MXPA98008504A

MXPA98008504A - Intercalated and exfoliated formed with n-alkenilic amidas and / or monomeros, oligomeros, and / or acrylic functional alylic and pirrolidone copolymer, and composite materials containing them

Info

Publication number: MXPA98008504A
Application number: MXPA/A/1998/008504A
Authority: MX
Inventors: W Beall Gary; Tsipursky Semeon; I Vinokour Elena
Original assignee: Amcol International Corporation
Priority date: 1997-10-15
Filing date: 1998-10-14
Publication date: 2000-08-01

Abstract

Nanocomposites are manufactured by the combination of a host material, such as an organic solvent or a matrix polymer, and exfoliated intercalates formed by contacting a phyllosilicate with an intercalant selected from the group consisting of: (1) a monomer of N-alkenyl amide and an allylic monomer, (2) an oligomer formed by the copolymerization of an N-alkenyl amide monomer and an allylic monomer, (3) a polymer formed by the copolymerization of an N-alkenyl amide monomer and a allylic monomer and (4) mixtures thereof, to adsorb the intercalant between the adjacent phyllosilicate platelets. Sufficient polymer is adsorbed between the adjacent phyllosilicate platelets to expand adjacent platelets, in order to increase the separation by at least about 10 Angstroms, preferably at least about 20 Angstroms (measured after removing the water), and up to about 100 Angstroms. Angstroms and preferably on the scale of about 30 to 40 Angstroms, such that interleaving can easily be exfoliated, for example, when mixed with an organic solvent or a polymeric melt, to provide a carrier material for drugs and the like, or to provide a matrix polymer / platelet composite material (nanocomposite) -explacing intercalary platelets

Description

INTERCALED AND EXFOLIATED FORMED WITH N-ALKENILIC AMIDAS AND / OR MONOMEROS, OLIGOMEROS, AND / OR COPICRYERS ALILICQS AND PIRROLIDQNA FUNCIONALES E ACRILATO, AND COMPOSITE MATERIALS THAT CONTAIN THEM FIELD OF THE INVENTION The present invention relates to materials in interleaved layers, already exfoliated thereof, manufactured by sorption (adsorption and / or absorption) of one or more oligomers or polymers between the flat layers of an inflatable layer material, such as a phyllosilicate material or other layered material, to expand the spacing between layers of the adjacent layers by at least about 10 Angstroms. More particularly, the present invention relates to interleaves having at least two layers of monomer, oligomer, and / or polymer molecules sorbed on the inner surfaces of the adjacent layers of the flat platelets of a layered material, such as a phyllosilicate, preferably a smectite clay, to expand the inter-layer spacing by at least about 10 Angstroms, more preferably by at least about 20 Angstroms, and most preferably to at least about 30-45 Angstroms, and up to about 100 Angstroms , or the disappearance of the periodicity. The resulting intercalates are not entirely organophilic or entirely hydrophilic, but a combination of the two, and can easily be exfoliated during blending with a thermoplastic or thermoforrable polymeric melt, preferably a thermoplastic matrix polymer, to improve one or more properties of the matrix polymer. The resulting matrix polymer / platelet composites are useful as long as polymer / filler composite materials are used, for example, as the external body parts for the automotive industry; the heat-resistant polymeric automotive parts in contact with an engine block; the rim rope for the radial rims; food wrap that has better gas impermeability; electric components; food grade beverage containers; and any other use wherein it is desired to alter one or more physical properties of a matrix polymer, such as the characteristics of elasticity and temperature, for example, the glass transition temperature and the high temperature resistance.

