Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • 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
  • A01N59/16—Heavy metals; Compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
  • C09C1/42—Clays
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/16—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/16—Biodegradable polymers

Definitions

• the present invention relates to active and / or bioactive nanocomposite materials generically based on the use of nano-clays as a support for the active substances.
• Said activity is obtained through the formulation of a specific type of additives based on sheets of natural and / or synthetic clays that are intercalated with metals and / or salts thereof with antimicrobial and / or oxygen sequestration capacity and / or with other organic, inorganic compounds or combination thereof that also have antimicrobial and / or antioxidant properties.
• the formulation of nanocomposite materials based on the incorporation of the aforementioned additives in a plastic matrix, or ceramic, by any method of manufacturing or processing of plastics or of preparation and processing of ceramic powders is described.
• the additives are incorporated into plastic matrices by methods of deposition and evaporation of the solvent (eg coatings and lamination), application of the mon-American solution followed by polymerization and curing or cross-linking or vulcanication, operations typically used during the formulation of thermosets and elastomers, by melt mixing processes (eg extrusion, injection, blowing) and / or in-situ polymerization methods.
• the nanocomposite materials with plastic matrix can be prepared by different procedures typically used in the processing and manufacturing of plastics, such as casting and / or rolling techniques (solvent dissolution and evaporation), melt mixing, thermosetting and elastomer formulation and of in-situ polymerization, for its advantageous application in both active packaging (as defined in national and international legislation on active and intelligent food packaging) of products of interest for food and antimicrobial plastics, antioxidants and oxygen sequestrants, in surgical equipment, as well as for applications in other sectors.
• casting and / or rolling techniques solvent dissolution and evaporation
• melt mixing thermosetting and elastomer formulation and of in-situ polymerization
• thermosetting and elastomer formulation and of in-situ polymerization for its advantageous application in both active packaging (as defined in national and international legislation on active and intelligent food packaging) of products of interest for food and antimicrobial plastics, antioxidants and oxygen sequestrants, in surgical equipment, as well as for applications in other sectors.
• nanocomposite materials with ceramic matrix these are incorporated during the preparation of powders typically used in the manufacture of ceramic products that involve grinding, atomization, pressing or extrusion, enamelling in the case of enameled, and cooked products.
• the present invention relates to the use of said materials for multisectoral applications.
• nanocomposites and their processing techniques are described in, for example, US Patent No. US 4739007; and more specifically in what concerns the present invention in WO2007074184A1.
• a new route for manufacturing nanocomposites that may or may not be biodegradable, with antimicrobial properties based on natural products and / or with the ability to fix or release controlled other active or bioactive substances is described.
• These nanocomposites based on phyllosilicates and / or synthetic double laminar hydroxides are interspersed with different organic modifiers, and once incorporated into thermoplastic and / or thermostable matrices, they are able to improve them. barrier properties to gases and vapors.
• the aforementioned documents are some examples of patents and literature on polymer clay nanocomposites prepared from modified clays. These documents describe a nanocomposite material such as an exfoliated or interleaved plate, with a touch structure of nanometric dimensions, comprising intercalated clay dispersed in a polymer matrix, such as an oligomer, a polymer, or a mixture thereof.
• a nanocomposite material such as an exfoliated or interleaved plate, with a touch structure of nanometric dimensions, comprising intercalated clay dispersed in a polymer matrix, such as an oligomer, a polymer, or a mixture thereof.
• US 4739007 describes the preparation of Nylon-6-clay nanocomposites from montmorillonites treated with alkylammonium salts by the melt mixing method.
• Microorganisms and in particular bacteria, are the main cause of diseases caused by the consumption of contaminated food. These can survive the heat treatment required for canning or contaminate the food after such treatment due to sutures or leaks from the container. In addition to its potential danger to health, the proliferation of microorganisms can cause alterations in food that in turn give rise to changes in the physical, chemical and organoleptic properties thereof. Some of the traditional preservation methods such as heat treatments, irradiation, modified atmosphere packaging or addition of salts, can not be applied to certain types of food such as vegetables, fruits and fresh meats or ready-to-eat products. On the other hand, the direct application of antibacterial substances on food has limited effects since they are neutralized and spread rapidly into the food.
• active packaging is a viable and advantageous way to limit and control bacterial growth in food, since antimicrobial agents migrate slowly from the material to the surface of the product.
• the migration can be as extensive as required, so that it covers the time of transport, storage and is guaranteed until consumption.
• the silver antimicrobial nanoadditives described in the present invention once incorporated into the containers, they can control the microbial contamination by inactivation of the enzymatic metabolism of the microorganisms.
• microorganisms are also undesirable in other sectors.
• it is essential to eliminate the risks of infection in invasive treatments, of open wounds, as well as in routine treatments.
• coatings with antimicrobial films of catheters and stethoscopes, and the elaboration of fabrics in fibers pretreated with silver nitrate or with broad-spectrum antibiotics for wound and burn treatments can be cited.
• the use of fibers pretreated with antibacterial agents limits the proliferation of microorganisms in the face of sweat, humidity and high temperatures, reducing bad body odors and risks of contagion.
• Fouling is the accumulation and deposition of biological material on surfaces exposed to various environmental conditions, such as boats, objects or painted systems exposed to high humidity conditions or other surfaces exposed to active, aggressive or environmentally adverse media.
• fuel consumption can increase up to 50% due to the hydrodynamic resistance offered by the accumulation of biological material in the hull.
• Antimicrobial systems can act as antifouling if they are applied in the form of layers on the surface of the boat, making fuel consumption optimal, and cleaning and maintenance operations less frequent.
