Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
  • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
  • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/16—Clays or other mineral silicates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
  • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
  • C01B33/40—Clays
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/02—Ingredients treated with inorganic substances
• • 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
  • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
• • 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
  • C01P2004/60—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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives

Definitions

• the present invention relates to nanocomposite materials comprising nano-clays as a support for particles of metal oxides that give the materials multifunctional properties.
• Said properties are obtained through the formulation of a specific type of additives based on sheets of natural and / or synthetic clays that are intercalated with metal oxides with antimicrobial and / or oxygen and / or catalytic and / or self-cleaning sequestrant capacity and / or anti-abrasive; and that they may optionally contain other organic, metallic, inorganic compounds or combination thereof that can play a role of compatibilization and / or dispersion and / or increase the functionality of metal oxides and / or provide new functionalities both Passive physical reinforcement as active such as biocide, antioxidant and chemical species absorbers.
• the formulation of nanocomposite materials based on the incorporation of said 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 in-situ polymerization, for application advantageous in antimicrobial, antioxidant, self-cleaning and oxygen sequestering plastic objects, in surgical equipment, coatings, packaging as well as for applications in other sectors.
• these additives are incorporated during the powder preparation processes typically employed 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 4739007; and more specifically with regard to 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 intercalated with different organic modifiers, and once incorporated into thermoplastic matrices and / or thermostable, they are able to improve the barrier properties of gases and vapors.
• 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.
• US4739007 describes the preparation of Nylon-6-clay nanocomposites from montmorillonites treated with alkylammonium salts by the melt mixing method.
• Metal oxides and hydroxides have been used since ancient times for the preparation of pigments and for the extraction of metallic elements. At present, they are also used in other more specific uses, derived from their physical properties and chemical behavior.
• Titanium dioxide in its crystallized anatase form is known to have photocatalytic properties that contribute to accelerating the degradation reactions of organic matter by the effect of ultraviolet light. This compound is used in anti-stain applications in coatings in the textile industry and also in the glazed materials industry.
• Zinc oxide is known for its antimicrobial properties and is used in the manufacture of antiseptic ointments and cosmetic products. It also has excellent properties in the ultraviolet, so it is used as a protective pigment against ultraviolet light.
• the crystalline aluminum and zirconium oxides are known for their high hardness, being used in the ceramic industry as refractory elements and in applications of polishing and abrasion materials.
• Bismuth oxides are used as disinfectants, in the vulcanizing of rubber, in catalysis processes and also as anti-flame and anti-smoke additives in polymeric materials.
• Iron oxides are used as pigments and, because they have a high surface adsorption capacity, they are used in water purification and gas absorption procedures.
• metal oxide particles whether or not supported on substrates such as clays. These methods include sol-gel hydrolysis and condensation processes of the metal oxide from the alkoxide or inorganic salts of the metal in aqueous solution, alcohols or organic solvents. Precipitation of metal oxide or hydroxide is achieved by hydrothermal processes, microwave heating, addition of bases or acids or electrodeposition. Sometimes a subsequent heat treatment is necessary to obtain the metal oxide from the hydroxide, or to obtain the metal oxide in the crystalline phase. Optionally, organic stabilizers and surfactants are added to control the size of the particles formed and prevent agglomeration.
• PCT application WO2001AU00821 describes the manufacture of metal oxide nanoparticles in an exfoliated sheet silicate support.
• JP19970160630 describes a material based on particles of metal oxide intercalated in clay after the formation of the former by solgel route.
• 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 packaging or contaminate the food after such treatment due to sutures or leaks from the container. In addition to its potential health hazard, the proliferation of microorganisms can cause alterations in food that in turn lead to changes in their physical, chemical and organoleptic properties. Some of the traditional preservation methods such as heat treatments, irradiation, modified atmosphere packaging or addition of salts, cannot be applied to certain types of foods such as vegetables, fresh fruits and meats or ready-to-eat products. On the other hand, the direct application of antibacterial substances on food has limited effects since they neutralize and diffuse rapidly into the food.
• active packaging is a viable and advantageous way to limit and control bacterial growth in foods, 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.
• antimicrobial nanoadditives described in the present invention once incorporated into the packages, they can control microbial contamination by inactivation of the enzymatic metabolism of microorganisms.
• the effect of Microorganisms are also undesirable in other sectors. In the medical field, it is essential to eliminate the risks of infection in invasive treatments, of open wounds, as well as in routine treatments.
• Antimicrobial systems can act as antifouling or self-cleaning if they are applied in the form of layers on the surface of the boat, making fuel consumption optimal, and cleaning and maintenance operations are 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.
• the metal oxides supported on substrates show totally different catalytic properties than those observed for the mass metal oxides.
• the catalytic behavior of these metal oxides is drastically enhanced when they are supported on substrates with elevated surface areas. Catalysis reactions occur on the surface of metal oxides, whereby a greater available surface area achieved from the decrease in the size of the oxide particles and / or by a homogeneous and effective dispersion in the support increases the catalytic efficiency. of these materials.
• the CN20091025061 patent describes the manufacture of a catalytic system for the treatment of biomass by ultraviolet light, based on metal oxides and S1O2 (clay).
• the CN20061089021 patent describes a catalyst for the cracking of petroleum substances based on metals in their maximum oxidation state supported on alumina or clay.
• US20030382742 discloses a metallocene catalyst based on agglomerated metal oxide and clay.
• JP20000090198 describes the manufacture of a catalyst for the decomposition of harmful substances based on an inorganic material (clay), a porous alumina type material and a laminar catalyst element resulting from incorporating a metal oxide into a sheet material.
• JP19970075108 describes the preparation of a photocatalytic absorber sheet composed of a photoreactive semiconductor, a metal oxide, clay as an absorber and antimicrobial cellulose.
• JP19950205046 describes the process of coating a clay with a metal oxide for high transparency cosmetic applications.
• JP19890146790 describes the production of a ceramic material with magnetic properties based on chromium slag and a clay with metal oxide.
• the present invention relates to new materials nanocomposites comprising nano-clays (lamellar phyllosilicates) that support metal oxides for incorporation in plastic and / or ceramic matrices, with both gas and vapor barrier properties, flame retardation, improved mechanical and thermal retardation with respect to the matrix, with additional capacity to block electromagnetic radiation (UV-Vis) and to allow the fixation and / or controlled release of active and / or bioactive substances, eg antimicrobial and / or antioxidant and / or oxygen sequestrant and / or self-cleaning and / or catalytic and which in turn are sufficiently compatible and thermally stable to allow manufacturing processes and processing of plastics and even ceramic cooking.
• nano-clays lamellar phyllosilicates
• the functional or active properties are generically conferred or reinforced by the incorporation into clays of oxides of zinc, zirconium, cerium, titanium, magnesium, manganese, palladium, aluminum, iron, copper, molybdenum, chromium, vanadium, cobalt or other metals of groups III to XII of the periodic table and which may optionally contain other organic, inorganic or metallic substances, either natural or synthetic, with, for example, biocidal, antioxidant and oxygen sequestrants in the structure of the nano-clays.
