MXPA97007943A

MXPA97007943A - Intercaled and exfoliated formed with monomeros, oligomeros and polimeros without evoh, and evoh composite materials containing the mis

Info

Publication number: MXPA97007943A
Application number: MXPA/A/1997/007943A
Authority: MX
Inventors: W Beall Gary; M Serrano Fernando; J Engman Steven
Original assignee: Amcol International Corporation
Priority date: 1996-12-06
Filing date: 1997-10-15
Publication date: 1998-10-30

Abstract

The nanocomposites are made by combining an EVOH matrix polymer and exfoliated interleaves formed by contacting a phyllosilicate with an interlayer without EVOH to adsorb or intercalate the interlayer between the adjacent phyllosilicate platelets. Sufficient intercalant is adsorbed between the adjacent phyllosilicate plates to expand adjacent platelets to a separation of at least about 5øA, preferably at least about 10øA (as measured after removal of water), up to about 100øA and preferably in the range of about 30-40øA, so that the interlayer can easily be exfoliated, for example, when mixed with the EVOH matrix polymer melt, to provide an EVOH / platelet (nanocomposite) matrix polymer composite that does not degrade to the EV matrix polymer

Description

INTERCALATED AND EXFOLIATED FORMED WITH MONOMERS, OLIGOMETERS AND POLYMERS WITHOUT EVOH; AND EVOH COMPOSITE MATERIALS CONTAINING THEMSELF Field of the Invention The present invention is directed to composites which are mixtures of interlayered, and / or cleaved laminated materials and EVOH matrix polymers. The interleaved laminates are made by sorption (adsorption and / or absorption) of one or more EVOH-free monomers, oligomers or polymers between the planar layers of a foamed stratified material, such as a phyllosilicate or other layered material, to expand the space between layers of adjacent layers to at least about 5 Á. More particularly, the intercalates have at least two layers of monomer, oligomer and / or non-EVOH polymer sorbed on the inner surfaces of adjacent layers of the flat platelets of a layered material, such as a phyllosilicate, preferably a smectite clay, for expanding the space between layers to at least about 5 Angstroms, preferably at least about 10 Angstroms, more preferably to at least about 20 Angstroms, and more preferably to at least about 30-45 Angstroms, up to about 100 Á, or the disappearance of the periodicity. The resulting intercalates are neither completely organophilic nor completely hydrophilic, but a combination of the two, and can easily be exfoliated by or during mixing with a melt of EVOH matrix polymer, without degrading the EVOH polymer. The resultant EVOH matrix polymer / plate composite materials are useful as long as EVOH polymer / filler composites are used, particularly to provide gas barriers, for example, as useful films in the food wrap having an impermeability to the substrate. improved gas; food grade beverage containers; automotive gas tank liners; and any other use wherein it is desired to alter one or more physical properties of an EVOH matrix polymer, such as elasticity, temperature, and gas impermeability characteristics. BACKGROUND OF THE INVENTION AND PREVIOUS TECHNIQUE It is well known that phyllosilicates, such as smectite clays, for example, sodium montmorillonite and calcium montmorillonite, can be treated with organic molecules, such as organic ammonium ions, to intercalate the organic molecules between adjacent flat layers of silicate, thereby substantially increasing the interlayer space between the adjacent silicate layers. The interleaved phyllosilicates, thus treated, can then be exfoliated, for example, the silicate layers are separated, for example, mechanically, by high shear mixing. When the individual silicate layers are mixed with a matrix polymer before, after or during the polymerization of the matrix polymer, for example, a polyamide-see 4,739,007; 4,810,734; and 5,385,776 - it has been found that substantially one or more properties of the polymer are improved, such as mechanical strength and / or high temperature characteristics. Examples of such prior art compounds, also called "nanocomposites", are set forth in the published PCT disclosure of Allied Signal, Inc. WO 93/04118 and in U.S. Patent No. 5,385,776, which discloses the mixture of platelet particles Individuals derived from interleaved layered silicate materials, with a polymer to form a polymer matrix having one or more properties of the matrix polymer, enhanced by the addition of the exfoliated interlayer. As disclosed in WO 93/04118, interleaving is formed (the interlayer space between adjacent silicate platelets is increased) by the adsorption of a silane coupling agent or an oniu cation such as a quaternary ammonium compound, which has a reactive group that is compatible with the matrix polymer. It is well known that such quaternary ammonium cations convert a highly hydrophilic clay, such as calcium or sodium montmorillonite, into an organophilic clay capable of sorbing organic molecules. A publication that exposes the direct intercalation (without solvent) of polystyrene and poly (ethylene oxide) in organically modified silicates is the Synthesis and Properties of Two-Dimensional Nanostructures by Direct Intercalation of Polymer Mel ts in Layered Silicates, (Synthesis and Properties of Bi-Dimensional Nanostructures Through the Direct Intercalation of Polymer Mergers in Stratified Silicatios) Richard A. Vaia, and others, Chem. Mater. , 5: 1694-1696 (1993). As also stated in Adv. Materials, (Materials Adv.) 7, No. 2: (1985), pp, 154-156, New Polymer Electrolyte Nanocomposite: Mel t Intercalation of Poly (Ethylene Oxide) in Mica-Type Silicates, (New Nanocomposites Polymer Electrolyte: Intercalation of Poly (Ethylene Oxide) Fusion in Mica Type Silicates), Richard A. Vaia, and others, poly (ethylene oxide) can be intercalated directly into Na montmorillonite and Li montmorillonite by heating up 80 ° C for 2-6 hours to achieve a space-d of 17.7 Á. The intercalation is accompanied by the displacement of water molecules, placed between the clay platelets with polymer molecules. However, apparently, the intercalated material could not be exfoliated and examined as a pellet. It was quite surprising to one of the authors of these articles that the exfoliated material could be made according to the present invention. Previous unsuccessful attempts have been made to intercalate polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVOH) and poly (ethylene oxide) (PEO) between the montmorillonite clay platelets. As described in the Interlayer Adsorption of Polyvinylpyrrolidone on Montmor illoni, Journal of Colloid and Interface Science, Vol. 50, No. 3, March 1975, pages 442-450 of Levy and others, attempts have been made to sip PVP (40,000 MW average) between monoionic plates of montmorillonite clay (Na, K, Ca and Mg) by successive rinsings with absolute ethanol, and then trying to sorbate the PVP by contact with solutions of PVP / ethanol / water at 1%, with varying amounts of water, through the replacement of solvent ethanol molecules that were swallowed in the rinse (to expand the platelets to about 17.7 Á). Only sodium montmorillonite expanded beyond a basal space of 20 Á (for example, 26 Á and 32 Á), in H + 2 at 5 +%, after contact with the PVP / ethanol / H20 solution. It was concluded that ethanol was necessary to initially increase the basal space for a subsequent sorption of PVP, and that the water did not directly affect the PVP sorption between the clay platelets (Table II, page 445), except for sodium montmorillonite. . The sorption was slow and difficult and had little success. In addition, as described in Adsorption of Polyvinyl Alcohols by Montmor i ll oniTe, Journal of Colloid Sciences, Vol. 18, pages 647-664 (1963) by Greenland, polyvinyl alcohols containing residual 12% acetyl groups, they could increase the basal space by only about 10A due to the polyvinyl sorbed alcohol (PVOH). As the polymer concentration in the solution containing intercalating polymer increased from 0.25% to 4%, the amount of sorbed polymer was substantially reduced, indicating that the sorption could only be effective under polymer concentrations in the polymer-containing composition intercalant, of the order of 1% by weight of polymer, or less. Such a diluted process for the intercalation of an interlayer in layered materials would be exceptionally costly in drying the layered interspersed materials for the separation of the interlayer from the polymer carrier, eg, water, and, therefore, apparently none was carried out. Later work towards commercialization. SUMMARY OF THE INVENTION This U.S. Patent No. 5,552,469, of the assignee incorporated herein by reference, describes the intercalation of silicate materials laminated by contact with a water soluble polymer, or polymerizable monomers that polymerize while intercalating to form soluble polymers. in water, such as polyvinylpyrrolidone or polyvinyl alcohol. U.S. Patent No. 5, 552,469 discloses mixtures of such intercalated and / or cleaved thereof, with various matrix polymers to improve one or more properties of the matrix polymers. One of the useful intercalating polymers, set forth in U.S. Patent No. 5,552,469, is an ethylene / vinyl alcohol copolymer (EVOH). At the time of filing the application leading to U.S. Patent No. 5,552,469, it was envisioned that good composite materials based on EVOH matrix polymers could be made by intercalating a layered silicate material, such as a phyllosilicate, with monomers , oligomers or polymers of EVOH and then the addition of the intercalated and / or exfoliated thereof to an EVOH matrix polymer. Surprisingly, it has been found that stratified silicate materials containing sodium ions in the interlayer spaces, eg, sodium montmorillonite or sodium bentonite, degrade the EVOH polymer that complexes to the internal platelet surfaces of the material. of layered silicate - substantially reducing by this one or more physical properties (eg, gas impermeability) of the composite material based on EVOH. In accordance with the principles of the present invention, it has been found that in order to provide a composite material containing a matrix polymer of EVOH, the interleaving and / or exfoliation thereof must be formed by intercalating the layered silicate material with an intercalating material without EVOH (monomer, oligomer or polymer) to complex the intercalator without EVOH to the platelet surfaces, thereby covering the sodium ions on the internal surfaces of the platelets with the intercalator without EVOH and protecting the matrix polymer of EVOH from the ions of Na + degradants of EVOH. It has been found that the EVOH matrix polymers are not degraded by the addition of an interlayer or exfoliate thereof, since the platelet surfaces containing Na + from the interlayer, or exfoliated from the layered silicate material, are complexed with an interlayer of monomer, oligomer or polymer without EVOH. Preferred intercalators are water-soluble polymers selected from the group consisting of polyvinylpyrrolidone (PVP); polyvinyl alcohol (PVOH); copolymers of vinyl acetate and vinyl pyrrolidone; and mixtures thereof. Better results are achieved by using an intercalant which is a monomer composition, an oligomer (defined herein as a pre-polymer having from 2 to about 15 recurring monomer units, (which may be the same or different) or one of polymer (defined herein as having more than about 15 recurring monomer units, which may be the same or different) for intercalation, having at least about 2%, preferably at least about 5% by weight intercalating monomer concentration intercalant oligomer or intercalating polymer, more preferably approximately 50% to approximately 80% by weight intercalant, based on the weight of the interlayer and the vehicle (eg, water and / or another solvent for the interlayer) to achieve a better sorption of the intercalant. intercalary between the phyllosilicate plates The interleaver without EVOH sips between, and complexes, the s silicate platelets and causes the separation or adds space between the adjacent silicate platelets and, for simplicity of description, the monomer, oligomer and / or polymer intercalators are called hereinafter the "intercalant", "monomer intercalant" , "intercalating monomer", "intercalating polymer", or "polymer intercalant". In this manner, the water-soluble or water-insoluble monomers, oligomers or polymers will be sucked sufficiently to increase the inter-layer spacing of the phyllosilicate in the range of about 5 A to about 100 A, for easier and more complete exfoliation. , in a commercially available process, without taking into account the particular phyllosilicate or intercalant polymer. According to an important feature of the present invention, better results are achieved by using a monomer, oligomer composition (defined herein as a pre-polymer having from 2 to about 15 recurring monomer units, which may be the same or different) or polymer (defined herein as having more than about 15 recurring monomer units, which may be the same or different), soluble in water or insoluble in water, for intercalation, having at least about 2% , preferably at least about 5% by weight, more preferably at least about 10% by weight of intercalant concentration, more preferably from about 30% to about 80% by weight of interlayer, based on the weight of the interlayer and the vehicle ( example, water with or without another solvent for the intercalant) in order to achieve a better sorption of the intercalant e the phyllosilicate platelets. Without taking into account the intercalant concentration in the liquid solvent of the intercalant composition, the intercalant composition must have an interlayer: proportion of stratified material of at least 1:20, preferably of at least 1:10, more preferably of at least 1: 5, and more preferably of at least 1: 4 to achieve efficient sandwiching of the interlayer between adjacent platelets of the layered material. The intercalant sorbed between, and permanently bound or complexed to, the silicate platelets causes separation or adds space between the adjacent silicate platelets and, for simplicity of description, the monomers, oligomers and polymers are hereinafter referred to as the "intercalant". " In this way, the intercalators will be sucked sufficiently to increase the spacing between the layers of the phyllosilicate in the range from about 5A to about 100A, preferably at least about 10A, for easier and more complete exfoliation, in a process commercially available, without taking into account the particular phyllo silicate or intercalary.

