the morphology and size of nano particle, 12 microscope of Philips Tecnai (Holland) of 80kV is used.
Nano particle is ultrasonically treated in ethanol, is subsequently deposited upon on copper mesh to check.
X-ray diffraction (XRD)
The crystal structure of the nano particle of CaO is analyzed on the diffractometer (Siemens D5000) of λ=Cu.Scanning range:
0°<2θ>80°。
Elongation strain test
Once obtaining nanocomposite by melt mixed, film is just prepared.For this purpose, weighing the composite wood of about 16g acquisition
Expect and 50 bars and 170 DEG C to 190 DEG C at a temperature of suppress in the press with heating plate, by polymer molding 3 minutes
Period simultaneously contacts pre-contact 2 minutes.Use water as cooling medium to cool down press, so that gained film be used to remove metal plate.You
24 hours periods are had to wait for stablize sample and allow secondary crystallization process.For mechanical analysis dynamometer, needs make
With the sample for using formed punch operating pressure to cut.Each film is cut into 4 samples, carries out extension test.
Differential scanning calorimetry, DSC
It is analyzed on differential scanning calorimetry (DSC).Firstly, weighing the nano-composite material membrane of 5mg to 6mg, deposition of aluminum
Lid.Sample is heated to 200 DEG C from 25 DEG C with 10 DEG C/min of rate under nitrogen atmosphere, be cooled to 25 DEG C and is again heated to
200℃。
Antimicrobial analysis
It is analyzed by colony counting method, this method allows to quantitatively determine through Colony Forming Unit (CFU) acquisition
The biocidal activity of nanocomposite.Nanocomposite is cut into 2.5 × 2.5cm square, original polymer conduct pair
According to, and inoculum density is 107The Escherichia coli of CFU/mL.Then in order to determine antimicrobial acivity, carrying out bed board concentration is 10- 1CFU/mL、10-2CFU/mL and 10-3The bacterium colony of CFU/mL counts, and quantitative to Colony Forming Unit, finally by using equation
Formula 1 obtains slip:
Wherein:
Bacterial flora in C=original polymer
Bacterial flora in M=nanocomposite
The characterization of nano particle
The measurement of CaO nano particle
In fig. 1 it is illustrated that the TEM image of the CaO nano particle obtained by sol-gel method.As it can be seen that pattern is in rule
The average particle size of spherical nanoparticle is mostly 55nm, shows that the method is effective.
Application method opinion 2 obtains the CaO nano particle that diameter is 25nm, as shown in Figure 2.
X-ray diffraction
Fig. 3 shows the X-ray diffractogram of the CaO nano particle through calcining.In this process, calcite (CaCO3) by
(CO is generated in its chemical transformation2Gas phase) and lose the mass percent of its weight.Analysis shows peak most outstanding is nanometer
Grain 2 θ=37 °, this with prediction cubic structure CaO and [Mirghiasi Z., Bakhtiari F., Darezereshki E.,
Preparation and characterization of CaO nanoparticles from Ca(OH)2by direct
Thermal decomposition method.Journal of Industrial] it is related.Outside CaO feature diffraction 34 ° and
Bragg reflection is presented at 54 ° of angle.The reflection corresponding to calcite calcium carbonate phase is observed under 28 °.This is because
The center of CaO particle, underheat are very small so that can ignore to retain trace calcite in calcining present invention
Disregard, therefore does not influence nano particle.On the other hand, CaO is very hydrophilic, and when contact environment moisture, immediate response generates a small amount of
Ca(OH)2, this is to observe to may be the peak due to caused by the calcium hydroxide phase of portlandite why at 18 °.
Finally, it may be said that CaO is polycrystalline particle.
The characterization of PE nanocomposite added with CaO
Thermal characteristics
Table 1 respectively illustrates the PE of the CaO nano particle with 20nm diameter obtained by differential scanning calorimetric analysis
Melting temperature, crystallization temperature, the result of melting enthalpy and crystallization percentage of nanocomposite.Added with calcium oxide nano particle
Polymer thermal characteristics it is constant.Nano particle by mixing 55nm obtains similar result.
Crystallization temperature, melting temperature and the crystallization percentage of the PE/CaO nanocomposite of 1. 20nm of table
Wherein:
Tc=crystallization temperature,
Tm=melting temperature,
ΔΗP=melting enthalpy
Xc=crystallization percentage
Mechanical property
Nanocomposite is characterized by elongation strain.In table 2, the nanometer for being mixed with that diameter is 25nm is also shown
The average value and phase of the parameter of the Young's modulus and yield strength of both the nanocomposite and polymeric matrix (PE) of particle
Answer standard deviation.
