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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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  • 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
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  • 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
  • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
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  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/201—Pre-melted polymers
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  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
  • C08J3/2056—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase the polymer being pre-melted
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
  • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
  • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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  • 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
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  • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
  • C08K7/24—Expanded, porous or hollow particles inorganic
  • C08K7/26—Silicon- containing compounds
• • 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
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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  • 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
  • C01P2004/03—Particle morphology depicted by an image obtained by SEM
• • C—CHEMISTRY; METALLURGY
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  • C08J2300/00—Characterised by the use of unspecified polymers
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/06—Polyethene
• • 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
  • C08K2201/008—Additives improving gas barrier properties
• • 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 based on a polymeric or plastic matrix and a laminar silicate (clay).
• the elaborated nanocomposites have better mechanical properties (for example stiffness, resistance to breakage), better thermal properties (for example, greater thermal stability) and better barrier properties to gases and vapors (for example to oxygen, water vapor, aromas) and do not need matrix-clay compatibilizing agents. They also present by default barrier to electromagnetic radiation in UV, Vis and IR and fire resistance, maintaining high levels of transparency and make use of substances allowed for food, pharmaceutical and biomedical contact.
• the application of these nanocomposites is multi-sectorial as for example for their advantageous application both in the packaging of products of interest for food and for applications in other sectors.
• the present invention refers to several procedures for the elaboration of these same nanocomposite materials.
• the nanocomposite materials once prepared can be transformed into the final product by any process of transformation of plastics, such as and without limiting sense blow molding, injection, extrusion or thermoforming.
• polymer / clay nanocomposites based on polyamide 6 are commercialized for applications related to the automotive industry or high barrier packaging.
• Polyamide 6 is a semi-crystalline thermoplastic that has good mechanical strength, toughness and high impact resistance; It has good sliding behavior, improving it with the addition of MoS2, it also has good wear resistance; Therefore, it is suitable as an engineering plastic for universal use, in mechanical construction and industrial maintenance work.
• the nanocomposites based on polyolefins are receiving special attention in the world of research due to the wide range of uses of this type of polymers, as well as the good properties of these materials, mainly their low cost, good processability and recycling capacity.
• the conventional compounds (microcomposites) of several polyolefins are already used in the industry, but the incorporation of a low content of dispersed charges in the polymer with at least one dimension in the order of nanometers, allows to achieve an improvement in the final properties of the material (nanocomposite) that is not possible to obtain with conventional loads. Thus, properties such as mechanical, thermal or gas barrier can be improved.
• these clays have been modified with surfactants (such as ammonium salts) to make them more similar to polymeric matrices. Furthermore, with this modification it is possible to increase the interlaminar (basal) spacing of the clay. Therefore, the size of the surfactant chains is of great influence to obtain a greater or lesser basal spacing when performing the clay modification. But in polyolefin matrices this is not enough to achieve a good exfoliation of the clay sheets by melt mixing.
• surfactants such as ammonium salts
• polyolefins such as polypropylene and polyethylene
• their non-polar nature means that there is no affinity between the polymer chains (hydrophobic) and clay (hydrophilic).
• many methods have been proposed in recent years. One of them is to functionalize the polymer matrix with functional polar groups through the use of a catalyst. Another possibility would be the incorporation of a percentage of compatibilizer (polyolefin already functionalized) to the polymer and clay system (for example Morawiec et al. Eur. PoI. J. 2005, 41, 1115).
• nanometric charges have been treated with aminosilanes before being mixed with a polyolefin matrix malleable or carboxylated, with the aim of favoring the interactions between the functionalized surface of the clay and the carboxyl or malleable groups.
• the mixing of the load and of the matrix of polyelefine was carried out by dissolving both components in xylene at 12O 0 C.
• the present invention describes nanocomposite materials with polymeric or plastic matrix and a laminar silicate (clay).
• the elaborated nanocomposites have greater mechanical properties (eg stiffness, resistance to breakage), better thermal properties (eg greater thermal stability) and better gas and vapor barrier properties (eg to oxygen).
• these nanocomposites also present a barrier to electromagnetic radiation, give fire resistance and minimally impact transparency.