• coating the interior with a film of antimicrobial compounds significantly reduces the growth of algae and the generation of bad odors, so that the quality of the water contained is guaranteed for longer.
• Plastic materials with antimicrobial properties can also be used in the manufacture of cranks, handlebars, handles and armrests of public transport elements, in railings and support points of places of high concurrence, in the manufacture of sanitary parts for public and mass use, as well as in headphones and microphones of telephones and audio systems of public places; kitchen tools and food transport, all this in order to reduce the risk of spreading infections and diseases. It is also of emerging interest to manufacture ceramic pieces that inhibit the proliferation of microorganisms on ceramic products, for example, the proliferation of fungi and molds on surfaces covered with ceramic tiles or on the junction points of these.
• the active properties are generically conferred or reinforced by the incorporation of substances based on silver, iron or other metals and / or organic natural or synthetic substances with for example biocidal capacity, antioxidant and sequestrant oxygen scavengers in The structure of the nanoarcillas.
• the incorporation of metallic biocides in clays is not only interesting for the manufacture of nanocomposites based on the addition of such additives to plastics, but, because biocides based on metallic metallics resist heat treatments, which may also be necessary for To favor the reduction of the salts of biocidal metals to their corresponding metals, they can also be used in the ceramic industry for the manufacture of ceramic and porcelain products with antimicrobial properties.
• Some metals such as iron, oxidize easily and therefore can be used to sequester oxygen in applications where this gas is a problem for product conservation.
• Some natural substances such as resveratrol have antioxidant and bioactive properties, that is, in addition to their antioxidant nature due to their ability to fix free radicals, they provide a health benefit when ingested if there is a migration from the plastic.
• nano-clay based antimicrobial nanoadditives allows to increase the efficacy of these products, due to the large dispersion exhibited by the nanoparticles in these matrices. Excellent results are thus obtained with lower proportions of nanoadditives, and the ceramic products can be formulated in a more efficient and versatile way since the antimicrobial is supported on the clays that are natural components of the ceramic matrix itself and therefore also result in a significant reduction in costs.
• the aforementioned examples also allow to define the field of application of the new nanocomposite materials with active properties based on metals and natural or synthetic substances, whose procedures for obtaining are detailed in this patent.
• the nanocomposite materials antimicrobial metals and some ammonium salts eg the hexadecyltrimethylammonium bromide allowed for food contact
• the present invention relates to active nanocomposite materials, obtained by the introduction of laminar nanoadditives with or without prior modification of antimicrobial and / or chitosan quaternary ammonium salts and / or derivatives of this antimicrobial which also include intercalated metal nanocomposite materials
• a first essential aspect of the present invention refers to nanocomposite materials that have a plastic matrix, or ceramic and are constituted from the incorporation of nanoadditives of clays of the laminar type.
• the plastic matrices are selected without limitation from the group consisting of thermoplastics, thermosets and elastomers such as polyolefins, polyesters, polyamides, polyimides, polyketones, polyisocyanates, polysulfones, styrenic plastics, phenolic resins, amidic resins, ureic resins, melamine resins, resins Polyester, epoxy resins, polycarbonates, polyvinyl pyrrolidones, epoxy resins, polyacrylates, rubbers and rubbers, polyurethanes, silicones, aramids, polybutadiene, polyisoprenes, polyacrylonitriles, PVDF, PVA, PVOH, EVOH, PVC, PVDC or biodegradable biomass materials as proteins, polysaccharides, lipids and biopolyesters or mixtures of all these and may contain all types of additives typically added to plastics to improve their manufacture and / or processing or their properties. Furthermore, said type of matrix is in a
• the ceramic matrices comprise and without limitation, water, clays (preferably kaolinites and occasionally montmorillonites), deflocculants, feldspar, feldspathic and occasionally sands, kaolin, carbonates and zirconium.
• the ceramic matrices of the enamel type and other type of ceramic coatings include and without limitation kaolin or a kaolinitic clay (5%) or montmorillonite (1%), feldspars, frits, silica and silica sands.
• said type of matrix is in a proportion from 5% to 99.99%; preferably from 20% to 99.99%, and more preferably from 65% to 99.99%.
• the matrices of plastic or ceramic type may contain agents with properties of barrier to electromagnetic radiation and fire resistance and other active or bioactive substances additional to the nano-clays, selected from the group consisting of metals and / or their salts organic and inorganic antimicrobial metals (preferably silver, copper, nickel or cobalt), oxygen sequestrants such as iron and its salts, low molecular weight substances that have an active or bioactive character selected from ethanol, or ethylene, or of the essential oils type (preferably thymol, carvacrol, linalool and mixtures), or small-sized antimicrobial peptides (preferably bacteriocins) natural or obtained by genetic modification (preferably nisins, enterokines, lacticines and lysozyme), quaternary ammonium salts, preferably those allowed for food contact, or natural or synthetic antioxidants (pref errably polyphenols such as, but not limited to, resveratrol or flavonoids, plant extracts such as, but
• an antioxidant such as resveratrol
• an oxygen sequestrant such as iron and iron salts
• the nano-clays are selected from the group consisting of laminar silicates and / or double laminar hydroxides. These above are selected without limitation from the group consisting of montmorillonite, kaolinite, bentonite, smectite, hectorite, sepiolite, gibsite, dicktite, nacritite, saponite, halloisite, vermiculite, mica, and / or mixtures thereof or with other phyllosilicates, mainly, with or without previous organic and / or inorganic surface modification. These materials are characterized in that they are introduced as laminar type charges with sizes in the range of nanometers in at least the thickness of the particle, in plastic matrices and in ceramic matrices to form the new active nanocomposites.