A phyllosilicate, such as a smectite clay, may be intercalated sufficiently for the subsequent exfoliation by sorption of monomers, polymers or oligomers having a carbonyl, hydroxyl, carboxyl, amine, amide, ether, ester, sulfate, sulfonate, sulfinate, sulphamate, phosphate, phosphonate, phosphinate functionality, or aromatic rings, including lactams, lactones, anhydrides, nitriles, n-alkyl halides, pyridines, or otherwise have a greater dipole moment at the time of water dipole (1.85 D) to provide the complexing or joining of the intercalator to the internal surfaces of the platelet by a mechanism selected from the group consisting of ionic complexation; electrostatic complexation; chelation; hydrogen bonding; ion-dipole; dipole / dipole; Van Der Waals force; and any combination thereof, between two functional groups of one or two intercalating molecules and the metal cations attached to the inner surfaces of the phyllosilicate platelets. The sorption and attraction or electrostatic binding of metallic cation of a platelet metal cation between two oxygen, sulfur, phosphorus, nitrogen or halogen atoms of the intercalating molecules; or the electrostatic bond between the cations between layers in hexagonal or pseudohexagonal rings of the smectite layers and an intercalating aromatic ring structure, increase the interlayer space between adjacent silicate platelets or other layered material to at least about 5A, preferably at least about 10 Á and more preferably at least about 20 Á, and more preferably in the range of about 30 Á to about 45 Á. Such interleaved phyllosilicates can easily be exfoliated on individual phyllosilicate platelets. Depending on the conditions to which the composition is subjected during the intercalation and exfoliation, particularly the temperature; the pH; and the amount of water contained in the intercalant composition, the interleaving and / or delaminated / carrier composition can be formed at any desired viscosity, for example, at least about 100 centipoise, preferably at least about 500-1000 centipoise, either gelled or no, and particularly at extremely high viscosities of about 5,000 to about 5,000,000 centipoise. The compositions are thixotropic so that shearing decreases viscosity for easier delivery, and then by reducing shear or eliminating shearing, the compositions will increase their viscosity. The intercalator is sandwiched between the adjacent platelet spaces of the stratified material for easy exfoliation and the complexes with the metal cations on the platelet surfaces where the polymer remains after interleaving or exfoliation thereof is combined with the vehicle / solvent or they add to a polymer melt. It follows that the interlayer coating on the surfaces of the clay plates is ionically complexed with the cations between layers and protects the Na + on the internal platelet surfaces from the degradation of the EVOH matrix polymer to which the intercalation is added and / or exfoliated. Interleaving or exfoliation participates (aids) in the viscosity and thixotropy of the vehicle / solvent composition and adds significant resistance characteristics, vapor impermeability and temperature to an EVOH matrix polymer. However, other forms of attachment such as hydrogen bonding or Van Der Waals forces or molecular complexing may also be responsible for the adhesion of the interlayer to the surfaces of the laminate material, either completely or in part. DEFINITIONS Whenever used in this Specification, the established terms will have the following meanings: "Stratified Material" will mean an inorganic material, such as a smectite clay mineral, which is in the form of a plurality of adjacent bonded layers and having a thickness, for each layer, from about 3 Á to about 50 Á, preferably about 10 Á, and includes ions of Na + on the internal platelet surfaces. "Platelets" will mean individual layers of the Stratified Material. "Interleaved" or "Interleaved" shall mean a Stratified Material that includes a monomer, oligomer and / or polymer intercalator, placed between adjacent platelets of the Layer Material to increase the interlayer space between adjacent platelets to at least 5A, preferably at least about 10 Á. "Collation" will mean a process to form an Interleaving. "Interlayer", "Intercalating Monomer" or "Intercalating Polymer" shall mean a monomer, an oligomer or a polymer that is not an EVOH copolymer, and which is sipped between the Laminated Material Platelets and complexed with the platelet surfaces for form an Interleaved "Intercalating Vehicle" shall mean a vehicle comprising water with or without an organic solvent used together with an Interlayer to form an Intercalating Composition capable of achieving the intercalation of the Layered Material. "Interleaving Composition" shall mean a composition comprising an Interleaver, an Interleaver Vehicle for the Interleaver, and a Stratified Material. "Sheeted" or "Sheeted" will mean individual platelets of an Interlayered Stratified Material so that adjacent platelets of Stratified Material Interleaved can be dispersed individually through an EVOH matrix polymer. "Exfoliation" will mean a process to form a Exfoliate from an Interleaved. "Nanocomposite" shall mean an EVOH copolymer having dispersed therein a plurality of individual platelets obtained from a stratified, exfoliated stratified material. "Matrix Polymer" will mean an EVOH copolymer in which the Interleaved and / or Exfoliate is dispersed to form a Nanocomposite. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph that delineates the space between layers for complexes of polyvinylpyrrolidone (PVP): smectite clay (intercalated) showing spaces d (001) and d (002), in Angstroms, between the clay platelets smectic versus the percentage of PVP sorbed, based on the dry weight of smectite clay; Figure 2 is a graph that delineates the space between layers for polyvinyl alcohol (PVOH) complexes: smectite clay (intercalated) showing a space d (001), in Angstroms, between the smectite clay platelets versus the PVOH percentage sorbed, based on the dry weight of smectite clay; Figure 3 is a x-ray diffraction pattern for a PVP complex (average molecular weight of 10,000): sodium montmorillonite clay, in Angstroms, in a weight ratio of PVP: clay of 20:80; Figure 4 is a x-ray diffraction pattern for a PVP complex (average molecular weight of 40,000): sodium montmorillonite clay, in Angstroms, in a weight ratio of PVP: clay of 20:80; Figure 5 is a x-ray diffraction pattern for a PVOH complex (average molecular weight of 15,000): sodium montmorillonite clay, in Angstroms, in a weight ratio of PVOH: clay of 20:80; Figure 6 is a x-ray diffraction pattern for a PVP complex: sodium montmorillonite clay, in Angstroms, in a weight ratio of PVP: clay of 20:80 (upper standard); and a x-ray diffraction pattern for a "100% sodium montmorillonite clay that has a cristobalite impurity (lower standard); Figure 7 is a x-ray diffraction pattern for a PVP complex: sodium montmorillonite clay, in Angstroms, in a weight ratio of PVP: clay 50:50 (superior pattern); and a x-ray diffraction pattern for a "100% sodium montmorillonite clay that has a cristobalite impurity (lower standard); Figure 8 is a portion of an x-ray diffraction pattern for a PVP: sodium montmorillonite clay, in Angstroms, at a PVP: clay ratio of 80:20, which shows a complex peak of PVP: clay or space d (001) of about 41 A; Figure 9 is a x-ray diffraction pattern for a mechanical blend of a polyamide and a dry sodium montmorillonite clay (about 8% moisture by weight) in a weight ratio of polyamide 80: sodium montmorillonite clay 20 (superior pattern); and a "100% sodium montmorillonite clay, with a cristobalite impurity, (lower standard), showing characteristic peaks of smectite clay d (001) at about 12.4 A, peaks of smectite clay at about 4.48 A; and a peak of cristobalite impurity at approximately 4.05 Á for both upper and lower standards.