Table 2. uses the PE of CaO as the mechanical property of the nanocomposite of matrix
E=Young's modulus or elasticity modulus,
ο ψ=yield strength or yield point
From Table 2, it can be seen that Young's modulus increases by 27%, this shows CaO nanometers when nano particle load capacity is 10%
The presence of particle will provide bigger rigidity for polymer.By mixing the nano particle modified through oleic acid, in addition 35%
When nano particle, Young's modulus increases.
Microbiological analysis result
The bacterium colony that table 3 shows the Escherichia coli of the PE nanocomposite of the CaO nano particle added with 55nm is formed
The result of the reduction percentage of unit (CFU).
Table 3. uses the E. coli bacteria of nanocomposite of the PE of unmodified 55nm CaO as matrix to reduce
Percentage
It is not fettered by specific theory, the antimicrobial acivity of calcium oxide may be because are as follows: calcium oxide is in water or vapor
In the presence of form calcium hydroxide, and generate Ca+2Ion can penetrate the cell membrane of microorganism, lead to bacterial penetration overbalance,
Eventually lead to cell death.
In table 4 and 5, show respectively using the nanocomposite of unmodified and modified 25nm nano particle to thin
The effect of bacterium.The percentage that reduces of bacterium increases with the percentage of nano particle.By with oleic acid to the surface of nano particle into
Row is modified, and which improve the dispersion of nano particle in the polymer, and this can permit improvement Biocidal properties, to generate
It is effective to the 99.99% of bacterium.
The Escherichia coli of the nanocomposite for the CaO that table 4. is 25nm using the unmodified diameter of PE matrix reduce hundred
Divide ratio
Table 5. reduces percentage using the Escherichia coli of the modification CaO Mod nanocomposite of PE matrix
In fig. 4 it is shown that contact after original PE and PE/CaO surviving bacteria.It should be noted that for mixing 10%w/w
Modified nanoparticles PE/CaO mod, bacterium due to nano particle presence and cannot survive.
Claims (10)
1. a kind of Biocidal polymers film is characterized in that the nano particle conduct of the calcium oxide (CaO) comprising size less than 55nm
Biocide and selected from polyethylene (PE), polypropylene (PP), polystyrene (PS), polylactic acid (PLA), poly(hydrobutyl ester) (PHB),
Polyglycolic acid (PGA) or both or more the mixture of person thermoplastic polymer.
2. Biocidal polymers film according to claim 1 is characterized in that the size of the CaO nano particle is less than
55nm。
3. Biocidal polymers film according to claim 1 is characterized in that the size of the CaO nano particle is less than
20nm。
4. Biocidal polymers film according to claim 1, wherein the total weight based on the film, described CaO nanometers
Grain exists with the amount of 3 weight % to 10 weight %.
5. Biocidal polymers film according to claim 1 is characterized in that the CaO nano particle is modified through oleic acid
The nano particle of CaO.
6. Biocidal polymers film according to claim 1, wherein the thermoplastic polymer is PE or PLA.
7. Biocidal polymers film according to claim 1 is characterized in that melting temperature is 100 DEG C.
8. Biocidal polymers film according to claim 1 is characterized in that crystallization temperature is 111 DEG C to 113 DEG C.
9. Biocidal polymers film according to claim 1 is characterized in that Young's modulus is 166MPa to 205MPa.
10. Biocidal polymers film according to claim 1 is characterized in that yield strength is 5.75MPa to 7.17MPa.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CL2016001863A CL2016001863A1 (en) | 2016-07-22 | 2016-07-22 | Polymer with incorporation of mgo and cao nanoparticles for food packaging. |
| CL1863-2016 | 2016-07-22 | ||
| PCT/CL2017/050035 WO2018014144A1 (en) | 2016-07-22 | 2017-07-19 | Polymer comprising cao nanoparticles for food packaging |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109952026A true CN109952026A (en) | 2019-06-28 |
Family
ID=57234078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780051744.8A Pending CN109952026A (en) | 2016-07-22 | 2017-07-19 | The polymer comprising CaO nano particle for food packaging |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN109952026A (en) |
| CL (1) | CL2016001863A1 (en) |
| MX (1) | MX2019000942A (en) |
| WO (1) | WO2018014144A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CL2019002565A1 (en) * | 2019-09-09 | 2019-11-29 | Univ Santiago Chile | Nanoparticles of calcium oxide and polymeric nanocomposites that comprise them, method of obtaining from natural solid food by-products / discards rich in calcium carbonate and method of preparing polymeric nanocomposites, and use as antimicrobial in films for food packaging or coatings of different surfaces |
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Also Published As
| Publication number | Publication date |
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| MX2019000942A (en) | 2019-11-28 |
| CL2016001863A1 (en) | 2016-09-16 |
| WO2018014144A1 (en) | 2018-01-25 |
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