• metal oxides such as titanium dioxide in its crystalline anatase form, have photocatalytic properties for the degradation of organic matter and therefore can be used in applications where you want to reduce the impact of stains of some organic substance.
• metal oxides such as zinc oxide have antimicrobial activity, and can be used in applications where microbial growth inhibition is required.
• Some metal oxides such as cerium (IV) oxide have antioxidant properties and therefore can be used in applications where the protection of a product against oxidation by free radicals and / or oxygen is necessary.
• Some metal oxides such as zirconium oxide or alumina have an exceptional hardness and therefore can be used in applications where it is required to provide abrasion resistance.
• nanoadditives based on clays and metal oxides in plastics, is advantageous given the large dispersion achieved by the functionalized and compatible nanoarcillas in the plastic matrices.
• nanoadditives give plastics additional reinforcements in passive properties, that is, in physical properties, and with new additions new on-demand functionalities are achieved with minimal impact on the inherently good properties of the plastic matrix, such as properties Optics and toughness.
• a first aspect of the present invention relates to nano-clays comprising metal oxides interspersed in their structure.
• nano-clays are understood as those laminar structures of micrometer-sized clay that are dispersed to nanometric size (below 100 nm) typically only in the thickness dimension when incorporated into plastic or ceramic matrices.
• the nano-clays of the present invention are selected from the group consisting of laminar silicates and / or double laminar hydroxides. More preferably, the nano-clays are selected from the group consisting of: montmorillonite, kaolinite, bentonite, smectite, hectorite, sepiolite, gibsite, dicktite, nacritite, saponite, haloisite, vermiculite, mica, and / or mixtures thereof. or with other phyllosilicates, mainly, with or without prior organic and / or inorganic surface modification.
• Another aspect of the present invention relates to the metals that form the oxides, which are selected from groups III to XII of the periodic table, in addition and, without limitation, of magnesium, calcium, aluminum and cerium.
• nano-clays that comprise metal oxides interspersed in their structure, which in turn, nano-clays, comprise additives (modifiers) that are incorporated into their structure causing a surface modification:
• the surface modification When the surface modification is applied, it also allows to introduce or accentuate the active activity by incorporating compatibilizers with active properties, increasing the compatibility between the nanowire and a plastic or polymeric matrix or ceramic, to get better exfoliation of clay.
• compatibilizers with active properties, increasing the compatibility between the nanowire and a plastic or polymeric matrix or ceramic, to get better exfoliation of clay.
• the additives that are incorporated into the structure of the nano-clays, causing a surface modification are selected from the group consisting of: a) expander precursors;
• the precursors of the expander type are selected from the group consisting of: dimethyl sulfoxide (DMSO), ethylene polyoxide, metal salts, N-methyl formamide (NMF), alcohols, acetates, hydrazine hydrate, water, anhydrous hydrazine, carboxymethyl starch, acetamide, starch, DMSO + methanol (MeOH), hydroxyethyl starch, hexanoic acid, hydroxypropyl starch, acrylamides, adonitol, glucose, archilamide, salicylic acid, caprolactam, glycolic acid, maleic acid, tannic acid, maleic acid, tannic acid, maleic acid , lactic acid, adipic acid acetic acid, acetaldehyde, sorbitan, butyric acid, tetrafluoroethylene, chlorotrifluoroethylene, vinyl pyrrolidone, hexamethylene,
• DMSO dimethyl s
• the expander type precursors are selected from the group consisting of DMSO, alcohols, acetates, or water or mixture thereof, and metal salts, selected from the group consisting of silver, copper, iron, titanium, cerium, zinc, nickel, calcium, manganese or cobalt. More preferably, the metal salts are selected from the group consisting of: silver nitrate, silver acetate, nickel chloride, cobalt chloride, copper nitrate, copper sulfate, calcium butyrate or manganese butyrate.
• the acetates are selected from the group consisting of: cellulose acetobutyrate, sucrose acetoisobutyrate, manganese acetate, vinyl acetate or potassium acetate.
• the compatibilizing agents are selected from the group consisting of metallic, inorganic, organic or hybrid substances. More preferably, they are selected from the group consisting of:
• the biopolymers may comprise plasticizers, crosslinkers, emulsifiers and / or surfactants and are selected from the group consisting of peptides and proteins, polysaccharides and polypeptides, lipids, nucleic acids and polymers of biodegradable nucleic acids and polyesters and polydroxyalkanoates.
• proteins such as polysaccharides
• polypeptides such as nucleic acid polymers
• proteins can be natural or synthetic, the latter being synthesized by chemical means or by genetic modification of microorganisms or plants.
• the natural or synthetic polysaccharides are selected from the group, and without limitation, formed by cellulose and derivatives, carrageenans and derivatives, alginates, chitin, glycogen, dextran, gum arabic and preferably chitosan or any of its derivatives both natural and synthetic, more preferably chitosan salts and even more preferably chitosan acetate.
• the proteins are selected without limitation from corn proteins (zein), elastin, gluten derivatives, such as gluten or its gliadin and glutenin fractions, gelatin, casein, agar-agar, collagen and soy proteins. and derivatives thereof.
• zein corn proteins
• elastin elastin
• gluten derivatives such as gluten or its gliadin and glutenin fractions
• gelatin casein
• agar-agar collagen and soy proteins. and derivatives thereof.
• the biodegradable polyesters are selected from the group consisting of polylactic acid, polyhydroxyalkanoates, polyglycolic acid, polylactic-glycolic acid, polycaprolactone, adipic acid and derivatives.
• the lipids are selected from the group consisting of: elastin, beeswax, carnauba wax, candelilla wax, shellac and fatty acids and monoglycerides and / or mixtures of all of the above.
• polydroxyalkanoates are made of polydroxybutyrate and their copolymers with valerate.
• the biomedical materials of the present invention are of the hydroxyapatite type.
• Natural or synthetic antioxidants are selected from polyphenols, such as, resveratrol or flavonoids, plant extracts such as, eugenol or rosemary extracts and vitamins, preferably tocopherols and tocotrienols or ascorbic acid / vitamin C.
• the quaternary ammonium salts of the present invention are preferably and without limitation those which are allowed for food contact (that is, they are included in the lists of monomers and other starting substances authorized by the legislation for use in the manufacture of plastic materials and objects) such as hexadecyltrimethylammonium bromide, N-methacryloxyethyl-N, N-dimethyl-N-carboxymethyl ammonium chloride and bis (2-hydroxyethyl) -2-hydroxypropyl-3- (dodecyloxy chloride) ) methylammonium and others such as mono- and di-alkyl ammonium chlorides and more preferably di (hydrogenated tallow) dimethylammonium chloride.
• the metal salts that are added as additives to the nano-clays are metal salts such as those of silver, iron, copper, titanium, zinc, cerium, zirconium, palladium, manganese, magnesium or nickel c)
• the functionalizing substances are catalytic, active or bioactive in order that they are intercalated and fixed or released in a controlled manner giving rise to compounds with active or bioactive capacity.