Figure 10 is a x-ray diffraction pattern for the mechanical mixture shown in the upper pattern (polyamide 80: sodium montmorillonite clay 20) of Figure 9, after heating the mechanical mixture to the melting temperature of the polyamide (superior pattern) to achieve intercalation and exfoliation, compared to the x-ray diffraction pattern for "montmorillonite" 100% sodium clay, which has a cristobalite impurity, (inferior pattern), showing the disappearance of the peak characteristic of smectic clay d (001) at approximately 12.4 Á; the peak d (020) at about 4.48 A, characteristic of platelets is individual ectics; and a characteristic peak of cristobalite impurity at approximately 4.08 Á (upper standard); Figure 11 is a x-ray diffraction pattern similar to Figure 9, showing a mechanical mixture of dimethylterephthalate (DMTPh) (70% by weight) and dry sodium montmorillonite clay (approximately 8% moisture) (30). % by weight), on a smaller scale to figure 1, which shows a characteristic peak of smectite clay d (001) at approximately 12.4 A for mechanical mixing; and a X-ray diffraction pattern for 100% DMTPh; Figure 12 is a x-ray diffraction pattern for the mechanical mixing 70:30 of DMTPh: clay shown in Figure 3, after heating the mixture to above the melting temperature of the DMTPh (approximately 230 ° C), showing the disappearance of the characteristic smectica clay peak d (001) (approximately 12. 4 A) for fusion, showing exfoliation, and a complex peak of DMTPh: clay (intercalated) at approximately 12. 5 Á; and a X-ray diffraction pattern for 100% DMTPh; Figure 13 is a x-ray diffraction pattern for a 230 ° C (complex) fusion of polyethylene terephthalate (PET): sodium montmorillonite clay in a weight ratio of PET: clay 90:10 (superior pattern), showing the disappearance of the smectite characteristic peak d (001) at approximately 12.4 Á for fusion, showing exfoliation; and a x-ray diffraction pattern for sodium bentonite of «100%, having an impurity cristobalite, (inferior pattern); Figure 14 is a x-ray diffraction pattern for a fusion at 250 ° C (complex) of hydroxyethylterephthalate (HETPh): sodium montmorillonite clay in a weight ratio of HETPh: clay of 60:40 (lower standard), showing the disappearance of the smectite characteristic peak d (001) at approximately 12.4 A for fusion, showing exfoliation; and a x-ray diffraction pattern for 100% HETPh (upper standard); Figure 15 is a x-ray diffraction pattern for a 250 ° C (complex) fusion of hydroxybutylterephthalate (HBTPh): sodium montmorillonite clay in a weight ratio of HBTPh: 70:30 clay (lower standard), showing the disappearance of the smectite characteristic peak d (001) at approximately 12.4 A for fusion, showing exfoliation; and a x-ray diffraction pattern for 100% HBTPh (lower standard); Figure 16 is a x-ray diffraction pattern for a polycarbonate complex: sodium montmorillonite clay in a molten mixture ratio (280 ° C) of polycarbonate: 50:50 clay, showing the disappearance of the characteristic smectite peak d (001) at about 12.4 A for melting, showing exfoliation; Figure 17 is a thermogravimetric analysis of 50.0 milligrams of a copolymer of ethylene vinyl alcohol (EVOH), without the addition of a phyllosilicate, analyzed from a starting temperature of 296.7 ° C, a peak temperature of 415.0 ° C, and a final temperature of 641.7 ° C, without showing peaks of decomposition (without degradation of EVOH); Figure 18 is a thermogravimetric analysis of a total of 20.0 milligrams of the same ethylene vinyl alcohol copolymer of Figure 17, complexed with sodium montmorillonite clay - the complex is then incorporated into an EVOH matrix polymer at a charge of 9.2% by weight - is analyzed through an initial temperature of 36.7 ° C and a final temperature of 690 ° C, showing peaks of decomposition at approximately 357 ° C and 472 ° C, indicating a large amount of polymer degradation. EVOH; Figure 19 is a thermogravimetric analysis of a total of 50.0 milligrams of polyvinyl alcohol (PVOH), complexed with the same sodium montmorillonite clay used in the analysis shown in Figure 18 - the complex is then incorporated into an EVOH matrix polymer at a charge of 4.29% by weight - analyzed through a start temperature of 46.7 ° C and a final temperature of 768.3 ° C, without showing decomposition of PVOH; Figure 20 is a thermogravimetric analysis of a total of 20.0 milligrams of polyvinylpyrrolidone (PVP), complexed with the same sodium montmorillonite clay used in the analysis shown in Figures 18 and 19 - the complex is then incorporated into a matrix polymer of EVOH at a load of 3.9% by weight - is analyzed through a starting temperature of 153.3 ° C and at a final temperature of 715.0 ° C, without showing decomposition of the PVP; and Figure 21 is a thermogravimetric analysis of a total of 20.0 milligrams of a polyvinylpyrrolidone / polyvinyl acetate copolymer, complexed with the same sodium montmorillonite clay used in the analyzes shown in Figures 18, 19 and 20 - the complex is then incorporated into an EVOH matrix polymer at a charge of 7.9% by weight - analyzed through a starting temperature of 155.0 ° C and a final temperature of 591.7 ° C, without showing decomposition of the polyvinylpyrrolidone / polyvinyl acetate copolymer. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The interlayer must have an affinity with the phyllosilicate so that it slugs between, and remains associated with the silicate platelets, in the spaces between layers, and after the exfoliation. According to a preferred embodiment of the present invention, the intercalant must include an aromatic ring and / or have a functionality selected from the group consisting of a carbonyl; carbóxilo; hydroxyl; amine; amide; ether; ester; sulfate; sulfonate; sulfinate; sulphamate; phosphate; phosphonate; or phosphinate structure; or otherwise has a dipole moment greater than the water dipole moment (> 1.85 D) to sufficiently join an internal surface of the phyllosilicate. By this it is deduced that the bonding of the intercalator to the platelet surfaces is by complexing or electrostatic metallic cation bonding, for example, chelation, of the metal cations of the phyllosilicate shear electrons with two carbonyls, two carbonyls, two hydroxyls , two oxygens, two amines, two S0X, two P0X (where x = 2, 3, or 4) and / or two amide functionalities of an intercalating molecule, or of two intercalating molecules adjacent to an inner surface of the platelets of phyllosilicate Such intercalants have sufficient affinity with the phyllosilicate platelets to provide sufficient inter-layer space for exfoliation, for example, of about 5A-100A, preferably about 10A-50A, and to maintain clamping to the surfaces of the layers. platelets, without the need for coupling agents or separation agents, such as the onium ion or silane coupling agents set forth in the prior art mentioned above. The interleaver sorption should be sufficient to achieve the expansion of adjacent platelets of the laminated material (when measured dry - having a maximum of about 5% by weight of water) towards an interlayer space of at least about 5A, preferably a space of at least about 10A, more preferably a space of at least 20A, and more preferably a space of about 30-45A. To achieve interleaves that can be easily exfoliated using the preferred water-soluble polymer intercalators discussed herein, such as polyvinylpyrrolidone, polyvinyl alcohol, vinyl acetate copolymers and vinyl pyrrolidone and mixtures thereof, the weight proportion of the intercalant and the stratified material, preferably a water-swellable smectic clay such as sodium bentonite, in the intercalant composition contacting the phyllosilicate should be at least about 1:20, preferably at least about 1:12 to 1:10, more preferably at least about 1: 5 to about 1: 3. It is preferred that the interlayer concentration in the intercalant composition, based on the total weight of the interlayer plus the intercalant vehicle (water plus any organic liquid solvent) in the intercalant composition is at least about 15% by weight, more preferably at least about 20% by weight intercalant, for example from about 20% -30% to about 90% by weight of intercalant, based on the weight of the intercalator plus the intercalant vehicle (water plus any organic solvent) in the intercalant composition during the intercalation.