• the active additives are in a proportion from 0.01% to 95%, preferably from 0.01% to 80% and more preferably from 0.01 to 10%.
• the active additives are in a proportion from 0.01 to 95%, by weight, preferably between 0.01% and 80% and more preferably from 0.01 to 35%.
• the active additives are in a proportion from 0.01% to 50%, preferably from 0.01% to 20% and more preferably from 0.01 to 15%.
• the superficial modification of the clay nanoadditives when applied allows, in addition to introducing or accentuating the active activity by incorporating compatibilizers with biocidal properties, increasing the compatibility between the clay and the matrix to achieve better exfoliation of the clay.
• a good morphology is achieved to improve the dispersion and surface exposure of the active antimicrobial substance and / or oxygen sequestrant, which are substances based on metals such as silver, copper, nickel, cobalt, iron, zinc and / or combinations of the same and / or their inorganic or organic salts, organic compounds, preferably salts allowed for food contact (that is that they are included in the lists of monomers and other starting substances authorized by the legislation to be used in the manufacture of materials and objects plastics) such as and without limitation the hexadecyltrimethylammonium bromide (who this invention has proven to be antimicrobial in itself), polyethylene glycol esters with aliphatic monocarboxylic acids (C6-C22) and their sodium and ammonium sulfates
• plastic materials In the case of plastic materials, they have active activity and improvements in their barrier properties and other physical properties, resistance to fire and allow blocking electromagnetic radiation, in addition to allowing controlled release of the same or other substances with active properties and / or bioactive with respect to the pure material. In the case of materials ceramic, more effective antimicrobial properties are obtained due to the nanoparticulation of the biocidal metal.
• nanocomposite materials are prepared in the case of plastics by means of lamination or coating techniques (casting of the solution), by application of the mon-American solution followed by polymerization and curing, operations typically used during the formulation of thermosets, by the above procedure but followed by crosslinking or vulcanizing, operations typically employed in the manufacture of elastomers, by melt mixing using conventional techniques for processing plastics from pellets and / or powder of the polymer or plastic or by in-situ polymerization.
• plastic nanocomposite materials are of particular interest in the food packaging industry, since these active packages allow to protect the product from the action of the microorganisms, protect the container itself and its oxidation content either by using antioxidants that sequester free radicals or oxygen scavengers that eliminate oxygen and / or the fixation and / or the controlled release of the same or other active substances and additionally, significantly improve the gas and vapor barrier properties, mechanical properties of UV barrier and others typically associated with the use of nano-clays.
• plastic and ceramic nanocomposite materials reinforced with nano-clays with active properties are useful in the medical-surgical, biomedical and pharmaceutical areas, for the manufacture and coating of equipment and materials used in routine and invasive treatments and in construction .
• a second essential aspect of the present invention refers to the process for manufacturing the nanocomposite materials described in the present invention, which may be based on structures such as lamellar phyllosilicates, including clays (eg montmorillonite, kaolinite, bentonite, smectite , hectorite, sepiolite, saponite, halloisite, vermiculite, mica) or synthetic or natural laminar double hydroxides of laminar structure and comprising the following steps:
• clays eg montmorillonite, kaolinite, bentonite, smectite , hectorite, sepiolite, saponite, halloisite, vermiculite, mica
• synthetic or natural laminar double hydroxides of laminar structure comprising the following steps:
• step 5) Obtaining fine laminar either in liquid suspension or by subsequent drying by the methods described in step 4) powder. These systems in both liquid and powder suspension are considered as the starting product of the present invention.
• the expanders are selected from the group consisting of DMSO, alcohols, acetates, or water and mixtures thereof, and metal salts of silver, copper, iron, nickel or cobalt, which activate the fines by an initial increase in the basal spacing of the sheets and modify the surface characteristics of the clay.
• the penetration of the precursors will be accelerated without limitation by the use of temperature, a homogenizer of turbulent regime, ultrasound, supercritical fluids, deflocculating agents such as acrylates and / or phosphates, pressure or mixture of the above.
• the drying of these, previously washed or not with water or alcohols can be carried out by evaporation in an oven, lyophilization, centrifugation and / or gravimetric processes in solution or turbo-dryers or by atomization.
• the solution of the interleaved precursor can be used, without a previous washing and / or drying process, as a starting means for the next stage of incorporation of the modifier.
• the compounds to be inserted are selected and without limitation from the group formed by PVOH, EVOH and derivatives of the same family, and / or biopolymers such as peptides and natural or synthetic proteins via chemical or genetic modification of microorganisms or plants and natural or synthetic polysaccharides via chemical or genetic modification of microorganisms or plants and polypeptides, lipids, nucleic acids and polymers of synthetic nucleic acids obtained chemically or by genetic modification of microorganisms or plants, and biodegradable polyesters such as polylactic, polylactic acid- glycolic, polycaprolactone, adipic acid and derivatives and polydroxyalkanoates, preferably polydroxybutyrate and their copolymers with valeriates, biomedical materials such as hydroxyapatites and phosphates of organic salts,
• Quaternary ammonium salts can also be intercalated - preferably salts allowed for food contact (that is, they are included in the lists of monomers and other starting substances authorized by the legislation to be used in the manufacture of plastic materials and objects) such as and without limiting sense hexadecyltrimethylammonium bromide, polyethylene glycol esters with aliphatic monocarboxylic acids (C6-C22) and their ammonium and sodium sulfates, perfluorooctanoic acid and its ammonium salt, copolymers of N-methacryloxyethyl-N chloride, N-dimethyl-N -carboxymethylammonium, bis (2-hydroxyethyl) -2-hydroxypropyl-3- (dodecyloxy) methylammonium chloride; and chitosan and its derivatives, silver, iron, copper, nickel and / or its organic or inorganic salts, and other particles or nanoparticles with antimicrobial properties,
• the inorganic material that is intercalated is based on metals such as silver or organic and / or inorganic salts of silver, copper, cobalt iron, nickel or other metals with antimicrobial power and / or oxygen sequestrant
• a physical treatment can be applied subsequently or chemical to change the oxidation state of the intercalated metal center, totally or partially.