• Functionalizing substances are selected from the group consisting of:
• antimicrobial peptides of small size preferably bacteriocins
• small size preferably bacteriocins
• genetic modification preferably nisins, enterokines, lacticins and lysozyme
• 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
• bioactive, therapeutic or pharmacological capacity such as drugs that require controlled release, enzymes, bioavailable calcium compounds, marine oils (omega 3 and 6), probiotics (lactic bacteria), prebiotics (non-digestible fiber) and symbiotics.
• organic and inorganic metal salts and / or oxides and / or metal particles preferably of silver, copper, cerium, zinc, magnesium, tin, manganese, palladium, iron, titanium, zirconium, nickel or cobalt
• metal particles preferably of silver, copper, cerium, zinc, magnesium, tin, manganese, palladium, iron, titanium, zirconium, nickel or cobalt
• These elements may be fixed and / or subsequently released to the product in a controlled manner (matrix control) and exercise their role. catalytic, active or bioactive, and / or can be released from the matrix and that the nano-clays control the kinetics (control of the nanoadditive).
• the proportion of metal compounds (in the form of a percentage of the metal element) in the nanowire is less than 99.9%, more preferably less than 70% and is even more preferably less than 50%.
• a second aspect of the present invention relates to nanocomposite materials comprising the nano-clays as defined above and a plastic or polymeric type matrix or a ceramic type matrix.
• plastic or polymeric matrices are selected from the group formed by matrices:
• thermoplastic, thermostable and elastomer matrices are selected from the following list: polyolefins, polyesters, polyamides, polyimides, polyketones, polyisocyanates, polysulfones, styrenic plastics, phenolic resins, amide resins, ureic resins, melamine resins, polyester resins, epoxy resins, polycarbonates, polyvinylpyrrolidones, epoxy resins, polyacrylates, rubbers and rubbers, polyurethanes, silicones, aramides, polybutadiene, polyisoprenes, polyacrylonitriles, PVDF (Polyvinylidene fluorine), PVA (polyvinyl acetate) vinyl alcohol), EVOH (copolymer of ethylene and vinyl alcohol (Ethylene-Vinyl-Alcoh, PVC (polyvinyl chloride) or PVDC (polyvinylidene chloride).
• the plastic matrix is in a proportion by weight with respect to the total nanocomposite material, from 5% to 99.99% both values inclusive. Preferably, both values are included in a proportion of 20% to 99.99%, and even more preferably from 90% to 99.99%.
• ceramic matrices include: i)
• fried food is understood as a mixture of inorganic chemical substances obtained by rapid cooling of a melt, which is a complex combination of materials, converting the chemical substances thus produced into insoluble vitreous compounds that are presented in the form of scales or granules. .
• This type of ceramic matrix with these elements is called enamel type ceramic matrix.
• the ceramic matrix is in a proportion by weight with respect to the total material of 5% to 99.99%. Preferably from 20% to 99.99%, and even more preferably from 65% to 99.99%.
• the nano-clays 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 or polymeric matrices and / or in ceramic matrices to form the new materials.
• the nano-clays are in a proportion from 0.01% to 95% with respect to the total nanocomposite material, preferably from 0.01% to 80% and more preferably from 0.01 up to 40%
• the nano-clays are in a proportion from 0.01 to 95% by weight with respect to the total nanocomposite material, preferably between 0.01% and 80% and more preferably from 0.01 to 35%.
• the nanoarcillas are in a proportion from 0.01% to 50% by weight with respect to the total nanocomposite material, preferably from 0.01% to 20% and more preferably from 0.01 to 15%.
• Another aspect of the present invention relates to the matrices of the nanocomposite material which further comprise additives with barrier properties to electromagnetic radiation and fire resistance and other substances with passive, active or bioactive properties additional to the nano-clays, selected from the group formed by:
• - 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, cinnamon derivatives, allyl isocyanate, linalool or any combination thereof), or antimicrobial peptides of small size (preferably bacteriocins) natural or obtained by genetic modification (preferably nisins, enterokines, lacticins and lysozyme),
• quaternary ammonium salts Preferably and without limitation, those which are allowed for food contact (that is, they are included in the lists of monomers and other starting substances authorized by law to be used in the manufacture of plastic materials and objects) such as hexadecyltrimethylammonium bromide, N-methacryloxyxyethyl-N, N-dimethyl-N-carboxymethylammonium chloride and bis (2- hydroxyethyl) -2-hydroxypropyl-3- (dodecyloxy) methylammonium chloride and others such as mono- and di chlorides -alkyl ammonium and more preferably di (hydrogenated tallow) dimethylammonium chloride ..
• monomers and other starting substances authorized by law to be used in the manufacture of plastic materials and objects such as hexadecyltrimethylammonium bromide, N-methacryloxyxyethyl-N, N-dimethyl-N-carboxymethylammonium
• 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
• 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
• bioactive, therapeutic or pharmacological capacity such as drugs that require controlled release, enzymes, bioavailable calcium compounds, marine oils (omega 3 and 6), probiotics (lactic bacteria), prebiotics (non-digestible fiber) and symbiotics; or
• the metals present as additives are selected from groups III to XII of the periodic table, in addition and, without limitation, of magnesium, Calcium, aluminum and cerium.
• the salts present as additives are selected without limitation from the group consisting of nitrates, sulfates, phosphates, acetates, chlorides, bromides.
• a third aspect of the present invention relates to a polymeric or ceramic article comprising the material described above.
• a fourth aspect of the present invention relates to the use of nano-clays for the manufacture of nanocomposite materials.
• a fifth aspect of the present invention relates to the use of nanocomposite materials comprising nano-clays and polymeric or ceramic matrices for the manufacture of polymeric or ceramic articles.
• a sixth aspect of the present invention relates to the use of polymeric or ceramic articles in the pharmaceutical, food, automotive, electronic, construction and all other sectors in which the properties of the materials presented herein are specified, how containers, plastic coatings, paints, plastic parts and accessories, ceramic surfaces, coatings, enamels, countertops, tiles and porcelain bathroom and kitchen pieces, among others.
• a seventh aspect of the present invention relates to a process for the synthesis of nano-clays comprising intercalated metal oxides comprising the following steps: a) Reduction of the size of natural clays by mechanical action, for example by means of grinding technologies. This process is carried out until obtaining a particle size below 30 microns in the D90. b) Classification in vibrotamiz, centrifuge, filtroprensa or any other dry or wet filtration system up to an interval between 0.1 to 100 microns, preferably a decrease in particle size is achieved below 25 microns and more preferably below 7 in the so-called D90 (no more than 10% of the material is above that value).
• step b) the following optional steps can be carried out: i) elimination of organic matter by decanting techniques, supernatant collection or by chemical reaction with oxidizing substances such as peroxides. ii) finer removal of crystalline oxides and hard particles not subject to modification either by centrifugation and / or gravimetric processes in solution or by turbo-dryers, preferably by a centrifugation process either wet or dry, followed or not by a atomization process with controlled depression or by any other industrial drying process including lyophilization. c) Obtaining fine laminates either in liquid suspension or powder well by subsequent drying by a centrifugation process either wet or dry, followed or not by an atomization process with controlled depression or by any other industrial drying process including lyophilization. d) Addition to the laminar structures in at least one step, of precursors of the expander type (table 1). These expanders are the same as described above.