It has been found that the interleaves of the present invention are increased in stepped mode of space between layers. If the phyllosilicate is contacted with a composition containing intercalant containing less than about 16% by weight intercalant, for example, from 10% to about 15% by weight intercalant, based on the dry weight of the phyllosilicate, an amplitude is absorbed of interlayer monolayer (interleaved) between, and complexed with, the adjacent platelets of the stratified material. A interlayer monolayer sandwiched between the platelets increases the inter-layer spacing from about 5A to less than 10A. When the amount of interleaver is in the range of about 16% to less than about 35% by weight, based on the weight of the dry layered material, the interlayer is sorbed in a bilayer, thereby increasing the interlayer gap to about 10. Á up to about 16 Á, as shown in Figures 1 and 2. In an interlayer filler in the interlayer composition from about 35% to less than about 55% interlayer, based on the dry weight of the contacted laminate, the space between layers is increased to about 20 Á to about 25 Á, corresponding to the three interlayer layers sorbed between and complexed with the adjacent platelets of the laminated material, as shown in FIGS. 1 and 2. In an intercalating polymer filler of approximately 55% up to about 80% interlayer, based on the dry weight of the stratified material dissolved or dispersed in the If the intercalant contains the interlayer space, it will increase to approximately 30A to approximately 35A, corresponding to 4 and 5 layers of intercalating polymer sorbed (interleaved) between and complexed with the adjacent platelets of the laminated material, as shown in FIGS. Figures 1 and 2. Such interleaves are especially useful in mixing with EVOH matrix polymers in the manufacture of polymeric articles from polymer / platelet composite materials; particularly in the manufacture of EVOH films having increased impermeability to air and oxygen; and for the mixture of the intercalated and interleaved exfoliated with polar solvents when modifying the rheology, for example, of cosmetics, drilling fluids of oil wells, paints, lubricants, lubricants of special nutritional quality in the manufacture of oil and grease, and Similary. Once exfoliated, intercalary platelets are predominantly separated completely on individual platelets that have intercalating molecules complexed with the platelet surfaces, and the originally adjacent platelets are no longer retained in a separate, parallel placement, but are free to move as predominantly individual platelets, intercalary covers (continuously or discontinuously) through an entire EVOH vehicle or through an entire EVOH matrix polymer melt to act similarly to a nanoscale filler material for the polymer of matrix. Predominantly individual phyllosilicate platelets, which have their platelet surfaces complexed with intercalating molecules, are dispersed randomly, homogeneously and uniformly throughout an entire vehicle, such as water or an organic liquid, or through a whole copolymer melt. of EVOH. Once the EVOH / platelet matrix polymer composite material is established and hardened into a desired shape, the predominantly individual phyllosilicate plates are fixed permanently in position and dispersed in a random, homogeneous and uniform manner, predominantly as individual platelets, throughout the entire matrix / platelet polymer composite. According to a preferred embodiment of the present invention, the phyllosilicate should include at least about 4% by weight of water, up to about 5000% of water, based on the dry weight of the phyllosilicate, preferably from about 7% to about 100% by weight. water, more preferably from about 25% to about 50% by weight of water, before or during contact with the interlayer to achieve a sufficient intercalation for exfoliation. Preferably, the phyllosilicate should include at least about 4% by weight of water prior to contact with the intercalant vehicle for efficient intercalation. For efficient exfoliation, the amount of interlayer in contact with the phyllosilicate of the intercalant composition, should provide a weight ratio of intercalant / phyllosilicate (based on the dry weight of the phyllosilicate) of at least about 1:20, preferably at least about 3.2: 20, and more preferably about 4-14: 20, to provide efficient sorption and complexation (intercalation) of the interlayer between the platelets of the laminated material, for example, phyllosilicate, (preferably from about 16% to about 70% by weight of interlayer, based on the dry weight of the layered silicate material). The intercalants are introduced in the form of a solid or liquid composition (solution or dispersion without mixture or aqueous, and / or with an organic solvent, for example, hydroalcoholic) having an intercalant concentration of at least about 2%, preferably of at least about 5% by weight of interlayer, more preferably from at least about 50% to about 100% by weight of interlayer in the interlayer / vehicle composition contacting the layered material (interleaving composition) for sorption and complexing of the interlayer. The intercalant can be water soluble, insoluble in water or partially soluble in water and can be added as a liquid or solid with the addition to the mixture of layered material of at least about 20% water, for example, from about 20% up to about 80%, preferably at least about 30% water to about 5000% water and / or another solvent for the interlayer, based on the dry weight of the layered material plus the interlayer. Preferably, about 30% to about 50% of water or other solvent must be included in the interleaving composition, so that less water or solvent is swallowed by the interleaving, thus requiring less drying energy after intercalation. The interleaver may be introduced into the spaces between each layer, almost each layer, or at least a predominance of the layers of the laminated material in such a way that the subsequently exfoliated platelet particles are preferably, predominantly less than about 5 layers in thickness; more preferably, predominantly about 1 or 2 layers thick; and more preferably, predominantly individual platelets. In the practice of this invention, any inflatable laminated material that sufficiently sucks the interlayer can be used to increase the interlayer gap between the adjacent phyllosilicate plates to at least about 5 A, preferably at least about 10 A (when the phyllosilicate is dry measure - having a maximum of approximately 5% by weight of water). Useful inflatable layered materials include phyllosilicates, such as smectite clay minerals, for example, montmorillonite, particularly sodium montmorillonite; magnesium montmorillonite and / or calcium montmorillonite; nontronite; beidelita; volconscoite; hectorite; saponite; sauconite; sobockita, stevensite; svinfordite; vermiculite; and the similar. Other useful stratified materials include micaceous minerals, such as illite and mixed stratified minerals of illite / smectite, such as ledikite and illite mixtures with the clay minerals mentioned above. Preferred foamable sheet materials are phyllosilicates of type 2: 1 having a negative charge in the layers varying in fillers from about 0.15 to about 0.9 per unit of formula and a proportionate number of interchangeable metal cations in the interlayer spaces. The most preferred stratified materials are smectite clay minerals such as montmorillonite, nontronite, beidelite, volconscoite, hectorite, saponite, sauconite, sobockite, stevensite and svinfordite. As used herein, "interlayer space" refers to the distance between the internal faces of adjacent dry layers as they are assembled in the laminated material before any delamination (exfoliation) takes place. The interlayer space is measured when the stratified material is "air dried", for example, it contains about 3-10% by weight of water, preferably of about 3-6% by weight of water, based on the dry weight of the laminated material. Preferred clay materials generally include interlayer cations such as Na +, Ca + 2, K +, Mg + 2, NH 4 + and the like, including mixtures thereof. The amount of interleaver interspersed in the inflatable laminate materials useful in this invention, so that the interleaved laminate material can be delaminated or delaminated into individual platelets, may vary substantially between about 10% and about 80%, based on the dry weight of the material of layered