• they are composed of materials allowed by the legislation for food, pharmaceutical and biomedical contact and do not need matrix-clay compatibilizing agents.
• a first essential aspect of the present invention refers to new nanocomposite materials comprising at least the following elements:
• a laminar silicate b) A polymeric or plastic matrix.
• the laminar silicate is a clay selected from the group formed by the dioctahedral or trioctahedral family, of a kaolinitic, gibsitic, dickitite, nacritic, halloysitic, montmorillonite, micelcea, vermiculitic or sepiolytic nature, and more preferably of kaolinitic nature.
• the layered silicate is a clay of the family of the type 1: 1 that is composed of a tetrahedral layer of silicate (with virtually no degree of substitution of silicon by other cations) bonded to a dioctahedral layer of the gibsite type.
• the chemical formula of this material is typically Al2S ⁇ 2 ⁇ 5 (OH) 4.
• the percentage of laminar silicate in the nanocomposite in the polymer clay ratio is from 0.05% to 98% by weight, the percentage being dependent on the desired final properties of the nanocomposite material.
• the clay percentage is between 0.01% and 98% and more preferably from 0.05 to 40%.
• the polymer matrix it can be selected of any type, thermoplastics, thermosets and elastomers such as polyolefins, Polyesters, polyamides, polyimides, polyketones, polyisocyanates, polysulfones, styrenic plastics, phenolic resins, amidic resins, ureic resins, melamine resins, polyester resins, epoxy resins, polycarbonates, polyvinylpyrrolidones, epoxy resins, polyacrylates, polychoscrylates, rubbers, polycrylates silicones, aramides, polybutadiene, polyisoprenes, polyacrylonitriles, PVDF, PVA, PVOH, EVOH, PVC, PVDC or biomass derivatives and biodegradable materials such as proteins, polysaccharides, lipids and biopolyesters or mixtures of all these and may contain all types of additives typically added to plastics to improve its manufacturing and / or processing or its properties.
• thermoplastics such as polyole
• polyolefins preferably of the type of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high density polyethylene, metallocene polyethylene and particularly those of ultra low density, polypropylene (PP), copolymers of ethylene, polyethylenes functionalized with polar groups and ionomers of ethylene or any combination thereof.
• polyolefins of the type of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and all families of polypropylenes (PP) and their copolymers are selected.
• the matrix can additionally incorporate agents or substances, including any nanoadditive or concentrate of nanoadditives thereof described in this document or of other nano-clays, with barrier properties to electromagnetic radiation, fire resistance or active substances and / or bioactive.
• the percentage of polymer matrix versus the amount of the clay nanoadditive is between 2 and 99.9%, preferably from 60% to 99.9%.
• These new nanocomposite materials are characterized in that they significantly improve in properties such as stiffness and mechanical resistance, resistance to rupture or thermal stability of the base polymer, as well as improvements in gas and vapor barrier properties, in the electromagnetic radiation barrier and in fire resistance. All these improvements are due to the morphology obtained that is formed by a combination of structures (intercalation, exfoliation and aggregation) where the dispersed particles are of the order of the few nanometers.
• a second essential aspect of the present invention refers to three different procedures for obtaining the same nanocomposite material, with the same properties and characteristics described above. These procedures are:
• a) Dissolve a polymer matrix in an organic solvent or mixture typically used, preferably based on xylene and benzonitrile. b) Maintaining a temperature range between 40 to 350 0 C with stirring to completely dissolve the matrix polymer.
• 3) Mixed in melt that without limitation includes the steps of: a) Melt the polymeric matrix and any additive of help for the hot processing of the plastic and / or to confer certain properties, at a temperature above its melting point in a mechanical mixer (range 40-350 0 C), preferably Banbury type or in an extruder. Heating the polymer matrix to the melting or softening point in a mechanical mixer or in a mixer, preferably of the internal mixer type or any batch or extruder system.
• a layered silicate in the form of dry or wet powder without surface modification and more preferably in a solvent suspension (it acts as a suspension medium for the laminar silicate and its function is to keep the clay exfoliated at the time of introducing it into Ia plastic matrix) of the group formed by water, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, glycols, ethers, glycol ethers, esters, ketones, nitriles, alcohols or any mixture thereof.