• NMF N-methyl formamide
• Adipic acid 1 .03 Polyethylene glycol M w 1000 1 .1 1
• Butyric acid 1 .01 Dipropylene glycol 1 .03
• - deflocculating agents such as acrylates and / or phosphates
• a stage iii) of drying the expanders can be carried out, after washing or not with water or alcohols.
• Said drying can be carried out by evaporation in an oven, lyophilization, centrifugation and / or gravimetric processes in solution or turbo-dryers or by atomization.
• Said precursors are selected from the group consisting of metal alkoxides or salts.
• Organic and / or inorganic metals such as silver, copper, iron, cerium, cobalt, tin, manganese, magnesium, palladium, titanium, nickel, zirconium, zinc or other metals, more preferably the metals are cerium, palladium, titanium , tin, magnesium, zinc and zirconium.
• Formulation of oxides by total or partial application of a physical or chemical treatment. In this way, the particles of the oxide or hydroxide are obtained from the metal precursor supported on the nano-clays.
• the formulation is carried out without limitation by sol-gel processes, chemical precipitation or hydrolysis by the addition of acids, bases, oxidizing substances, reduction and subsequent total or partial oxidation, or solvents, hydrothermal precipitation, electrodeposition, annealing at high temperatures (100-1200 ° C), UV radiation, infrared radiation and / or microwave radiation.
• sol-gel processes chemical precipitation or hydrolysis by the addition of acids, bases, oxidizing substances, reduction and subsequent total or partial oxidation, or solvents
• hydrothermal precipitation, electrodeposition annealing at high temperatures (100-1200 ° C), UV radiation, infrared radiation and / or microwave radiation.
• stage iv) of the addition of functionalizing substances having an active or bioactive character or catalyst of the activity of the metal oxides is carried out so that they are well intercalated and they are fixed or they are released in a controlled way giving rise to compounds with active or bioactive or catalytic capacity reinforcing the active effect.
• 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 oils, probiotics, symbiotics or prebiotics (non-digestible fiber), or ammonium salts preferably mono- and di-alkyl ammonium chlorides and more preferably di (hydrogenated tallow) dimethylammonium chloride and hexadecyltri
• the contents to be added are generally less than 80% by volume of the solution, preferably less than 50% and more preferably less than 20%.
• 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.
• metal salts it may or may not be a total or partial reduction of these to their metallic state by, without limitation, chemical methods (use of reducing agents without limiting sense sodium borohydride, ethanol, sulphite and sodium bisulfite, ascorbic acid), by application of heat or by means of UV-Vis radiation.
• metal salts it may or may not be possible to obtain all or part of the metal oxide by the methods mentioned above.
• an optional step v) of intercalation in aqueous base or with polar solvents, of compatibilizing or intercalating agents selected from metallic, inorganic, organic or hybrid substances can be carried out in the laminar structure.
• the compounds to be intercalated are selected without limitation from the group consisting of 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.
• polyesters such as polylactic, polylactic-glycolic acid, polycaprolactone, adipic acid and derivatives and polydroxyalkanoates, preferably polydroxybutyrate and their copolymers with valerates, biomedical materials such as hydroxyapatites and phosphates of organic salts, and natural antioxidants or synthetic (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).
• biodegradable polyesters such as polylactic, polylactic-glycolic acid, polycaprolactone, adipic acid and derivatives and polydroxyalkanoates, preferably polydroxybutyrate and their copolymers with valerates, biomedical materials such as hydroxyapatites and phosphates of organic salts, and natural antioxidants or synthetic (
• Quaternary ammonium salts such as mono- and di-alkyl ammonium chlorides and more preferably di (hydrogenated tallow) dimethylammonium chloride may also be intercalated although salts allowed for food contact (ie collected in the lists of monomers and other starting substances authorized by law to be used in the manufacture of plastic materials and objects) such as and without limitation the hexadecyltrimethylammonium bromide, polyethylene glycol esters with monocarboxylic aliphatic acids (C6-C22) and their sulfates ammonium and sodium, perfluorooctanoic acid and its ammonium salt, copolymers of N-methacryloxyxyethyl-N, N-dimethyl-N-carboxymethyl ammonium chloride, bis (2-hydroxyethyl) -2-hydroxypropyl-3- (dodecyloxy) methylammonium chloride; and chitosan and its derivatives, and salts of metals
• the organic material that is intercalated is the EVOH or any material of the same family with molar contents of ethylene preferably less than 48%, and more preferably less than 29%, they are brought 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.
• deflocculating agents are added to facilitate processing, such as and without limiting sense polyphosphates and / or acrylates.
• An eighth aspect of the present invention relates to a process for the manufacture of the nanocomposite materials described above, which comprises the addition of nano-clays in solid or liquid state comprising oxides intercalated to a plastic or polymer matrix or to a ceramic matrix.
• active nano-clays with the intercalated metal oxides, active organic and inorganic metal salts (preferably of silver, iron, copper, titanium, zinc, manganese, cerium, palladium, magnesium, tin, nickel or cobalt) and / or any other type of active and bioactive substances without limitation of those mentioned above in order to reinforce or complement the catalytic, active or bioactive effect of the nanocomposite.
• active substances may be natural or synthetic antioxidant substances such as those described above.
• 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.
• nanocomposite material is reinforced with nano-clays containing metal salts such as zinc, silver, titanium, cerium, tin, magnesium, manganese, zirconium, palladium, iron, molybdenum, cobalt or other metals with active or passive properties. It can be applied, whether it has been done before or not, a physical or chemical treatment to change the state of oxidation, totally or partially, of the metallic center interspersed in the plastic or ceramic matrix either before, during or after forming.
• metal salts such as zinc, silver, titanium, cerium, tin, magnesium, manganese, zirconium, palladium, iron, molybdenum, cobalt or other metals with active or passive properties
• These treatments include no limitation: high temperature annealing (100-1200 ° C), UV radiation, infrared radiation, microwave radiation and / or chemical treatment with acids, bases, oxidizing agents, reduction followed by total or partial oxidation, reducers or solvents
• high temperature annealing 100-1200 ° C
• UV radiation infrared radiation
• microwave radiation and / or chemical treatment with acids, bases, oxidizing agents, reduction followed by total or partial oxidation, reducers or solvents
• a ninth aspect of the present invention relates to a process for the manufacture of a polymeric article comprising the addition of the nano-clays described above during any one of the steps of processing of a polymeric or plastic matrix or of a ceramic matrix.
• the processing of the polymeric or plastic matrix is carried out by any manufacturing method related to the plastics processing industry such as extrusion, application and curing processes typically used to manufacture and shape thermostable and elastomers, injection, blowing, compression molding, resin transfer molding, calendering, thermal shock, ultrasonic internal mixing, coextrusion, co-injection and any combination thereof.