• These treatments include non-limiting sense: annealing at high temperatures (250-1200 0 C), UV radiation, infrared radiation, microwave radiation, chemical reduction by ethanol and / or NaBH 4 and / or other chemical reducing agents.
• the degree of oxidation of the metal center will have been modified, totally or partially, (silver, copper, iron, nickel, zinc, cobalt, or other metal used), giving the material antimicrobial properties and / or more or less intense oxygen sequestrants.
• the organic material that is intercalated is the EVOH or any material of the family thereof with molar contents of ethylene preferably less than 48%, and more preferably less than 29%, these are taken to saturation in aqueous medium or in solvents specific alcoholic and mixtures of alcohols and water, more preferably water and isopropanol in proportions in volume of water greater than 50%.
• biopolymers with or without plasticizers, with or without crosslinkers and with or without emulsifiers or surfactants or other nanoadditives are from the group consisting of synthetic and natural polysaccharides (vegetable or animal) such as cellulose and derivatives, carrageenans and derivatives, alginates, dextran, gum arabic and preferably chitosan or any of its natural and synthetic derivatives, more preferably chitosan salts and even more preferably chitosan acetate, and both plant and animal derived proteins and corn proteins (zein), gluten derivatives, such as gluten or its gliadin and glutenin fractions and more preferably gelatin, casein and soy proteins and derivatives thereof, as well as natural or synthetic polypeptides preferably of the elastin type obtained by chemical or modification genetics of microorganisms or plants, lipids such as beeswax, car wax nauba, candelilla wax, shellac and fatty acids and monog
• the degree of deacetylation will preferably be greater than 80% and more preferably greater than 87%.
• the penetration of the precursors will be accelerated by the use of temperature, a homogenizer of turbulent regime, ultrasound, pressure or mixture of the above.
• the active substances will be ethanol, or ethylene, or of the essential oils type (preferably thymol, carvacrol, linalool and mixtures), or natural antimicrobial peptides (preferably bacteriocins) or obtained by genetic modification (preferably nisins, enterokines, lacticins and lysozyme ), or natural or synthetic antioxidants (preferably polyphenols, such as, but not limited to, resveratrol or flavonoids, plant extracts such as, but not limited to, eugenol or rosemary extracts and vitamins, preferably tocopherols and tocotrienols or ascorbic acid / vitamin C) or drugs, or bioavailable enzymes or calcium compounds, marine, probiotic, symbiotic or prebiotic oils (non-digestible fiber), or organic and inorganic metal salts (preferably of silver, copper, iron, nickel or cobalt) or mixture of above.) - These elements are expected to be fixed and / or subsequently released from the nanocomposite towards the
• the contents to be added are generally less than 80% by volume of the solution, preferably less than 12% and more preferably less than 8%.
• the penetration of these substances will be accelerated and without limitation through the use of temperature, a homogenizer of turbulent regime, ultrasound, pressure or mixture of the above.
• deflocculating agents can be contemplated to facilitate the processing, such as and without limitation polyphosphates and / or acrylates.
• both the nano-clays and the complementary compounds mentioned above can be added during their processing using any manufacturing method related to the plastics processing industry such as extrusion, application and curing processes typically used to manufacture and forming thermosetting and elastomers, injection, blowing, compression molding, resin transfer molding, calendering, thermal shock, ultrasonic internal mixing, co-extrusion, co-injection and mixing of these.
• antioxidant substances may be processed by any plastics processing method to obtain a concentrate or to obtain pellets that can be processed by any plastics processing method to obtain plastic articles.
• the polymeric or plastic matrix in this invention the term plastic and polymer is used interchangeably but it is intended to mention both, that is to polymers and plastics
• the polymeric or plastic matrix can be of any thermoplastic, thermoset or elastomer or derivatives of biomass and biodegradable materials such as proteins, polysaccharides, lipids and biopolyesters or mixtures of all these and may contain all types of additives that improve the properties of the barrier to electromagnetic radiation and fire resistance and / or other nanoadditives other than described in this application and which are typically added to plastics to improve their processing or their properties.
• precipitation by evaporation of the resulting nanoadditive and modifying set and, optionally, of the plastic matrix can also be carried out in dissolution, using drying methodologies such as heating and / or centrifugation and / or gravimetric processes in solution or turbo-dryers and / or atomization; by cooling or by adding a precipitating agent to form either a powder of the additive or a masterbatch or Io which is also a concentrate of the nanoadditive in a plastic matrix.