• a solvent suspension acts as a suspension medium for the laminar silicate and its function is to keep the clay exfoliated at the time of introducing it into Ia plastic matrix
• Water or low molecular weight alcohols are preferably selected because they are not harmful to health or the environment, and are more compatible with natural clays, and are also readily available and do not cause damage during the process and do not damage The properties of pure material.
• the dispersion can be done with the assistance of mechanical agitation or homogenization (ultraturrax, ultrasound, etc.) and temperature control.
• the percentage of solvent used in relation to that of clay is between 1% and 99.99% by weight, preferably between 5 and 80% and more preferably between 10% and 60% by weight.
• the ratio of the clay-solvent system / s to the amount of polymer is between 0.01% to 98% and more preferably between 1% and 70%.
• the clay concentrate can be processed, for example to obtain pellets, by any method of manufacturing plastics together with additives typically used to formulate or process plastics or alternatively it can be added to the same or another plastic matrix by any method of processing plastics and adding any additive typically added in the formulation or processing of plastics.
• any other additive including any nanoadditive or concentrate of nanoadditives thereof described above or of other nano-clays, typically used as a barrier to electromagnetic radiation and / or fire resistance and / or active and / or bioactive.
• a last fundamental aspect of the present invention refers to the use of the new nanocomposite materials in different sectors or for different applications due to their improved properties, as described above and without limiting sense, such as: Packaging and packaging materials either with improved mechanical, thermal and / or barrier properties or to reduce the thickness of these, eg to reduce the consumption of plastic per container, given the best properties presented by them, - In automotive parts or in biomedical applications
• Figure 1 is an SEM image (Scanning electron microscopy) of a nanocomposite sample of LDPE (Low Density Polyethylene: Low Density Polyethylene) with an approximate 7% by weight of unmodified natural kaolinite clay incorporated into the polyethylene melt system in an ethanol solution.
• LDPE Low Density Polyethylene: Low Density Polyethylene
• Figure 2 is an image of SEM (Scanning electron microscopy) of a nanocomposite sample of LDPE (Low Density Polyethylene: Low Density Polyethylene) with approximately 7% by weight, of unmodified natural montmorillonite clay , incorporated into the polyethylene melt system in an ethanol solution.
• LDPE Low Density Polyethylene: Low Density Polyethylene
• Figure 3 is an image of SEM (Scanning electron microscopy) of a nanocomposite sample of LDPE (Low Density Polyethylene: Low Density Polyethylene) with an approximate 7% by weight of montmorillonite clay modified with salts of ammonium (Cloisite ® 20A) and added to the melt polymer in powder form.
• LDPE Low Density Polyethylene: Low Density Polyethylene
• montmorillonite clay modified with salts of ammonium
• nanocomposites formed by a low density polyethylene that incorporate a kaolinitic clay (which until now has not been previously used by other authors in polyolefin nanocomposites) was carried out. Said clay is added to the system in molten dispersed in a polar solvent, typically water or alcohols.
• a polar solvent typically water or alcohols.
• the results obtained were compared with nanocomposites prepared from the incorporation of a clay of modified montmorillonite nature with ammonium salts and also with those prepared with natural montmorillonite clay (without surface modification treatment). This comparison is important because the clay that is mostly used in polyethylene nanocomposites (and also polypropylene) is montmorillonitic.
• a morphological analysis was performed by scanning electron microscopy (SEM) and the differences in the type of dispersion of the clay and the final aggregate size were observed.
• SEM scanning electron microscopy
• Montmorillonitic clay modified with commercial salts (Cloisite ® 20A) is dispersed, in part, in small aggregates of great aspect ratio and size of the nanometers, but part of the clay is added forming large tactids of several microns.
• object of this invention by adding the untreated kaolinitic clay, object of this invention, a nanocomposite is obtained in suspension where all the particles are homogeneously dispersed in the order of the nanometers in the form of small tactides (formed by a small number of lamellae). Due to these differences in morphologies, positive differences in the nanocomposites prepared by the addition of liquid kaolinite to the plastic are observed.

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