• any manufacturing method related to the plastics processing industry such as extrusion, application and curing processes typically used to manufacture and shape thermostable and elastomers, injection, blowing, compression molding, resin transfer molding, calendering, thermal shock, ultrasonic internal mixing, coextrusion, co-injection and any combination thereof.
• the polymeric or plastic matrix is selected from the group consisting of the materials and optionally additives described above that improve the properties of electromagnetic radiation and fire resistance and are typically added to plastics to improve their processing or properties. .
• organic and / or inorganic metal salts with active or passive properties can be added together with other catalytic, active or bioactive substances at any stage of the manufacturing or processing of ceramic materials, although Preferably they will be added during the modification of the powders before atomization.
• Polymer matrix additive concentrates can be treated in the following ways:
• c) is processed by any manufacturing process related to the plastics processing industry such as extrusion, injection, blow molding, compression molding, resin transfer molding, calendering, thermal shock, internal mixing, ultrasound, coextrusion, coinjection and mixing of these.
• the compounds with catalytic capacity refers to facilitating or increasing the effect contributed by metal oxides with active properties.
• Fig. 1 corresponds to X-ray diffractograms (WAXS) obtained from a sample of montmorillonite-type clay modified with titanium oxide and silver nitrate (temperature resistant antimicrobial) and subsequent calcination by the method described in Example 1, and a sample of the same type of unmodified clay with titanium oxide and unmodified with silver nitrate.
• Fig. 2 shows that montmorillonite-type clays modified with titanium oxide and silver nitrate show photocatalytic capacity and degrade organic matter, in this case the coffee stain 8 days after being irradiated with UV.
• Fig. 3 shows that the montmorillonitic and kaolinitic clays modified with titanium oxide and silver nitrate show photocatalytic capacity and degrade organic matter, in this case the coffee stain after 8 days of being irradiated with UV.
• Fig. 4 shows the films of PVA and LDPE (low density polyethylene) and their nanocomposites with the montmorillonite clays modified with (1 or 5%) of silver nitrate, and in the first case also with a 20% surfactant .
• PVA and LDPE low density polyethylene
• Fig. 5 The images of the ceramic control coating without clays are observed as a function of the UV irradiation time. As well as the coating with the titanium oxide in the pure anatase phase and the coatings with the clays modified with the titanium oxide and silver depending on the irradiation time.
• Fig. 6 shows the X-ray diffractogram of kaolinite clays prepared according to the procedure described in example 5.
• Fig. 7 shows the X-ray diffractogram of montmorillonite clays prepared according to the procedure described in example 5.
• Fig. 8 the images of the control samples (pure anatase and unmodified montmorillonite clay) are observed as a function of the UV irradiation time, as well as the clay with titanium oxide and cerium nitrate.
• Fig. 9 shows the X-ray diffractogram of montmorillonite clay modified with SnÜ2 and ⁇ 2 prepared according to the procedure described in example 6.
• Fig. 10 the images of the control samples (pure anatase and unmodified clay) are observed as a function of the UV irradiation time. As well as the clay images with SnÜ2 and ⁇ 2.
• Fig. 1 1 X-ray diffractogram of kaolinite clay modified with ZnO prepared according to the procedure described in example 8.
• Fig. 12 corresponds to X-ray diffractograms (WAXS (high-angle X-ray diffraction)) a sample of unmodified montmorillonitic clay and the same clay modified with cerium nitrate, using ammonium hydroxide as an oxidizing agent by the method described in example 9, to obtain cert oxide montmorillonite (Ce0 2 -MMT).
• WAXS high-angle X-ray diffraction
• Fig. 13 is an image obtained by transmission electron microscope (TEM) in which the main morphologies that can be observed in the nanoloads obtained in Example 9 are presented.
• the image corresponds to an aggregate of montmorillonite-type clay sheets modified with cerium nitrate, using ammonium hydroxide as an oxidizing agent, to obtain cerium oxide montmorillonite (Ce0 2 -MMT), by the method described in Example 9.
• Fig. 14 it is an EDAX image (X-ray analysis by electron scattering) in which the appearance and morphology of the montmorillonite clay modified with cerium nitrate is presented, using ammonium hydroxide as an oxidizing agent, to obtain montmorillonite from cerium oxide (Ce0 2 -MMT), by the method described in Example 9.
• EDAX image X-ray analysis by electron scattering
• Fig. 15 corresponds to X-ray diffractograms (WAXS) obtained from a sample of montmorillonitic clay modified with cerium nitrate and reduced with ascorbic acid, to obtain metallic cerium montmorillonite (Ce ° -MMT), by the method described in Example 10, and a Sample of the same type of unmodified clay.
• WAXS X-ray diffractograms
• Fig. 16 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 montmorillonite-type clay sheets modified with cerium nitrate and reduced with ascorbic acid, to obtain metallic cerium montmorillonite (Ce ° -MMT), by the method described in Example 10.
• Fig. 17 it is an EDAX image in which the appearance and morphology of the montmorillonitic clay modified with cerium nitrate is presented, using ascorbic acid as a reducing agent, to obtain metallic cerium montmorillonite (Ce ° -MMT), by means of the method described in Example 10.
• Fig. 18 corresponds to X-ray diffractograms (WAXS) obtained from a sample of montmorillonitic clay type with cerium (IV) ammonium nitrate, subsequently oxidized with ammonium hydroxide and calcined, to obtain cerium oxide montmorillonite ( Ce02-MMT), by the method described in Example 1 1, and a sample of the same type of unmodified clay.
• WAXS X-ray diffractograms
• Fig. 19 corresponds to the X-ray diffractograms (WAXS) of a sample of unmodified montmorillonite clay and the same clay modified with cerium nitrate, using sodium bisulfite as a reducing agent by the method described in example 12, to obtain montmorillonite of metallic cerium (Ce ° -MMT).
• WAXS X-ray diffractograms
• Fig. 20 corresponds to X-ray diffractograms (WAXS) of a sample of unmodified montmorillonitic clay, of the same clay modified with hexadecyltrimethylammonium bromide (CTABCTAB), and of the same modified clay of hexadecyltrimethylammonium bromide (CTABCTAB) and with ammonium nitrate and cerium (IV), using sodium borohydride as a reducer, by method described in Example 13, to obtain organomodified montmorillonite with CTABCTAB and metallic cerium (Ce ° -20% CTABCTAB-MMT).
• WAXS X-ray diffractograms
• Fig. 21 corresponds to the X-ray diffractograms (WAXS) of a sample of unmodified montmorillonite clay and the same clay modified with cerium nitrate, using sodium borohydride as a reducing agent by the method described in Example 14, to obtain montmorillonite of metallic cerium (Ce ° -MMT).
• WAXS X-ray diffractograms
• Fig. 22 corresponds to the X-ray diffractograms (WAXS) of a sample of unmodified montmorillonite clay and the same clay modified with cerium nitrate and iron chloride, using ascorbic acid as a reducing agent by the method described in the Example 15, to obtain montmorillonite of iron (II) and metallic cerium (Ce ° -Fe (ll) -MMT).