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 molecules organic between the adjacent flat silicate layers, thereby substantially increasing the interlayer separation 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 mixing with high shear stress. The individual silicate layers, when mixed with a matrix polymer, before, after, or during the polymerization of the matrix polymer, for example, a polyamide - see U.S. Patent Nos. 4,739,007; 4,810,734; and 5,385,776 -, substantially improve one or more polymer properties, such as mechanical strength and / or high temperature characteristics. Examples of these prior art compounds, also referred to as "nanocomposites", are disclosed in the published TCP disclosure of Allied Signal, Inc., WO 93/04118, and in U.S. Patent Number 5,385,776 , which discloses the mixture of particles in individual platelets derived from silicate materials in interleaved layers, with one polymer, to form a polymer matrix having one or more properties of the matrix polymer improved by the addition of the exfoliated interlayer . As disclosed in International Publication Number WO 93/04118, interleaving is formed (the separation between layers, between the adjacent silicate platelets is increased) by the adsorption of a silane coupling agent or an onium cation, such as a quaternary ammonium compound, having a reactive group which be compatible with the matrix polymer. It is well known that these quaternary ammonium cations convert a highly hydrophilic clay, such as sodium or calcium montmorillonite, into organophilic clay capable of sorbing the organic molecules. A publication that discloses the direct intercalation (without solvent) of polystyrene and poly (ethylene oxide) in organically modified silicates, is Synthesis and Properties of Two-Dimensional Nanos tructs by Direct Intercalation of Polymer Mel ts in Layered Silicates, Richard A. Vaia et al., Chem. Mater. , 5: 1694-1696 (1993). Also, as disclosed in Adv. Materials, 7, Number 2: (1985), pages 154-156, New Polymer Electrolyte Nanocompositions: Mel t Intercalation of Poly (Ethylene Oxide) in Mica-Type Silicates, Richard A. Vaia et al., Poly (ethylene oxide) ) can be intercalated directly in the montmorillonite sodium and lithium montmorillonite by heating up to 80 ° C for 2 to 6 hours, to achieve a separation d of 17.7 Angstroms. The intercalation is accompanied by the displacement of water molecules, arranged between the clay platelets and the polymer molecules. However, apparently, the interleaved material could not be exfoliated, and was tested in the form of a granule. It was very surprising to one of the authors of these articles that the exfoliated material could be manufactured in accordance with the present invention. Previous attempts have been made to intercalate polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and poly (ethylene oxide) (PEO) between the montmorillonite clay platelets with little success. As described in Levy et al., Interlayer Adsorption of Polyvinylpyrrolidone on Montmorilloni, Journal of Colloid and Interface Science, Volume 50, Issue 3, March 1975, pages 442-450, attempts were made to sorb polyvinylpyrrolidone (average molecular weight of 40,000) between the monoionic montmorillonite clay platelets.