• the organic and / or inorganic metal salts with active properties can be added together with other active or bioactive substances in any of the stages of the manufacture or processing of the ceramic materials, although they will preferably be added during The preparation of powders before atomization
• the polymer matrix additive concentrates can be treated in the following ways: a) it is crushed to produce a particulate product by grinding. b) is processed using any plastics processing methodology to obtain solid state pellets. c) is processed by any manufacturing process related to the plastics processing industry such as extrusion, injection, blowing, compression molding, resin transfer molding, calendering, thermal shock, internal mixing, ultrasound, coextrusion, coinjection and mixing of these. d) it is used as an additive on any plastic matrix (including the biopolymers and biomedical materials mentioned) in a conventional plastics processing route such as those mentioned above.
• the nanocomposite material when reinforced with nano-clays containing metals such as silver or organic and / or inorganic salts of silver, copper, cobalt, nickel or other metals with antimicrobial power, iron and / or its salts, it can be applied, both if it has been done before or not, a physical or chemical treatment to change the oxidation state, totally or partially, of the metallic center interspersed in the plastic or ceramic matrix either before, during or after forming.
• These treatments include without limiting sense: annealing at high temperatures (250-1200 0 C), UV radiation, infrared radiation, microwave radiation, chemical reduction by ethanol and / or NaBH 4 and / or other chemical reducing agents.
• the degree of oxidation of the metal center will have been modified, giving the material advantageous antimicrobial and / or oxygen sequestration properties.
• a third essential aspect of the present invention refers to the use of nanocomposite materials obtained to reinforce the antimicrobial activity in multisectoral applications in which it is required to limit microbial proliferation through the use of plastic materials and ceramic compounds, particularly in applications of packaging and general packaging of food and food components (in the case of polymeric materials), in biomedical, medical-surgical and pharmaceutical applications, or in antifouling applications, in construction applications for enamels, tiles, thermosets and waxes, in applications for personal hygiene products and food containers, greenhouse films, in contact applications in busy places such as supermarkets, carts, stands, linear, countertops, kitchens, escalators or airports, in textile applications, such as gas barriers, vapors , solvents and org products anodes, such as aromas and components of aromas, oils, fats and hydrocarbons, and mixed products of an organic and inorganic nature, for applications that require biodegradable or compostable character, for active packages that require the fixation and / or controlled release of substances of low molecular weight, for applications that
• nanocomposite materials will also serve as materials with electromagnetic radiation and fire resistance barrier properties. All the features and advantages set forth, as well as other features of the invention, can be better understood with the following examples. On the other hand, the examples shown below are not limited but illustrative so that the present invention can be better understood.
• Figure 1 corresponds to the X-ray diffractograms (WAXS) obtained from a sample of montmorillonite-type clay modified with hexadecyltrimethylammonium bromide (organic antimicrobial, expanding and compatibilizing agent) and silver nitrate (temperature resistant antimicrobial), using ethanol as a reducing agent by the method described in Example 1, and a sample of the same type of unmodified clay.
• WAXS X-ray diffractograms
• Figure 2 is an image obtained by transmission electron microscope (TEM) in which the main morphologies that can be observed in the nanoloads obtained according to the present invention are presented.
• the image corresponds to an aggregate of montmorillonite-type clay sheets modified with hexadecyltrimethylammonium bromide and silver nitrate, using ethanol as a reducing agent, by the method described in Example 1.
• the nanoparticles of silver formed on the surface can be observed.
• Figure 3 corresponds to X-ray diffractograms (WAXS) obtained from a sample of kaolinitic clay (pretreated with DMSO) modified with hexadecyltrimethylammonium bromide (organic antimicrobial, expanding and compatibilizing agent) and with silver nitrate (resistant antimicrobial at the temperature), using UV radiation as a reducing agent by the method described in Example 2, and a sample of the same type of unmodified clay (pretreated with DMSO).
• WAXS X-ray diffractograms
• Figure 4 is an image obtained by transmission electron microscope (TEM) in which the main and typical morphologies that can be observed in the nanoloads obtained according to the present invention are presented.
• the image corresponds to an aggregate of kaolinitic clay sheets (pretreated with DMSO) modified with hexadecyltrimethylammonium bromide and silver nitrate, using UV radiation as a reducing agent, by the method described in Example 2.
• Figure 5 is an image obtained by transmission electron microscope (TEM) of an aggregate of montmorillonite-type clay sheets interspersed with silver nitrate, using ethanol as the reducing agent, by the method described in Example 3.
• TEM transmission electron microscope
• Figure 6 is an image obtained by transmission electron microscope (TEM) of an aggregate of kaolinitic clay sheets (pretreated with DSMO) interspersed with silver nitrate, using UV radiation as a reducing agent, by the method described in Example 4.
• TEM transmission electron microscope
• Figure 7 corresponds to an image obtained by transmission electron microscope (TEM) of a film obtained by casting polylactic acid nanocomposite with 10% kaolinite-type clay (pre-treated with DSMO) interspersed with silver nitrate, by the method described in Example 5
• TEM transmission electron microscope
• Figure 8 shows the improvement in water vapor permeability obtained in a nanocomposite film of polylactic acid with 10% kaolinite clay (pretreated with DMSO) interspersed with silver nitrate with respect to a film of pure polylactic acid (Example 5)
• Figure 9 corresponds to an X-ray diffraction spectrum (WAXS) obtained from a sample of montmorillonite-type clay modified with 10% w / w trans-resveratrol, by the method described in Example 8.
• WAXS X-ray diffraction spectrum
• Figure 10 corresponds to the graph of oxidation inhibition in head space of linoleic acid by action of montmorillonitic clays with 10% of antioxidants (trans-resveratrol or ⁇ -tocopherol), by the methods described in Examples 8 and 9.
• Figure 11 corresponds to an X-ray diffraction spectrum (WAXS) obtained from a sample of montmorillonite-type clay modified with 10% w / w ⁇ -tocopherol, by the method described in Example 9.