• WAXS X-ray diffractograms
• Fig. 23 corresponds to X-ray diffractograms (WAXS) of a sample of unmodified montmorillonite clay and the same clay modified with cerium chloride and zirconium oxynitrate, using high temperature ammonium hydroxide as oxidizing agents, according the method described in Example 16, to obtain montmorillonite cerium oxide and zirconium oxide (Ce0 2 / Zr0 2 -MMT).
• WAXS X-ray diffractograms
• Fig. 24 corresponds to the graph of contact oxidation inhibition (DPPH method) by action of cerium clays, the preparation of which is described in examples 9 to 16.
• Fig. 25 corresponds to the graph of oxygen scavenging capacity in head space of cerium clays, whose preparation is described in examples 9 to 17.
• Fig. 26 corresponds to the graph of contact oxidation inhibition (DPPH method) by action films of HDPE and PET composites with cerium clays, whose preparation is described in examples 17 and 18.
• Fig. 27 corresponds to the plot of oxygen sequestering capacity in headspace of films of HDPE and PET composites with cerium clays, the preparation of which is described in examples 17 and 18.
• Example 1 Synthesis and intercalation of Titanium oxide in modified montmorillonite clays with 5% by mass of silver nitrate and its subsequent calcination at 500 ° C for 1 h obtaining the anatase phase of TiO 2 .
• the clay modified with 5% AgNO3 was dispersed in isopropanol, under ambient conditions, at a rate of 10g of clay per 100 g of solvent, and 70 g of Titanium IV Isopropylate (TPT) were added to the dispersion.
• TPT Titanium IV Isopropylate
• the dispersion was kept under stirring for 5 min; 18g of H 2 O was added, where gelation was observed under ambient conditions; It was subsequently dried at 60 ° C for 24 hours and calcined at 500 ° C for 1 hour.
• the clay obtained was characterized by X-ray diffraction ( Figure 1) and X-ray fluorescence (Table 2).
• Figure 1 The diffractograms of Figure 1 demonstrate that modifying agents (silver particles and titanium oxide) and the heat treatment has caused a disorganization of the clay sheets indicated by the disappearance of the characteristic basal peak of the unmodified clay.
• the Anatase phase of Ti0 2 is observed, obtained after calcination.
• X-ray fluorescence Table 2 a content of 49.46% of the titanium oxide in the clays was observed, as well as a content of 1.40% of silver.
• Table 2 X-ray fluorescence (WAXS) obtained from a sample of montmorillonite-type clay modified with titanium oxide and silver nitrate (temperature resistant antimicrobial) and its subsequent calcination by the method described in Example 1 .
• WAXS X-ray fluorescence
• Example 2 (Reference example) Synthesis and intercalation of titanium oxide in montmorillonite and kaolinite clays calcined at 500 ° C for 1 h to obtain the ta2 anatase phase and subsequently modified with 5% by mass of silver nitrate .
• Montmorillonite and kaolinite clays (treated with dimethylsulfoxide) are suspended in isopropanol with a ratio of 10g of clay in 100 ml of solvent.
• 70 g of titanium IV isopropylate (TPT) is added to the dispersion.
• the dispersion was kept under stirring for 5 min; 18g of H2O was added, where gelation was observed under ambient conditions; It was subsequently dried at 60 ° C for 24 hours and calcined at 500 ° C for 1 hour. Finally, they were modified with 5% silver nitrate, at ambient conditions, at a rate of 1 g of AgNÜ3 per 100 ml of H 2 0 and 20g of calcined clay.
• the dispersion was refluxed for 6 hours at 70 ° C. It was finally filtered by suction and dried at 70 ° C in vacuo.
• the photocatalytic capacity of this clay was determined, containing about 50% of titanium oxide in Anatase phase and 5% of silver nitrate and against UV radiation.
• the degradation of organic matter based on coffee was studied.
• Figure 3 shows the images of the control clay as a function of the UV irradiation time. As well as clay with titanium oxide and silver and depending on the irradiation time. From Figure 3, it can be seen that at 7 days the clay with Anatase phase titanium oxide degrades the coffee stain, just like pure titanium oxide. However, clay without titanium oxide still shows the coffee stain.
• the antimicrobial effectiveness of coatings on enamels was evaluated at a rate of 0.2 g of clay per square meter using the ISO 22196 methodology.
• Example 3 (Reference Example) Development of nanocomposites based on PVA and LDPE and clays modified with titanium and silver and clays modified with titanium and cerium.
• PVA films about ⁇ ⁇ thick were prepared by the casting method, using water as a solvent.
• the proportion of clay by weight is 10% with respect to the polymer.
• the clay was added to the water, dispersed with ultraturrax and the proportional part of PVA was added.
• the solution was kept under stirring at 70 ° C for 2 hours. Subsequently, the Petri dish casting was performed, obtaining the films by evaporation of the solvent (water) at 24 hours.
• LDPE films were prepared by melt mixing in internal mixer and subsequent pressing. The processing conditions were 150 ° C, 100rpm and 5min.
• the clays used for this study were prepared following the procedure of Example 1 and the procedure of Example 5.
• Example 4 (Reference Example) Development of ceramic coatings based on varnishes and clays modified with titanium and silver.
• Varnishes with the modified clays were prepared following the procedure of Example 1 and Example 2.
• the proportion of clay by weight is about 5% with respect to the varnish.
• the clay was added to the varnish, magnetic stirring was applied for 5 minutes. Subsequently, the coatings were made on the ceramic materials.
• Example 5 (Reference example) Synthesis and intercalation of titanium oxide in montmorillonite and kaolinite type clays calcined at 500 ° C for 1 h obtaining the anatase phase of Ti0 2 and subsequently modified with 5% by mass nitrate of cerium (Ce (NÜ3) 2) -
• Montmorillonite clays previously modified with 20% by weight of CTAB
• kaolinites treated with dimethylsulfoxide
• isopropanol with a ratio of 10g of clay in 100 ml of solvent.
• 70 g of Titanium IV Isopropylate (TPT) is added to the dispersion.
• the dispersion was kept under stirring for 5 min; 18g of H 2 0 was added, where gelation was observed under ambient conditions; It was subsequently dried at 60 ° C for 24 hours and calcined at 500 ° C for 1 hour.
• Table 4 shows the result of the chemical analysis by X-ray fluorescence performed on montmorillonite clay prepared according to the procedure described above.
• Figure 6 shows the X-ray diffractogram of kaolinite clays prepared according to the procedure described above.
• Figure 7 shows the X-ray diffractogram of montmorillonite clays prepared according to the procedure described above.
• Figures 6 and 7 show the presence of the diffraction peaks characteristic of the anatase phase.
• the photocatalytic capacity of this clay was determined, containing about 50% of titanium oxide in anatase phase and 5% of cerium nitrate and against UV radiation. The degradation of organic matter based on coffee was studied.