(Na, K, Ca, and Mg) by successive washes with absolute ethanol, and then trying to suck the polyvinylpyrrolidone by contact with 1 percent solutions of polyvinylpyrrolidone / ethanol / water, with different amounts of water, by replacing the molecules of the ethanol solvent that were sipped in the wash (to expand the platelets to about 17.7 Angstroms). Only sodium montmorillonite had expanded beyond a baseline separation of 20 Angstroms (eg, 26 Angstroms and 32 Angstroms), with 5+ percent H2O, after contact with polyvinylpyrrolidone / ethanol / H20 solution. It was concluded that ethanol was needed to initially increase the basal separation for a subsequent sorption of the polyvinylpyrrolidone, and that the water did not directly affect the sorption of the polyvinylpyrrolidone between the clay platelets (Table II, page 445), except for the montmorillonite. of sodium. The sorption was delayed and difficult, and had little success. Furthermore, as described in Greenland, Adsorption of Polyvinyl Alcohols by Montmorilloni, Journal of Colloid Sciences, Volume 18, pages 647-664 (1963), polyvinyl alcohols containing 12 percent residual acetyl groups, could increase the separation basal only by approximately 10 Angstroms, due to polyvinyl alcohol sorbed (PVOH). As the concentration of the polymer in the solution containing intercalating polymer increased from 0.25 percent to 4 percent, the amount of sorbed polymer was substantially reduced, indicating that sorption could only be effective at polymer concentrations in the polymer. composition containing intercalating polymer, in the order of 1 percent polymer or less. This dilution process for intercalation of the polymer in the layered materials would be exceptionally expensive to dry the materials in interleaved layers, for the separation of the intercalated polymer carrier, for example, water, and therefore, apparently no further work was done to its marketing. In accordance with an important feature of the present invention, the best results are achieved by using a monomer, an oligomer (defined herein as a prepolymer having from 2 to about 15 recurring monomer units, which may be the same or different), or a polymer composition (defined herein as having more than about 15 recurring monomer units, which may be the same or different), for interleaving, having at least about 2 percent, preferably at least about 5 percent in concentration weight of intercalating monomer, intercalating oligomer, or intercalating polymer, more preferably from about 50 percent to about 80 weight percent of monomer, oligomer, and / or polymer, based on the weight of the monomer, oligomer, and / or polymer and carrier (e.g., water and / or an organic solvent for the monomer inte rcalant, the intercalating oligomer, or the intercalating polymer), to achieve a better sorption of the monomers, oligomers, or intercalating polymers between the phyllosilicates platelets, and in such a way that less drying is required after the intercalation. The monomer, oligomer, or polymer sorbed between the silicate platelets that causes separation or aggregate spacing between the adjacent silicate platelets, and for simplicity of description, the monomers, oligomers, and polymers are hereinafter referred to as the "intercalante", or the "intercalating monomer", or the "intercalating polymer". In this manner, the water-soluble or water-insoluble oligomers or polymers will be sucked sufficiently to increase the separation between layers of the phyllosilicate in the range of about 10 Angstroms to about 100 Angstroms, for easier and more complete exfoliation, in a process commercially viable, regardless of the particular phyllosilicate or intercalant polymer. In accordance with an important feature of the present invention, the best results are achieved by using a monomer or oligomer (defined herein as a prepolymer having from 2 to about 15 recurring monomer units, which may be the same or different) or polymer composition (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 percent, preferably at least about 5 percent by weight, more preferably at least about 10 percent by weight concentration of intercalating monomer, intercalating oligomer, or intercalating polymer, more preferably from about 30 percent to about 80 percent by weight of monomer and / or oligomer and / or polymer, based on the weight of the monomer, or ligomer, and / or intercalating polymer and the carrier (eg, water with or without an organic solvent for the monomer, oligomer, or intercalating polymer), to achieve "a better sorption of the intercalating polymers between the phyllosilicate platelets. Regardless of the concentration of the monomer and / or intercalating polymer in the liquid solvent of the interleaver composition, the interleaver composition should have a interlayer: layer ratio of at least 1:20, preferably at least 1:10, more preferably at least 1: 5, and most preferably about 1: 4, to achieve efficient intercalation of the monomer or polymer between adjacent platelets of the layered material. The monomer, oligomer, or intercalating polymer sorbed between, and permanently bound to, the silicate platelets, causes separation or aggregate spacing between the adjacent silicate platelets, and for simplicity of description, the monomers, oligomers, and polymers intercalators are hereinafter referred to as the "intercalant", or the "intercalating monomer", or the "intercalating polymer". In this way, the oligomers or polymers will be sucked sufficiently to increase the separation between layers of the phyllosilicate on the scale from about 10 Angstroms to about 100 Angstroms, for one. Easier and more complete exfoliation, in a commercially viable process, regardless of the particular phyllosilicate or intercalant polymer. A phyllosilicate, such as a smectite clay, can be intercalated sufficiently for subsequent exfoliation by sorption of the monomers, oligomers, or polymers having carbonyl, hydroxyl, carboxyl, amine, amide, ether, ester, sulfate, sulfonate functionalities. , sulfinate, sulphamate, phosphate, phosphonate, phosphinate, or aromatic rings, to provide metal cation chelate type linkage between two functional groups of one or two intercalating polymer molecules and the metal cations bonded to the inner surfaces of the platelets of filosilicato. The sorption and electrostatic attraction of the metal cation or the bonding of a platelet metal cation between two oxygen or nitrogen atoms of the intercalating molecules; or the electrostatic bond between the cations between layers in the hexagonal or pseudo-hexagonal rings of the smectite layers and an aromatic ring structure of monomer, oligomer, or intercalating polymer, increases the interlayer separation between adjacent silicate platelets or other material in layers at least about 10 Angstroms, preferably at least about 20 Angstroms, and more preferably on the scale from about 30 Angstroms to about 45 Angstroms. These interleaved phyllosilicates can easily be exfoliated on individual phyllosilicate platelets. Depending on the conditions to which the composition is subjected during intercalation and exfoliation, particularly temperature; the pH; and the amount of water contained in the interleaver composition, the interleaving and / or exfoliate / carrier composition can be formed to any desired viscosity, for example, of at least about 100 centipoise, preferably at least about 500 to 1,000 centipoise, either gelled or not, and particularly to extremely high viscosities of about 5,000 to about 5,000,000 centipoises. The compositions are thixotropic, such that the shear stress will lower the viscosity for easier delivery, and then, by reducing the shear stress or eliminating shear, the compositions will increase their viscosity. The monomer, oligomer, or intercalating polymer, is sandwiched between the adjacent platelet spaces of the layered material for easy exfoliation, and complexed with the metal cations found on the surfaces of the platelets where the interlayer remains. of its intercalation or exfoliation, and it is combined with the carrier / solvent, or added to a polymer melt. It is theorized that the interlayer coating on the surfaces of the clay platelets is ionically complexed with the cations between layers, and participates (aid) in the viscosity and thixotropy of the carrier / solvent composition, and adds strength characteristics, vapor impermeability. , and significant temperature to a matrix polymer. However, other forms of bonding, such as hydrogen bonding or Van Der Waals forces, or molecular complex formation, may also be responsible for the adhesion of the interlayer to the surfaces of the layered material, either entirely or partly.