• WAXS X-ray diffraction spectrum
• Figure 12 corresponds to an X-ray diffraction spectrum (WAXS) obtained from a sample of montmorillonite-type clay modified simultaneously with 20% w / w hexadecyltrimethylammonium bromide and 5% eugenol, by the method described in the Example 10.
• WAXS X-ray diffraction spectrum
• Figure 13 corresponds to the% DPPH inhibition in EVOH films with different trans-resveratrol contents prepared by the precipitation method, by the procedure described in Example 11.
• Figure 14 corresponds to the% DPPH inhibition in EVOH films with %% kaolinite and different resveratrol contents prepared by the procedure described in example 12.
• Figure 15 corresponds to the% inhibition of oxidation of linoleic acid in head space by effect of EVOH films + 1% of antioxidant, according to the procedure described in example 13.
• Figure 16 corresponds to the percentages of DPPH radical inhibition at zero time and at 21 days of exposure of EVOH films. with and without kaolinite, with 1% antioxidant, exposed to direct artificial light, 24 0 C and 40% RH.
• Figure 17 shows that the EVOH films added powder with 0.1 to 1% resveratro! they have AO capacity between 18.8 and 85.4% (with respect to DPPH turn) 1 and that e! EVOH added with 1% resveratro! they have antioxidant capacity superior to the film added with 1% BHT.
• Figure 18 shows that e! LDPE film added with 1% t-resveratro! The liquid route has 88% antioxidant capacity (with respect to the DPPH turn), clearly superior to the unadditioned LDPE film.
• Example 1 Synthesis and intercalation of metallic silver nanoparticles in montmorillonite-type clays modified with 33% by mass of hexadecyltrimethylammonium bromide, using ethanol as a reducing agent. Initially, the clay already modified was dispersed with 33% hexadecyltrimethylammonium bromide in ethanol, at ambient conditions, at a rate of 1g of clay per 100 g of solvent, and 0.05 g of AgN03 was added to the dispersion. The dispersion was refluxed at 7O 0 C for 6 hours; subsequently, the dispersion was allowed to decant, the excess solvent was removed and the clay was dried in a convection oven for 1 h at 7O 0 C. The clay obtained was characterized using X-ray diffraction (see Figure 1) and electron microscopy of transmission (see Figure 2). The diffractograms of Ia
• Figure 1 demonstrate that the modifying agents (silver particles and hexadecyltrimethylammonium bromide) have been intercalated between the sheets, according to the displacement of the basal peak at lower angles (from 6.38 to 5.26). From the TEM images it was determined that in this case the silver nanoparticles reached between 3 and 23 nm, the average size being 16 nm; and that said nanoparticles are presumably located in the interlaminar spaces of the clay, on the surface and edges. In another study, the antimicrobial capacity of this clay with 5% silver nitrate compared to Salmonella spp. A pathogenic microorganism of food origin was used, such as Salmonella spp.
• CECT 554 which was obtained from the Spanish Type Culture Collection (Valencia, Spain).
• the conditions of the study were fixed in the use of the bacterium in the middle exponential phase and with an initial concentration of the microorganism of approximately 10 5 CFU / mL.
• the experimental part was carried out using an adaptation of the macrodilution method established for the determination of the bactericidal activity of antimicrobial agents approved in 1999 by the National Committee for Clinical Laboratory Standards. According to this method, 100 mg of the clay was introduced, which had a final concentration of 5% silver and 33% of hexadecyltrimethylammonium bromide in a sterile tube containing 10 mL of Mueller Hinton Broth (MHB) broth.
• MLB Mueller Hinton Broth
• the tube was inoculated with 0.1 mL of a Salmonella spp. under the conditions described above.
• two tubes containing sample without silver were inoculated (one with clay of the same type without any modification and another with clay of the same type modified with 33% hexadecyltrimethylammonium bromide), and another tube without sample that would serve as a control.
• all the tubes were incubated at 37 0 C for 24 hours.
• 0.1 mL of each sample were seeded in Triptona Soy Agar plates (TSA). After 24 hours of incubation at 37 0 C, were counted viable cells in the plate.
• TSA Triptona Soy Agar plates
• the clay pretreated with dimethylsulfoxide is dispersed in water, at a rate of 1g of clay per 100 g of solvent, and subsequently 0.05g of AgNO 3 and 0.33 g of hexadecyltrimethylammonium bromide were added.
• the dispersion was maintained under vigorous and constant magnetic stirring under a source of UV radiation of 30 W and 235 nm wavelength.
• the time of exposure to UV radiation was 24 hours, then the solid was filtered by suction and dried in a convection oven at 70 0 C for 1 h.
• the clay obtained was characterized using X-ray diffraction (see Figure 3) and transmission electron microscopy (see Figure 4).
• the clay was dispersed in ethanol, at ambient conditions, at a rate of 1g of clay per 100 g of solvent, and 0.1g of AgNO 3 was added to
• the dispersion This was refluxed at 7O 0 C for 6 hours; subsequently the dispersion was allowed to decant, the excess solvent was removed and the clay was dried in a convection oven for 1 h at 7O 0 C.
• the clay obtained was characterized using X-ray diffraction (see Figure 5). The diffractograms of Figure 5 indicate that there is no displacement of the signal from the basal peak (6.38; 2 ⁇ ) after the incorporation of silver nanoparticles to the clay.
• the clay pretreated with dimethylsulfoxide is dispersed in water at ambient conditions, at a rate of 1g of clay per 100 g of solvent, and subsequently 0.05g of AgNO 3 was added.