• FIG 8 shows the images of the control samples (pure anatase and unmodified montmorillonite clay) as a function of the UV irradiation time, as well as the clay with titanium oxide and cerium nitrate. From Figure 9, it can be seen that within 2 days the clay with anatase titanium oxide and cerium nitrate degrades the coffee stain, while pure titanium oxide only partially degrades it. Therefore the titanium oxide supported on the Clay and doped with cerium is more efficient than pure anatase.
• Example 6 (Reference example) Synthesis and intercalation of tin dioxide (SnÜ 2 ) in cassiterite phase and titanium oxide (T1O2) in anatase phase in montmorillonite type clays calcined at 300 ° C for 4h.
• Montmorillonite clays are suspended in water with a ratio of 20g of clay in 100 ml of solvent.
• the concentration of SnS0 4 is 150g per liter of HCI solution.
• the clay precipitate and SnÜ 2 is filtered, washed and dried at 120 ° C for 2h.
• TPT Titanium IV Isopropylate
• Table 5 shows the result of the chemical analysis by X-ray fluorescence performed on a clay prepared according to the procedure described above.
• Figure 9 shows the X-ray diffractogram of the clay prepared according to the procedure described above. The peaks corresponding to the anatase phase of ⁇ 2 and the cassiterite phase of SnÜ2 can be distinguished.
• the photocatalytic capacity of this clay was determined containing about 42% of titanium oxide in anatase phase and 16.4% of tin dioxide in cassiterite phase and against UV radiation. The degradation of organic matter based on coffee was studied.
• Example 7 (Reference example) Synthesis and intercalation of zirconium dioxide (ZrÜ2) in kaolinite clays calcined at 600 ° C for 4h.
• Kaolinite clay is suspended in water with a ratio of 20g of clay in 100 ml of solvent.
• a solution of zirconium oxynitrate (ZrO (N0 3 ) 2) is added in water (2.7g of ZrO (NÜ3) 2 in 200ml of water).
• NH3 (28% vol.) Is added until a pH of 10 is reached.
• the mixture is kept in suspension for 1 h. during this time ZrOH precipitates.
• the clay and ZrOH precipitate is filtered, washed and dried at 120 ° C for 2h. Subsequently it is calcined at 600 ° C for 4h to obtain ZrO 2 .
• Table 6 shows the result of the chemical analysis by X-ray fluorescence performed on a clay prepared according to the procedure described above.
• Example 8 (Reference example) Synthesis and intercalation of zinc oxide (ZnO) in kaolinite clays (pretreated with DMSO).
• a solution of zinc nitrate (Zn (NO3) 2) with a ratio of 13.08g of Zn (NO3) 2 in 400ml of water is prepared.
• 25g kaolinite clay (pretreated with DMSO) is suspended in the solution of Zn (NÜ3) 2-
• a solution of NaOH 24g of NaOH in 400ml of water
• the mixture is kept in suspension at 60 ° C for 2h and during this time ZnO precipitates.
• the clay and ZnO precipitate is filtered, washed in methanol and dried at 120 ° C for 2h under vacuum.
• Figure 1 1 shows the X-ray diffractogram of the clay prepared according to the procedure described above.
• Films of LDPE and its nanocomposite with 5% of the clay described above were prepared by melt mixing in internal mixer and subsequent pressing.
• the processing conditions were 150 ° C, 100rpm and 5min.
• Example 9 Synthesis and intercalation of cerium (IV) oxide (ceria, Ce0 2 ) in montmorillonite type clays, using ammonium hydroxide as oxidizing agent. Preparation of Ce0 2 MMT.
• the diffractograms of Figure 12 demonstrate that there is no displacement of the basal peak after modification (12.5 °, 2 ⁇ ), which indicates that there is no intercalation in the clay of the cerium oxide formed.
• the resulting material contains Ce0 2 (cerianite), with its own reflections at 28.64 °, 47.29 ° and 56.40 ° (2 ⁇ ).
• Example 10 synthesis and intercalation of metallic cerium (Ce 0 ) in montmorillonite type clays, using ascorbic acid as a reducing agent. Preparation of Ce ° MMT that evolve totally or partially to cerium oxide by oxygen uptake
• the diffractograms of Figure 15 show baseline peak displacement from 7.03 ° to 5.67 ° (2 ⁇ ), which corresponds to an increase in interlaminar distance as a result of the modification.
• Example 1 1 Synthesis and intercalation of cerium (IV) oxide (ceria, CeÜ 2 ) in montmorillonite clays, using high ammonium hydroxide temperature as oxidizing agents. Preparation of Ce02-MMT.
• the clay obtained was characterized using X-ray diffraction and compared with the unmodified starting clay (see Figure 18).
• the diffractograms of Figure 18 demonstrate that there has been a disorganization in the crystalline structure as a result of the chemical and thermal treatment applied to obtain the cerium oxide (IV) supported in the clay. This disorganization is evidenced by the widening of reflections at low angles.
• the chemical analysis of the Ce0 2 MMT clay obtained by this method indicates that it contains 16% Ce.
• Example 12 Synthesis and intercalation of metallic cerium (Ce 0 ) in montmorillonite type clays, using sodium bisulfite as a reducing agent that evolve totally or partially to cerium oxide by oxygen uptake. Preparation of Ce ° MMT.
• Example 13 Synthesis and intercalation of metallic cerium (Ce 0 ) in organomodified montmorillonite clays with 20% hexadecyltrimethylammonium bromide (CTAB), using sodium borohydride as a reducing agent that totally or partially evolve to cerium oxide by oxygen uptake . Preparation of Ce ° -20% CTAB-MMT.
• the clay was filtered by suction and dried in a vacuum oven for 2 h, at 85 ° C.
• the clay obtained was characterized using X-ray diffraction and compared with the starting clay as well as with the unmodified clay (see Figure 20).
• the diffractograms of Figure 20 show that the modification of natural clay with hexadecyltrimethylammonium bromide (CTAB) leads to an opening of the interlaminar distance (displacement of the basal reflection at lower angles).
• CTAB hexadecyltrimethylammonium bromide
• subsequent modification with cerium nitrate and subsequent reduction with sodium borohydride of the organomodified clay with CTAB causes disorganization in the laminar structure of the clay, which is evident from the low intensity and width of the basal peak.
• Example 14 Synthesis and intercalation of metallic cerium (Ce 0 ) in montmorillonite clays, using sodium borohydride as a reducing agent that evolve totally or partially to cerium oxide by oxygen uptake.
• Ce ° MMT Preparation of Ce ° MMT. Initially, a 0.6M solution of Ce (N03) 3 * 6H 2 0 was prepared, and the unmodified montmorillonite clay was dispersed in this solution, at a rate of 0.06 g per ml of solution. The dispersion was stirred for 24 h at 40 ° C, after which the heat source was turned off and nitrogen began to bubble into the dispersion. Maintaining nitrogen bubbling and constant stirring, a 10% w / w solution of sodium borohydride is slowly added.
• the resulting dispersion was stirred for 2h at room T. Finally, the clay was filtered by suction, washed with acetone and dried in a vacuum oven for 2 h, at 85 ° C.