silicate. In the preferred embodiments of the invention, the amounts of intercalators employed, with respect to the dry weight of the layered material being interleaved, will preferably vary from about 8 grams interlayer / 100 grams layered material (dry basis), more preferably at least approximately 10 grams of interlayer / 100 grams of laminated material, up to approximately 80-90 grams of interlayer / 100 grams of laminated material (dry basis). The most preferred amounts are from about 20 grams interlayer / 100 grams stratified material to about 60 grams interlayer / 100 grams stratified material (dry basis). The intercalators were introduced into (slurried within) the spaces between layers of the stratified material in one of two ways. In a preferred intercalation method, the layered material is intimately mixed, for example, by extrusion, with a concentrated intercalant or intercalant / water solution, or intercalant / organic solvent, for example, ethanol solution. To achieve the best interleaving for the exfoliation, the layered / interlayer mixture contains at least about 8 wt% interlayer, preferably at least about 10 wt% interleaver, based on the dry weight of the layered material. The intercalant vehicle (preferably water, with or without an organic solvent, for example, ethanol) can be added by solubilizing or dispersing the interlayer in the vehicle first; or the dry intercalant and the relatively dry phyllosilicate (preferably containing at least about 4% by weight of water) can be mixed and the intercalant vehicle added to the mixture, or to the phyllosilicate before adding the dry interlayer. In each case, it has been found that the surprising sorption and complexation of the intercalant between the platelets is achieved at relatively low loads of intercalant vehicle, especially H20, for example, of about 4% by weight of water, based on the dry weight of the phyllosilicate. . When the phyllosilicate is intercalated in the form of a mixture (eg, 900 pounds of water, 100 pounds of phyllosilicate, 25 pounds of polymer) the amount of water can vary from a preferred minimum of at least about 30% by weight of water, without upper limit for the amount of water in the intercalant composition (the phyllosilicate intercalate is easily separated from the intercalant composition). Alternatively, the intercalant vehicle, eg, water, with or without an organic solvent, can be added directly to the phyllosilicate before the intercalant is added, either dry or in solution. The sorption of the intercalating molecules can be carried out by exposing the layered material to dry or liquid intercalating compositions containing at least about 2% by weight, preferably at least about 5% by weight intercalant, more preferably at least about 50% by weight. interlayer, based on the dry weight of the stratified material. Sorption can be aided by exposure of the intercalating composition to heat, pressure, ultrasonic cavitation or microwaves. According to another method for sandwiching the interlayer between the platelets of the layered material and for exfoliating the interlayer, the layered material, which contains at least about 4% by weight of water, preferably about 10% to about 15% by weight of water, it is mixed with a solubilized intercalant (in a vehicle of water or organic solvent) in a sufficient proportion to provide the organic) in a sufficient proportion to provide at least about 8% by weight, preferably at least about 10% by weight of intercalant , based on the dry weight of the stratified material. The mixture is then extruded preferably for a faster intercalation. In addition, the mixture can be heated to at least the melting temperature of the interlayer, and preferably to at least about 40-50 ° C above the melting temperature of the interlayer for faster intercalation. In accordance with an important embodiment of the present invention, one or more polymerizable monomers can be interspersed between the platelets of the layered material, or simply mixed with the exfoliated layered material, and the polymerizable monomer (s) polymerized ( n) while interspersed between the platelets, or while they are in contact with the interleaved or interleaved exfoliate. The polymerizable monomer (s) can be, for example, a mixture of an acrylic acid and a polymerization initiator for the acrylic acid to produce water-soluble polyacrylic acid or polyacrylate acid; or a degrading agent can be added to produce a water insoluble polymer; or the monomer (s) may be any of the polymerizable organic liquids, which are polymerized to form a polymer, such as the water-soluble polymer set forth in U.S. Patent No. 4,251,576, incorped herein by reference. reference. The suitable insoluble polymerizable monomer (s) in water (s) can be, for example, a mixture of a suitable diamine and a dicarboxylic acid for the reaction to produce a polyamide, example, nylon; or the monomer (s) may be any of the polymerizable organic liquids, which are polymerized to form a water insoluble polymer, set forth in U.S. Patent No. 4,251,576, incorped herein by reference. Preferred polymer intercalators are water soluble, such as polyvinylpyrrolidone (PVP) having a monomeric structure (I) as follows: : D The water solubility of the PVP can be adjusted according to (1) the degree of hydrolysis of the polyvinylpyrrolidone, and (2) by the formation of a metal salt of PVP, such as sodium or potassium. PVP can be hydrolyzed to structure (II): (ID and PVP can be interspersed in the salt form, eg, sodium or potassium polyvinylpyrrolidone.) Preferred PVP intercalants, and the following PVP derivatives, must have a weight molecular weight in the range from about 100 to about 100,000 or more, more preferably from about 1,000 to about 40,000. Other suitable vinyl polymers, soluble in water, include poly (vinyl alcohol) Polyvinyl alcohols work best when they are essentially completely hydrolyzed, for example, acetyl groups at 5% or less, preferably at least 1% acetyl groups. The lower molecular weight PVOH 's work better, for example, an average molecular weight of from about 2,000 to about 10,000, but the higher molecular weights also work, for example, up to about 100,000. Polymers and copolymers of polyacrylic acid and partially or completely neutralized salts, for example, metal salts, are also suitable, having monomer units: and are commercially available as CARBOPOL resins from B. F. Goodrich and PRIMAL resins from Rohm & Haas. A slight degradation is acceptable, since water solubility is retained. The average molecular weights, for the polyacrylic polymers and copolymers described above and below, of about 10,000 or less, for example 200-10,000, are more easily intercalated, but higher molecular weights of up to about 100,000 or more also work. Other suitable intercalating polymers are disclosed in U.S. Patent No. 5,552,469, of this assignee, incorporated by reference. Suitable insoluble water-insoluble intercalating polymers include polyamides; polyesters; polycarbonates; polyurethanes; polyepoxides; polyolefins; polyalkylamides; and mixtures thereof. Suitable water-insoluble polymers include: polyethers (polymers and copolymers) based on ethylene oxide, butylene oxide, propylene oxide, phenols and henols; polyesters (polymers and copolymers) based on aliphatic and aromatic diols, and aliphatic and aromatic dibasic acids; polyurethanes based on aliphatic and aromatic diisocyanates, and aliphatic and aromatic diols; polyamides (polymers and copolymers) based on (a) aliphatic and aromatic diamines, and aliphatic and aromatic dibasic acids; (b) aliphatic and aromatic amino acids; polycarbonates (polymers and copolymers) based on carbonic acid and aromatic diols; polycarbonates (polymers and copolymers) based on dianhydride of tetrabasic acids and diamines and other heterochain polymers; vinyl polymers and copolymers based on vinyl monomers, styrene and styrene derivatives; acrylic polymers and copolymers based on acryl monomers; copolymers based on styrene, vinyl and acryl monomers; polymers and copolymers of polyolefins based on ethylene, propylene and other alpha-olefin monomers; polymers and copolymers based on dienes, isobutylenes and the like; and copolymers based on monomers of dienes, styrene, acryl and vinyl. The thermosetting resins based on water-soluble prepolymers, include prepolymers based on formaldehyde: phenols (phenol, cresol and the like); urea; melamine; melamine and phenol; urea and phenol.