• the dispersion was kept under vigorous and constant magnetic stirring. under a source of UV radiation of 30 W and 235 nm wavelength.
• the time of exposure to UV radiation was 24 hours, after which purpose the solid was filtered by suction and dried in a convection oven at 70 0 C for 1 h.
• the TEM image of Figure 6 shows an average size of reduced silver particles of 15 nm, and that these are found on the surfaces and edges of the clay sheets.
• a film of silver polylactic acid / nano-clay nanocomposite was obtained by evaporation of the solvent at ambient conditions, a process called "casting.” These nanocomposites were characterized by studying their morphology by transmission electron microscopy (TEM, see Figure 7), as well as their water vapor and antimicrobial barrier properties. Additionally, the water permeability (see Figure 8) of this film of polylactic acid and 10% by weight of clay with antimicrobial properties was studied, using ASTM E96, A 25 0 C and 75% relative humidity. The addition of antimicrobial clay to the polymer matrix causes a permeability reduction of 26.8%, so that the composite material presents a better water barrier than pure polylactic acid.
• the films were weighed, both from the control without clay and from the sample with antimicrobial clay, and introduced into 1OmL of sterile culture medium. They were stored at 4 0 C for four weeks, prior to inoculation with Salmonella spp. Considering that the films contained 10% clay, and in turn that clay contained 5% silver nitrate, the final concentration of silver nitrate that has been used is 300 ppm, the minimum concentration being bactericidal (in this case, reduce the population to zero) of Salmonella around 100 ppm. The films contain an amount of silver 3 times higher than the bactericidal dose when used in suspension. After four weeks of storage and continuous release, the controls show an increase in the number of viable three orders of magnitude, while in the sample of PLA film with 10% clay interspersed with silver the viable three orders of reduction are reduced. magnitude (see Table 6).
• chitosan films were weighed and stored at 4 0 C for 12 hours before inoculation with Salmonella spp.
• the weights used were: 25, 50 and 75 mg of film, which were placed in 10 mL tubes with sterile culture medium.
• Chitosan films contained 10% clay, which in turn contained 5% silver, so the final concentrations of silver nitrate used are as follows: 25 mg of chitosan film contained 0.125 mg of silver nitrate ; 50 mg of film contained 0.25 mg of silver; and 75 mg of film contained 0.375 mg of silver.
• EVOH film samples with 10% clay interspersed with silver nitrate reduced 100 times the number of viable at the time of inoculation and then, 100 times more after 72 hours of incubation.
• the samples of PVOH films with 10% silver clay showed a reduction of four orders of magnitude of the number of viable at the moment of the inoculation of the sample and total inhibition after 72 hours of incubation.
• two bottles were prepared as controls: one that contained only the fatty acid, and another that in addition to the fatty acid contained a vial with unmodified clay.
• the three bottles were stored for 48 hours in a room heated to 24 0 C, 75% RH, and under direct artificial light. After this time the bottles were opened, and in each one 10 mL of 10% w / w solution of trichloroacetic acid and 7 mL of 20 mM solution of 2-thiobarbituric acid were added. The bottles were shaken and incubated for 30 min at 97 0 C. Subsequently the samples were centrifuged, aliquots of the aqueous phase were taken and diluted 10 times.
• the bottle was then sealed tightly with a plastic cap.
• two bottles were prepared as controls: one that contained only the fatty acid, and another that in addition to the fatty acid contained a vial with unmodified clay.
• the three bottles were stored for 48 hours in a room heated to 24 0 C, 75% RH, and under direct artificial light. After this time the bottles were opened, and in each one 10 ml_ of 10% w / w solution of trichloroacetic acid and 7 ml_ of 20 mM solution of 2-thiobarbituric acid were added. The bottles were shaken and incubated for 30 min at 97 0 C.
• Example 10 Simultaneous modification of montmorillonite type clay with 20% w / w of hexadecyltrimethylammonium bromide and 5% w / w of euqenol. Initially 4 g of hexadecyltrimethylammonium bromide was dissolved in a solution 20% v / v ethanol at 40 0 C, using magnetic stirring. Then 1 g of eugenol and 20 g of clay were added. A homogenizer was used at high revolutions for 10 min to favor the dispersion of the clay in the solution. It was connected to reflux and maintained under vigorous stirring at 40 0 C for 24 h.
• the resulting clay was filtered by suction and dried in convection oven at 60 0 C for 6 h.
• the dried modified clay was characterized by X-ray diffraction (see Figure 12).
• the displacement of the basal peak from 7.07 to 5.66 (2 ⁇ ) indicates an increase in the interlaminar spacing of the order of 0.31 nm, calculated from Bragg's law. This change in spacing is evidence of the entry of modifying agents in the clay galleries.
• the EVOH-antioxidant compound was precipitated by slowly dropping the hot solution in a stream of fresh water. Excess water precipitated compound was removed, cut into small pieces and dried in Ia convection oven at 60 0 C for 14 hours. This procedure allowed to prepare EVOH compounds with 1%, 5% and 10% trans-resveratrol, using the proportions indicated in Table 9. Subsequently, the film was prepared using a press. The samples were transformed into plates of approx. 100 microns thick by compression molding in a hydraulic press, at 22O 0 C and 2MPa pressure for 4 minutes. The plates of the samples are cooled slowly inside the press by water flow.
• the antioxidant effect was determined by contact of the EVOH films obtained, using the method of discoloration of the DPPH radical (2,2-diphenyl-1-pyrilhydracil). For this they were weighed, in duplicate. 3Gmg portions of each film and placed in 1.5 mL plastic tubes.