• the clay obtained was characterized using X-ray diffraction and compared with the unmodified starting clay (see Figure 21). Judging by the diffractograms of Figure 23, the cerium (III) intercalation treatment followed by the reduction with sodium borohydride causes total disorganization of the clay laminar structure.
• Example 15 Synthesis and intercalation of metallic cerium (Ce 0 ) and iron (II) (Fe (ll) in montmorillonite clays, using ascorbic acid as a reducing agent that evolve totally or partially to cerium oxide by oxygen uptake. of Ce ° -Fe (ll) MMT.
• a 0.6M solution of Ce (N03) 3-6H 2 0 and a 0.85M solution of FeCl3-6H 2 0 were prepared.
• the metal solutions were mixed and the montmorillonite clay was dispersed in this mixture at a rate of 0.06 g per ml of solution.
• the dispersion was stirred for 24 h at 40 ° C, after which a 30% w / w solution of ascorbic acid was added.
• the resulting dispersion was stirred for 4h at 70 ° C.
• the clay was filtered by suction, washed with acetone and dried in a vacuum oven for 2 h, at 85 ° C.
• the clay obtained was characterized using X-ray diffraction and compared with the unmodified starting clay (see Figure 22).
• the diffractograms of Figure 22 show displacement of the basal peak of the modified clay, from 7.07 ° to 6.07 ° (2 ⁇ ), which corresponds to an opening of the interlaminar distance of 0.2 A as a result of the intercalation of reaction products.
• the chemical analysis of clay reveals 8.72% of Ce and 2.74% of Fe.
• Example 16 Synthesis and intercalation of cerium (IV) oxide (ceria, CeÜ 2 ) and zirconium oxide (ZrÜ 2 ) in montmorillonite type clays, using ammonium hydroxide as oxidizing agent. Preparation of Ce0 2 / r0 2 -MMT.
• the diffractograms of Figure 23 show the change of physical phase due to the heating at 600 ° C, the temperature above which the clays undergo dehydroxylation.
• the characteristic reflections of the cerium and zirconium mixed oxide appear between 29 and 35 0 (2 ⁇ ).
• the chemical analysis of the resulting clay shows 48.15% of Ce and 7.54% of Zr.
• Example 17 Preparation of high density polyethylene (HDPE) composites with 10% Ce ° MMT clays (reduced with ascorbic acid, sodium borohydride and sodium bisulfite that evolve totally or partially to cerium oxide by oxygen uptake.
• HDPE high density polyethylene
• Example 18 Preparation of polyethylene terephthalate (PET) composites with 15% Ce ° MMT (reduced with ascorbic acid), Ce ° MMT (reduced with sodium bisulfite) and Ce ° -Fe (ll) -MMT (reduced with ascorbic acid ) that evolve totally or partially to cerium oxide by oxygen uptake.
• PET polyethylene terephthalate
• Example 19 Antioxidant capacity of Ce0 2 -MMT (oxidized with ⁇ 4 ⁇ , with and without calcination), Ce ° MMT (reduced with ascorbic acid), Ce ° MMT (reduced with sodium bisulfite), Ce ° MMT (reduced with sodium borohydride), Ce ° - Fe (ll) -MMT (reduced with ascorbic acid) and Ce0 2 / Zr02-MMT.
• the contact antioxidant effect of cerium clays was determined using the DPPH radical discoloration method (2,2-diphenyl-1-picrylhydracil). For this, weighed in 3 ml glass vials, in triplicate, 30mg portions of each clay. 1 mL of a 0.05g / L stock solution of DPPH in methanol was added in each tube, whose absorbance at 517 nm of is 1.2. In parallel, three control samples without clay containing 1 mL of DPPH were prepared. Samples and controls were allowed to incubate in the dark for 24 ° C for 24 hours. Next, the samples were filtered and The absorbance of the supernatant at 517 nm was measured. The results are expressed in% DPPH inhibition:
• % DPPH inhibition (Abs control - Abs sample) / Abs control
• Figure 24 shows that in all cases DPPH inhibition is greater than 50%, being particularly high (greater than 90%) in Ce ° MMT clays (reduced with ascorbic acid) and double iron and cerium clay Ce ° - Fe (ll) MMT.
• Ce ° MMT clays reduced with ascorbic acid
• Ce ° - Fe (ll) MMT double iron and cerium clay
• the Ce0 2 / r0 2 -MMT clay showed lower antioxidant capacity, although not negligible, of the order of 25%.
• the results show that these clays, to a greater or lesser extent, are capable of trapping free radicals, an activity that can extend to free radicals in oxygen. Therefore, these clays have antioxidant capacity.
• Example 20 Oxygen sequestering capacity of Ce ° MMT (reduced with ascorbic acid), Ce ° MMT (reduced with sodium bisulfite), Ce ° MMT (reduced with sodium borohydride), Ce ° -Fe (ll) -MMT ( reduced with ascorbic acid) and bisulfite / MMT.
• Ce ° MMT (ascorbic acid)> Ce ° MMT (sodium bisulfite) »Ce ° -Fe (ll) MMT, Ce 0 (sodium borohydride)
• Example 21 antioxidant capacity of HDPE and PET composites with cerium clays.
• the antioxidant effect by contact of the HDPE and PET composites, described in examples 17 and 18, was determined using the method of discoloration of the DPPH radical (2,2-diphenyl-1-picyrylhydracil). For this, weighed in 3 ml glass vials, in triplicate, 30mg portions of each film. 1 mL of a 0.05g / L stock solution of DPPH in methanol was added in each tube, whose absorbance at 517 nm of is 1.2. In parallel, three control samples without film containing 1 mL of DPPH were prepared. Samples and controls were allowed to incubate in the dark for 24 ° C for 24 hours. Next, the absorbance at 517 nm was measured. The results are expressed in% DPPH inhibition:
• % DPPH inhibition (Abs control - Abs sample) / Abs control
• Figure 26 shows that PET + 15% Ce ° -Fe (ll) MMT and HDPE + 15% Ce ° MMT (ascorbic acid) composites exhibit superior ability to capture free radicals (DPPH inhibition> 75%), comparatively with PET and HDPE composites with Ce ° MMT (reduced with NaBH 4 and sodium bisulfite), which exhibit medium free radical scavenging capacity (inhibition between 25 and 47%).
• Example 22 Oxygen sequestering capacity of the HDPE and PET composites with cerium clays, described in examples 17 and 18. 1.5 g of each film was weighed, in duplicate, in 40 ml vials. Within each vial, a cell with 1 ml of water was placed to ensure 100% relative humidity inside, and each vial was closed with a traffic light cap, with open-closed switch and needle inlet. The caps were left in the "closed" position during the test. The vials were placed in a heated space at 25 ° C, under constant artificial light. The oxygen content was measured between 1 and 60 days, using an oxygen sensor. The sequestering capacity results are shown in Figure 27.
• the graph of volume of oxygen consumed / g clay vs. time indicates that the PET composite with Ce ° MMT (reduced with bisulfite) consumes up to 0.8ml in 60d.
• the HDPE composite with cerium clay a quarter of oxygen, which can be translated into an effect of the polymer matrix.

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