Polyurethanes based on: toluene diisocyanate (TDI) and monomeric and polymeric diphenylic methane diisocyanates (MDI); hydroxy-terminated polyethers (polyethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene oxide and the like); Amino-terminated polyethers, polyamines (tetraethylenediamine, ethylenediamine, hexamethylenediamine, 2,2-dimethyl, 3-propanediamine; melamine, diaminobenzene, triaminobenzene and the like); polyamidoamines (for example, hydroxy-terminated polyesters); unsaturated polyesters based on anhydrides and maleic and fumaric acids; glycols (ethylene, propylene), polyethylene glycols, polypropylene glycols, aromatic glycols and polyglycols; unsaturated polyesters based on vinyl, allyl and acrylic monomers; epoxides, based on biphenol A (2,2'bis (4-hydroxyphenyl) propane) and epichlorohydrin; epoxy prepolymers based on monoepoxy and polyepoxy compounds and unsaturated compounds a, β (styrene, vinyl, allyl, acrylic monomers); polyamides 4-tetramethylene diamine, hexamethylenediamine, melamine, 1,3-propanediamine, diaminobenzene, triaminobenzene, 3, 3 ', 4,' -bitriaminobenzene; 3, 3 ', 4,4'-biphenyltetramine and the like). Polyethyleneimines; amides and polyamides (di-, tri-, and tetra-acid amides); hydroxyphenols (pyrogallium, gallic acid, tetrahydroxybenzophenone, tetrahydroquinone, catechol, phenol and the like); anhydrides and polyanhydrides of di-, tri-, and tetra-acids; polyisocyanurates based on TDI and MDI; polyimides based on pyromellitic dianhydride and 1,4-phenyldiamine; polybenzimidozoles based on 3, 3 ', 4'-biphenyltetramine and isophthalic acid; polyamide based on unsaturated dibasic acids and anhydrides (maleic, fumaric) and aromatic polyamides; alkyd resins based on dibasic or anhydride aromatic acids, glycerol, trimethylolpropane, pentaerythritol, sorbitol and long chain, fatty, unsaturated carboxylic acids (the latter, derived from vegetable oils); and prepolymers based on acrylic monomers (hydroxy or carboxy functional). The amount of interleaving and / or stratified exfoliated material included in an EVOH matrix polymer to form composite materials based on EVOH polymer can vary widely depending on the proposed use of the material. The barrier properties and the thermal resistance (charge deflection temperature, DTUL), substantially improved, are imparted by platelet particle concentrations of about 1% to about 5% by weight, particularly of 2.5-5% in a polymer of EVOH matrix. Similarly, substantially improved strength is imparted by platelet particle concentrations greater than about 1.5%, including the nanoscale layered materials of this invention. It is preferred that the platelet load be less than about 10%. The platelet particle loads within the range of about 0.05% to about 40% by weight, preferably from about 0.5% to about 20%, more preferably from about 1% to about 10% of the composite material significantly improve the modulus, stability dimensional, and resistance. In general, the amount of platelet particles incorporated into the EVOH matrix polymer is less than about 90% by weight of the mixture, and preferably from about 0.01% to about 80% by weight of the composite mixture, more preferably from about 0.05% to about 40% by weight of the polymer / particle mixture, and more preferably from about 0.05% to about 20% or 0.05% to about 10% by weight. According to an important characteristic of the present invention, the interleaved phyllosilicate can be made in a concentrated form, for example, 10-90%, preferably 20-80% interleaver and 10-90%, preferably 20-80% interleaved phyllosilicate which can be dispersed in an EVOH matrix polymer and exfoliated before or after addition to the EVOH polymer melt at a desired platelet charge. Exfoliation of the interleaved laminate material should provide delamination of at least about 90% by weight of the interleaved material to provide a composition comprising a polymer matrix having substantially uniformly dispersed platelet particles therein. Some interleaves require a shear rate greater than about 10 sec-1 for such relatively thorough exfoliation. Other interlayers are exfoliated naturally or by heating to the melting temperature of the intercalating polymer, or when applying pressure, for example, from 0.5 to 60 atmospheres above the environment, with or without heating. The upper limit for the shear rate is not critical taking into account that the shear rate is not so high as to physically degrade the polymer. In the particularly preferred embodiments of the invention, when shearing is employed for peeling, the shear rate is greater than about 10 sec-1 to about 20,000 sec-1, and in the most preferred embodiments of the invention the shear rate is from about 100 sec. "1 to about 10,000 sec" 1. When shearing is employed for the exfoliation, any method for applying shear to the flowable mixture can be used or any polymer melt can be used. The shearing action can be provided by any suitable method, for example by mechanical means, by thermal shock, by pressure alteration, or by ultrasonics, all known in the art. In particularly useful processes, the flowable polymer mixture is sheared by mechanical methods in which portions of the melt are caused to flow past other portions of the mixture by the use of mechanical means, such as agitators, Banbury® type mixers, Brabender® type mixers, long continuous mixers, and extruders. Another method employs thermal shock in which shear is achieved by alternately raising or lowering the temperature of the mixture, causing thermal expansions and resulting in internal stresses causing shearing. In still other procedures, shear is achieved by sudden pressure changes in pressure alteration methods; by ultrasonic techniques in which the cavitation or resonant vibrations cause portions of the mixture to vibrate or be excited in different phases and thus be subjected to shear. These methods for shearing meltable polymer blends and polymer melts are merely representative of useful methods, and any method known in the art for shearing polymer blends and flowable polymer melts can be used. Mechanical shearing methods such as by extrusion, injection molding machines, Banbury® type mixers, Brabender® type mixers and the like can be employed. Shearing can also be achieved by introducing the polymer melt at one end of the extruder (single or double screw) and receiving the sheared polymer at one end of the extruder. The temperature of the polymer melt, the length of the extruder, the residence time of the melt in the extruder and the design of the extruder (single screw, twin screw, number of flights per unit length, depth of the channel, the flight safety margin, the mixing zone, etc.) are several variables that control the amount of shear to be applied. The exfoliation must be thorough enough to provide at least about 80% by weight, preferably at least about 85% by weight, more preferably at least about 90% by weight, and more preferably at least 95% by weight of delamination of the layers to form platelet particles dispersed substantially homogeneously in the polymer matrix. As they are formed by this process, the platelet particles dispersed in the EVOH matrix polymers have the thickness of the individual, or small, layers smaller than about 10, preferably less than about 5 and more preferably less than about 3 of the layers, and still more preferably 1 or 2 layers. In the preferred embodiments of this invention, the intercalation and delamination of each interlayer space is completed so that all or substantially all of the individual layers delaminate with each other to form separate platelet particles. In cases where the intercalation between some layers is incomplete, those layers will not delaminate in a polymer melt, and will form platelet particles comprising those layers in a coplanar aggregate. The effect of adding on the matrix polymer of EVOH the dispersed, particulate, nanoscale platelet particles, derived from the interleaves formed in accordance with the present invention, is typically an increase in gas impermeability, modulus of traction and / or ultimate tensile strength or an increase in the final resistance to impact or glass transition temperature (Tg). The molding compositions comprising the EVOH matrix polymer containing a desired platelet load obtained from the exfoliation of the interleaves made according to the invention are remarkably suitable for the production of sheets and panels having valuable properties. Such sheets and panels can be configured by conventional processes such as vacuum processing or by hot pressing to form useful objects. The sheets and panels according to the invention are also suitable as coating materials for other materials such as wood, glass, ceramics, metal and other plastics. The sheets and panels can also be laminated with other plastic films and this is preferably effected by coextrusion, the sheets being joined in the molten state. The surfaces of the sheets and panels, including those in patterned form, can be improved or terminated by conventional methods, for example by varnishing or by the application of protective films. Polymer / platelet composite materials are especially useful for the manufacture of extruded films and film laminates, such as films for use in food packaging. Such films can be manufactured using conventional film extrusion techniques. The films are preferably from about 10 to about 100 microns, more preferably from about 20 to about 100 microns and more preferably from about 25 to about 75 microns in thickness. The homogeneously distributed platelet particles and the matrix polymer forming the nanocomposites are formed into a film by suitable film forming methods. Typically, the composition is melted and forced through a film-forming nozzle. The nanocomposite film can go through stages to cause the platelets to be oriented additionally so that the major planes through the platelets are substantially parallel to the main plane through the film. One method to do this is to extend the film biaxially. For example, the film extends in the axial or machine direction by tension rollers that push the film as it is extruded from the nozzle. The film extends simultaneously in the transverse direction by holding the edges of the film and separating them. Alternatively, the film extends in the transverse direction by using a tubular film nozzle and inflating the film as it passes from the tubular film nozzle. The films may exhibit one or more of the following benefits: increased module; increased moisture resistance; increased dimensional stability; decreased moisture adsorption; decreased permeability to gases such as oxygen and liquids, such as water, alcohols and other solvents. The following specific examples are presented to illustrate the invention more particularly and are not construed as limitations thereto. EXAMPLE 1 Preparation of Clay Complexes - PVP (Intercalated) Materials: Clay - sodium montmorillonite; PVP - molecular weights of 10,000 and 40,000. To prepare complexes (intercalated) of Clay (sodium montmorillonite) - PVP we use three different processes for the intercalation of the polymer: 1. Mixing the PVP / water solution at 2% with the clay / water suspension at 2% in one enough ratio to provide a polymer concentration of at least about 16% based on the dry weight of the clay. 2. Dry clay powder (approximately 8% by weight moisture) was gradually added to the PVP / 2% water solution in a sufficient proportion to provide a polymer concentration of at least about 16% based on weight of clay. 3. Dry PVP was mixed with dry clay, the mixture was hydrated with 35-38% water, based on the dry weight of the clay, and then extruded. Mixtures of 1 and 2 were stirred at room temperature for 4 hours.