• EVOH-32 compounds were prepared using the melt mixing method for the direct additivation of the polymer with antioxidant.
• the three zones of the plastgraph were preheated to 220 0 C, and maintaining a shear of 5 rpm, a total of 16 g material was introduced into the mixing chamber by alternating polymer and antioxidant. Subsequently, the shear was increased to 100 rpms and mixed for 3 min. After this time, the hot material was recovered. Subsequently, once the material had cooled, the films were prepared using a press. The samples were transformed into plates of approx.
• the EVOH-trans-resveratrol compound was precipitated by slowly dropping the hot solution in a stream of fresh water. Excess water precipitated compound was removed, cut into small pieces and allowed to dry in five Ia convection oven at 60 0 C for 14 hours.
• the equivalent of 1% w / w trans-resveratrol was dissolved with respect to the total dry mass (polymer + transverave resveratrol) in a hot dispersion of kaolinite in 50% v / v isopropanol.
• the dispersion with hot antioxidant was added to the EVOH solution, and the magnetic stirring and heating under reflux were maintained for 1 hour. The precipitation is executed in a manner similar to that already indicated.
• the films of the 15 EVOH nanocomposites were prepared using a press. The samples were transformed into plates of approx. 100 microns thick by compression molding in a hydraulic press, at 22O 0 C and 2MPa pressure for 4 minutes. The plates of the samples are cooled slowly inside the press by water flow. Subsequently the antioxidant effect was determined
• EVOH-32 (with 32 molar ethylene) was used as the base polymer, and the polymer additive method consisted in adding the antioxidant -resveratrol 97% - powder, previously dried, to the molten polymer.
• the processing conditions are indicated in Table 11.
• BHT butylhydroxytoluene
• LDPE low density polyethylene
• resveratrol 97% were used.
• the polymer additivation method consisted of adding a supersaturated solution of t-resveratrol in isopropanol to the mass of molten polymer Extrusion conditions are presented in Table 13. This procedure allowed to prepare LDPE compounds with 1% of t-resveratrol. Subsequently, the films were prepared using the hot plate press. The samples were transformed into plates of approx. 100 microns thick by compression molding in the press at 200 ° C and 2 MPa of pressure for 4 minutes.
• the sample plates were slowly cooled by means of a water flow to room temperature. Subsequently, the antioxidant effect was determined by contact of the LDPE films obtained, using the method of discoloration of the DPPH radical (2,2-diphenyl-1-pyrilhydracil). To do this, 30mg portions of each film were weighed in triplicate and placed in 1.5 mL plastic tubes. 1 mL of a 0.05g / L stock solution of DPPH in methane was added in each tube. The absorbance at 517 nm of this stock solution is 1, 2. approximately. In parallel, three control samples without film containing 1 mL of DPPH were prepared. The samples and controls were left to incubate in dark at to 24 0 C for 24h.
• DPPH radical 2,2-diphenyl-1-pyrilhydracil
• Figure 18 shows that the LDPE film added with 1% liquid t-resveratrol has an 88% antioxidant capacity (relative to DPPH turn). clearly superior to the LDPE film without guessing.
• Example 17 Manufacture of LDPE compounds with a load of 5% modified montmorillonite with 40% hexadecyltrimethylammonium bromide and 5% ammonium-iron sulfate!), By extrusion via powder additive. Initially, ammonium iron (II) sulfate was dissolved in ethanol, under nitrogen bubbling. Subsequently, the modified clay was dispersed with 40% hexadecyltrimethylammonium bromide in the iron (II) solution using magnetic stirring, maintaining nitrogen bubbling. The proportion of iron (II) salt used was 5% by weight with respect to the mass of unmodified clay, at a rate of 20 g of clay per 100 ml of solvent.
• ammonium iron (II) sulfate was dissolved in ethanol, under nitrogen bubbling.
• the modified clay was dispersed with 40% hexadecyltrimethylammonium bromide in the iron (II) solution using magnetic stirring, maintaining nitrogen bubbl
• the clay dispersion in metallic solution was refluxed at 7O 0 C for 6 hours under an inert atmosphere. Subsequently, the dispersion was allowed to decant, the excess solvent was removed and the clay was dried in a vacuum oven for 1 h at 7 ° C. The clay was stored under vacuum in the dark.
• LDPE low density polyethylene
• C16 hexadecyltrimethylammonium bromide
• ll ammonium sulfate - iron
• the films were prepared using a press.
• the samples were transformed into plates of approx. 100 microns thickness by compression molding in a hydraulic press at 200 0 C and 2 MPa pressure for 4 minutes.
• the plates of the samples are cooled slowly inside the press by water flow.
• the oxygen sequestering effect of the LDPE films was determined.
• pieces of 4cmx2cm films were introduced in 20 ml vials containing air at atmospheric conditions and containing a vial with water that generates an activity of one in the head space.
• Films of LDPE + 5% clay modified with C16 and ammonium-iron sulfate (ll) and un-additive LDPE films were tested in triplicate. Three controls without film were also added.
• the oxygen content is determined using an oximeter. Initially the oxygen content within the vials is 20.9% (Table 16). After two days, the percentage of oxygen remains at the same initial value in the control and in vials containing unadditioned LDPE film. Vials containing salt-modified clay and iron nanoparticles have reduced their oxygen content to 20.1% (3.8% reduction in oxygen content). The results indicate that the clay containing iron nanoparticles is active once incorporated into a polyolefin matrix due to the effect of moisture.

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