DEFINITIONS Whenever used in this Report Descriptive, the stipulated terms will have the following meanings: "Layered 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 Angstroms to about 50 Angstroms, preferably about 10 Angstroms. "Platelets" will mean the individual layers of the Layered Material. "Interleaved" shall mean a Layered Material that includes oligomer and / or polymer molecules disposed between adjacent platelets of the Layered Material, to increase interlayer spacing, between adjacent platelets, up to at least about 10 Angstroms, preferably at least approximately 20 Angstroms. "Collation" will mean a process to form an Interleaving. "Intercalary monomer" shall mean a mixture of an N-alkenyl amide, such as N-vinyl lactam, and an allylic monomer capable of copolymerizing before or after intercalation between adjacent platelets of a Material in layers. "Intercalating Polymer" or "Intercalating Oligomer", or "Intercalating" will mean an oligomer or polymer polymerized from the Intercalary Monomer mixture that is sorbed between the Platelets of the Layered Material, and complex form with the surfaces of the platelets to form an Interleaved "Intercalary Carrier" shall mean a carrier comprising water with or without an organic solvent used in conjunction with an Intercalary Monomer, Intercalating Oligomer, or Intercalating Polymer, to form an Intercalary Composition capable of achieving the intercalation of the Layered Material. "Interleaving Composition" shall mean a composition comprising an Intercalary Monomer, and / or a Intercalary Oligomer, and / or an Intercalant Polymer, a Intercalary Carrier will pause the Intercalary Monomer or Intercalating Polymer, and a Layered Material. "Sheeted" will mean the individual platelets of an Interleaved Layer Material, such that adjacent platelets of the Interleaved Layer Material can be individually dispersed throughout a matrix polymer, or through a carrier material, such as water, an alcohol or glycol, or any other organic solvent. "Exfoliation" will mean a process to form a Exfoliate from an Interleaved. "Nanocomposite" shall mean an oligomer, polymer, or copolymer having dispersed therein, a plurality of individual platelets obtained from a Layered Interleaved Layer Material. "Matrix Polymer" will mean a thermoplastic or thermoplastic polymer where the Interleaved and / or Exfoliated is dispersed, to form a Nanocomposite.