This weight ratio of Clay: PVP was changed from 80:20 to 20:80. These experiments showed that all the preparation methods produced the Clay-PVP complexes (intercalated), and the intercalation results do not depend on the preparation method (1, 2 or 3) or molecular weight of the intercalating polymer (PVP), but they depend on the amount of PVP sorbed between the clay platelets. In Table 1 the results of the X-ray diffraction for the Clay-PVP complexes with different proportions of components were demonstrated. The graph of these data is shown in Figure 1. From these data (Table 1, Figure 1) one can observe the stepped character of the intercalation while the polymer is being sucked in the interlayer space between the adjacent platelets of the montmorillonite clay. Values d (001) are increased from 12 Á for clay without PVP sorbed to 24-25 Á of space between adjacent platelets with 20-30% PVP sorption. The next 30-32 Á spacing step occurs when the content of sorbed PVP increases to 40-60%. Further increasing the content of PVP sorbed to 70-80% increases the values d (001) to 40-42 Á. There are reflections d (002) together with reflections d (001) in X-ray patterns of all the obtained complexes (Table 1, Figure 1). This indicates the regularity of the structures of the Clay - PVP complex.

TABLE 1 * Percent by weight, based on the dry weight of the clay.

EXAMPLE 2 Preparation of Clay Complexes - PVOH (Intercalated) Materials: Clay - sodium montmorillonite; PVOH - degree of hydrolysis 75-99%, - molecular weights of 5,000 and 8,000.

To prepare complexes (intercalated) of Clay (sodium montmorillonite) - PVOH we provide three different processes for the intercalation of the polymer: 1. Mixing the PVOH / water solution at 2% with the clay / water suspension at 2% in one proportion sufficient to provide a polymer concentration of at least about 16% based on the dry weight of the clay, 2. Dry clay powder was gradually added to the PVOH / 2% water solution in a sufficient proportion to provide a polymer concentration of at least about 16% based on the weight of the clay. 3. The dry clay was moistened with a PVOH / water solution at a moisture content of 20-80% water, and then extruded. Mixtures 1 and 2 were stirred at room temperature for 4 hours. The weight ratio of Clay: PVOH was changed from 80:20 to 20:80. Some of the exfoliates were studied by X-ray diffraction. These experiments showed that all the preparation methods produced the complexes of Clay-PVOH (intercalated), and the intercalation results do not depend on the method of preparation (1, 2 or 3) or the molecular weight of the intercalating polymer (PVOH), or degree of hydrolysis, but depend on the concentration of PVOH sorbed between the clay platelets. In Table 2 the results of the X-ray diffraction for the Clay-PVOH complexes with different proportions of components were demonstrated. The graph of these data is shown in Figure 2. From these data (Table 2, Figure 2) one can observe the stepped character of the increase in values d (001) from 12 Á for clay without PVOH sipped up to 22- 25 A of space between the adjacent platelets with 20-30% PVOH sorption. The next step up to 30-33 A occurs when the content of sorbed PVOH increases to 35-50%. An additional increase in the content of PVOH sorbed to 60-80% increases the values d (001) to 40-45 Á. The heating of the samples at 120 ° C for 4 hours insignificantly changed the values d (001) (Table 2, Figure 2).

TABLE 2 * Percent by weight, based on the dry weight of the clay, The graphs of Figures 3 to 5 are X-ray diffraction patterns of mixtures of different intercalants of water-soluble polymers with sodium bentonite clay. The pattern of Figures 3 and 4 is taken from polyvinylpyrrolidone at 20% by weight of intercalated clay (average molecular weight = 10,000 for Figure 3).; 40,000 for Figure 4) and 80% by weight of sodium bentonite clay. The mixtures were formed by mixing PVP and clay from a 2% PVP solution and a 2% sodium bentonite dispersion in a ratio of 1: 4, respectively. As shown, PVP: clay is complexed since no smectite peak d (001) appears at approximately 12.4 A. Similar results are shown for 20% polyvinyl alcohol, 80% sodium bentonite, as shown in figure 5, mixed in the same way and in the same proportion. The peak d (001) of non-exfted sodium bentonite clay (stratified) appears at about 12.4 A, as shown in the X-ray diffraction pattern for sodium bentonite clay (containing about 10% by weight) of water) in the lower X-ray diffraction patterns of Figures 6 and 7. The graphs in Figure 6 are X-ray diffraction patterns of sodium bentonite clay (montmorillonite) and a PVP complex: clay that was obtained by extruding a mixture of polyvinylpyrrone at 20% by weight (molecular weight 10,000) and 80% sodium bentonite clay (containing an impurity cristobalite having a space d, of approximately 4.05 A) with 35% water by dry clay weight. As shown in Figure 6, the PVP clay is complexed since no smectite peak d (001) appears at approximately 12.4 A. There are basal spaces with a peak d (001) of PVP complex: clay at approximately 24 A and a peak d (002) of PVP complex: clay at approximately 12 A, which is shown close to the regular structure of this compound interspersed with a PVP: clay ratio equal to 1: 4. The graphs of Figure 7 are X-ray diffraction patterns of sodium bentonite clay (montmorillonite) and a PVP clay complex which was obtained by extruding a mixture of 50% polyvinylpyrrone by weight (10,000 molecular weight) and 50% sodium bentonite clay (containing a cristobalite impurity having a space d, of about 4.05 A) with 35% by weight of dry clay water. As shown in figure 7, the PVP: clay complexes since no smectite peak d (001) appears at approximately 12.4 A. There are basal spaces with a peak d (001) of PVP complex: clay at about 32 A and a peak d (002) of PVP complex clay at approximately 16 A, which is shown close to the regular structure of this compound intercalated with a PVP-clay ratio equal to 1: 1. When the mechanical mixtures of powdered sodium bentonite clay (containing approximately 10% by weight of water) and powdered polyvinylpyrrone polymer (PVP) were mixed with water (approximately 75% by weight of clay), the polymer was interspersed between the bentonite clay platelets, and an exothermic reaction occurred, which is deduced, resulted from the polymer bonded to the internal faces of the clay platelets sufficiently for the exftion of the intercalated clay. It should also be noted that exftion did not occur unless the bentonite clay included water in an amount of at least about 4% by weight, based on the dry weight of the clay, preferably from about 10% to about 15% water . Water can be included in the clay as it is received, or it can be added to the clay before or during contact with the polymer. It should also be noted that the exftion occurred without shearing - the stratified clay was naturally exfted after sufficient intercalation of the polymer between the stratified bentonite platelets - if the interleaving was obtained by the use of sufficient water, for example, about 20 % up to about 80% by weight, based on the dry weight of the clay, for a sufficient migration of the polymer towards the spaces between layers, and preferably also an extrusion; or by heating the mixtures to at least the melting temperature of the intercalating polymer, while the clay includes at least about 5% by weight of water, for the intercalation of the polymer. The X-ray diffraction pattern of Figure 8 shows that at a ratio of 80% PVP, 20% clay, the periodicity of the compound intercalated with a PVP clay ratio equal to 4: 1 is increased to approximately 41 A EXAMPLE 3 The upper X-ray diffraction pattern shown in Figure 9 was taken on a mechanical mixture of 80% by weight of polyamide and 20% by weight of sodium bentonite clay. The lower X-ray diffraction pattern was taken in a 100% sodium bentonite clay. The polyamide was not sandwiched between the clay platelets since the mixture was dry (the clay contained approximately 8% by weight of water) and the polyamide was not melted. As shown in Figure 1, both diffraction patterns show characteristic d (001) 12.45 A and peak characteristic d (020) 4.48 A of non-exfoliated smectic clays and a peak characteristic of 4.05 A of a cristobalite impurity. As shown in Figure 10, when the mechanical blend of 80% polyamide, 20% sodium bentonite was heated to the melting temperature of the polyamide, and preferably at least above about 40-50 ° C, the melting temperature of the polymer for a faster intercalation, eg, 230 ° C, (see the upper X-ray diffraction pattern for fusion) the peak d (001) of the smectite at 12.45 A was no longer present, since that the polyamide was interspersed between the clay platelets and the platelets exfoliated, thereby eliminating the periodicity characteristic d (001) of the aligned smectic platelets. The mechanical mixture was melted by heating the mixture to the melting temperature under an upper space of N2 to avoid oxidation. The lower X-ray diffraction pattern of Figure 10 is again the 100% sodium bentonite standard for comparison. Alternatively, the mechanical mixture could be mixed with about 10% by weight, preferably from about 20% to about 50% by weight of water or organic solvent, based on the total weight of the mixture, and extruded to achieve intercalation and exfoliation . EXAMPLE 4 Similar to Figure 9, the X-ray diffraction pattern shown in Figure 11 was taken from a mechanical mixture of 70% by weight of dimethylterephthalate and 30% by weight of sodium bentonite clay. Due to the different scales of Figure 3 versus Figure 9, the smectic peak d (001) at approximately 12.4 A is not as high. The lower X-ray diffraction pattern of Figure 11 is 100% dimethylterephthalate. As shown in Figure 12, when the mechanical mixture is subjected to a temperature above the melting temperature of dimethylterephthalate, of approximately 230 ° C, the smectic peak d (001) 12.4 A disappears, since the clay is intercalated with the polymer and exfoliates (inferior pattern), while it appears for mechanical mixing (superior pattern). EXAMPLE 5 The upper X-ray diffraction pattern of Figure 13 was taken from a fusion of 90% by weight of polyethylene terephthalate (PET) and 10% by weight of sodium bentonite clay (containing about 8% by weight) moisture) . The lower standard was taken from 100% sodium bentonite which shows the smectic characteristic peak d (001) at approximately 12.4 (12.37) A, and the characteristic peak d (020) at 4.47 A. When heated to the melting temperature of the PET (upper X-ray diffraction pattern), the smectic peak d (001) disappears as the PET is sandwiched between the clay platelets and the platelets are exfoliated. EXAMPLE 6 Figure 14 shows X-ray diffraction patterns of a molten mixture (250 ° C) of 60 wt% hydroxyethylterephthalate (HETPh) and 40 wt% sodium bentonite (containing about 8 wt% moisture) ), for the inferior pattern, and 100% HETPh for the superior pattern. As shown, no characteristic smectic peak d (001) appears at approximately 12.4 A for the molten mixture while the characteristic peak d (020) exists at approximately 4.48 A, indicating that the clay was interspersed with the HETPh, and the platelets are exfoliated. EXAMPLE 7 Figure 15 shows X-ray diffraction patterns of a molten mixture (250 ° C) of 70% by weight hydroxybutylterephthalate (HBTPh) and 30% sodium bentonite (which contains approximately 8% by weight of moisture). As shown, no characteristic smectic peak d (001) appears at approximately 12.4 A for the molten mixture, indicating that the clay was intercalated with the HBTPh, and the platelets exfoliated. EXAMPLE 8 Figure 16 shows an X-ray diffraction pattern of a molten mixture (280 ° C) of 50% by weight of polycarbonate and 50% by weight of sodium bentonite (containing about 8% by weight of moisture). As shown, no characteristic smectic peak d (001) appears at about 12.4 A for the molten mixture, indicating that the clay was intercalated with the polycarbonate, and the platelets exfoliated. The thermogravimetric analysis graph of Figure 18, as compared to Figure 17, shows that the EVOH complexed with sodium montmorillonite clay - the complex was then added to an EVOH matrix polymer - resulting in the substantial decomposition of the EVOH complexed However, by complexing the clay with an interlayer without EVOH (Figures 19, 20 and 21), the complexed clay plates can be added to an EVOH matrix polymer without intercalating decomposition, and without degrading the EVOH matrix polymer. Numerous modifications and alternative embodiments of the invention will be apparent to those skilled in the art in view of the foregoing description. According to the foregoing, this description is proposed only as illustrative and for the purpose of teaching those skilled in the art the best way to carry out the invention. The details of the structure may vary substantially without departing from the spirit of the invention, and exclusive use is reserved for all modifications that come within the scope of the appended claims.

Claims

NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and therefore the property described in the following claims is claimed as property. A composite material comprising a copolymer of ethylene vinyl alcohol in an amount of about 40% to about 99.95% by weight of the composite material, and about 0.05% to about 60% by weight of an interlayer of phyllosilicate or exfoliated platelets of said interleaved of phyllosilicate, formed said intercalated by the contact of a phyllosilicate with a composition containing intercalant of vinyl acetate without ethylene, said composition having a concentration of said intercalant of at least about 2% by weight intercalant, to achieve the sorption of the interlayer between adjacent spaced layers of the phyllosilicate to expand the spacing between a predominance of the adjacent phyllosilicate platelets to at least about 5A, when measured after the interleaver sorption.
2. A composite material according to claim 1, characterized in that the intercalant concentration in said composition contacting the phyllosilicate is at least about 5% by weight.
3. A composite material according to claim 1, characterized in that the intercalant concentration in said composition contacting the phyllosilicate is at least about 15% by weight.
4. A composite material according to claim 3, characterized in that the intercalant concentration in said composition contacting the phyllosilicate is at least about 20% by weight.
5. A composite material according to claim 4, characterized in that the intercalant concentration in said composition contacting the phyllosilicate is at least about 30% by weight.
6. A composite material according to claim 5, characterized in that the intercalant concentration in said composition contacting the phyllosilicate is in the range of about 50% to about 80% by weight.
7. A composite material according to claim 5, characterized in that the intercalant concentration in said composition contacting the phyllosilicate is in the range of about 50% to about 100% by weight.
8. A composite material according to claim 1, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is initially at least about 16% by weight, based on the dry weight of the contacted phyllosilicate.
9. A composite material according to claim 8, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is initially in the range of about 16% to about 70% by weight, based on the dry weight of the contacted phyllosilicate.
10. A material. compound according to claim 9, characterized in that the concentration of intercalant in the composition contacting the phyllosilicate is initially in the range of about 16% to less than about 35% by weight, based on the dry weight of the contacted phyllosilicate.
11. A composite material according to claim 9, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is initially in the range of about 35% to less than about 55% by weight, based on the dry weight of the contacted phyllosilicate. .
12. A composite material according to claim 9, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is 70% by weight, based on the dry weight of the contacted phyllosilicate.
13. A composite material according to claim 1, characterized in that the interleaving is selected from the group consisting of polyvinylpyrrolidone; polyvinyl alcohol; polyvinyl acetate / polyvinylpyrrolidone copolymers and mixtures thereof.
14. A composite material according to claim 13, characterized in that the intercalant is polyvinyl alcohol having less than about 5% by weight of acrylic substituents.
15. A composite material according to claim 14, characterized in that the intercalant is polyvinyl alcohol having less than about 1% by weight of acrylic substituents.
16. A composite material according to claim 1, characterized in that the intercalant is selected from the group consisting of N-methylpyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, and mixtures thereof.
17. A composite material according to claim 1, characterized in that the intercalant has an average molecular weight in the range of about 225 to about 1,000,000.
18. A composite material according to claim 17, characterized in that the interlayer has an average molecular weight in the range of about 225 to about 10,000.
19. A method for making the composite material according to claim 1, characterized in that it contains about 40% to about 99.95% by weight of an EVOH matrix polymer, and about 0.05% to about 60% by weight of exfoliated platelets of a phyllosilicate material , which comprises: contacting the phyllosilicate with a composition containing intercalant without EVOH comprising at least about 2% by weight of said interlayer, to achieve the intercalation of said interlayer between said adjacent phyllosilicate platelets in an amount sufficient to separate said platelets from adjacent phyllosilicate at a distance of at least about 5 A; and combining the platelets intercalated with said EVOH polymer.
The method according to claim 19, characterized in that it further includes the steps of heating the polymer sufficiently to provide the flow of said polymer and the delamination of the platelets of said phyllosilicate; and dispersing said delaminated platelets through said EVOH matrix polymer.
The method according to claim 19, characterized in that said intercalant-containing composition includes a vehicle comprising from about 5% to about 95% by weight of organic solvent, based on the total weight of said composition contacting said phyllosilicate.
22. The method according to claim 21, characterized in that said vehicle comprises from about 5% to about 95% of an aliphatic alcohol.
The method according to claim 22, characterized in that said alcohol is selected from the group consisting of methanol, ethanol, and mixtures thereof.
A method according to claim 19, characterized in that the phyllosilicate has a moisture content of at least about 4% by weight, and said intercalant composition includes at least about 5% by weight of an interlayer without EVOH in a liquid carrier.
The method according to claim 24, characterized in that said intercalant-containing composition includes a liquid carrier capable of solubilizing the intercalant, in an amount of about 5% to about 95% by weight, based on the total weight of said intercalant composition.
26. The method according to claim 25, characterized in that said vehicle comprises from about 30% to about 40% by weight of water, based on the total weight of the intercalant composition.
27. The method according to claim 26, characterized in that said liquid carrier comprises from about 35% to about 40% by weight of water. The method according to claim 25, characterized in that said vehicle comprises from about 5% to about 50% by weight of water, based on the total weight of the intercalant composition. The method according to claim 28, characterized in that the phyllosilicate is contacted with said interlayer in the form of a composition comprising an intercalant and water, and wherein the intercalant concentration in said intercalant composition is at least about 8% in weight, based on the dry weight of the phyllosilicate.