SUMMARY OF THE INVENTION Briefly stated, the present invention relates to interleaves formed by contacting a layered phyllosilicate are an intercalating monomer, an intercalating oligomer, and / or an intercalating polymer, to be slurried or intercalated into the monomer and / or intercalating polymer, or in the mixtures of intercalating monomers and intercalating polymers, between the adjacent phyllosilicate platelets. Sufficient monomer, oligomer, and / or intercalating polymer is sorbed between adjacent phyllosilicate platelets to expand the spacing between adjacent platelets (separation between layers) by a distance of at least about 10 Angstroms, preferably up to at least about 20 Angstroms ( measured after removing the water), and more preferably on the scale of about 30 to 45 Angstroms, so that the interleaving can be easily exfoliated, sometimes in a natural manner, without requiring a shear stress. Sometimes, interleaving requires shear stress that can be easily performed, for example, when mixing the interlayer with the polymer melt, to provide a matrix / platelet or nanocomposite polymer composite - platelets being obtained by exfoliating the phyllosilicate interspersed The monomer, oligomer, and / or intercalating polymer has affinity for the phyllosilicate, such that it is sorbed between, and remains associated with, the silicate platelets in the interlayer spaces, and after the exfoliation. Hereby, it is theorized that the bonding of the monomer and the polymer to the surfaces of the platelets is by electrostatic metal cation bonding, or complex formation, eg, chelation, of the metal cations of the phyllosilicate which shares electrons with two functionalities of carbonyl, carboxyl, hydroxyl, and / or amide, of an intercalating polymer molecule, or of two adjacent intercalating polymer molecules with an inner surface of the phyllosilicate platelets. These intercalants have sufficient affinity for the phyllosilicate platelets, in order to provide sufficient separation between layers for exfoliation, for example, from about 10 Angstroms to 100 Angstroms, preferably from about 10 Angstroms to 50 Angstroms, and to maintain the bond to the platelet surfaces, without the need for coupling agents or separating agents, such as the onium ion or silane coupling agents disclosed in the aforementioned prior art. The interleaver sorption should be sufficient to achieve expansion of the adjacent platelets of the layered material (when measured dry - having a maximum of about 5 weight percent water) to a separation between layers of at least about 10 Angstroms , preferably a separation of at least about 20 Angstroms, and more preferably a separation of about 30 to 45 Angstroms. To achieve the interleaves that can easily be exfoliated using the preferred intercalators disclosed herein, the weight ratio of the monomer, oligomer, intercalating polymer to the layered material, preferably a water-swellable smectite clay such as sodium bentonite. , in the interlayer composition making contact with the phyllosilicate, it should be at least about 1:20, preferably at least about 1:12 to 1:10, more preferably at least about 1: 5, and most preferably about about 1: 5 to about 1: 3. It is preferred that the concentration of the intercalating monomer and / or intercalating oligomer and / or intercalating polymer in the interlayer composition, based on the total weight of the intercalating monomer and / or intercalating oligomer and / or intercalating polymer, plus the intercalating carrier (water plus any organic liquid solvent) in the interleaver composition, be at least about 15 weight percent, more preferably at least about 20 weight percent interleaver, eg, from about 20 percent to 30 percent and to about 90 weight percent intercalating monomer, intercalating oligomer, or intercalating polymer, based on the weight of the interlayer plus the intercalating carrier (water plus any organic solvent) in the interlayer composition during intercalation. It has been found that the interleaves of the present invention increase in the separation between layers in steps. If the phyllosilicate is contacted with a composition containing intercalating monomer, or a composition containing intercalating oligomer, or a composition containing intercalating polymer, containing less than about 16 weight percent intercalant, for example, percent to about 15 weight percent interlayer, based on the dry weight of the phyllosilicate, a single interlayer layer width is swallowed (interspersed) between the adjacent platelets of the layered material. A single layer of intercalator sandwiched between the platelets increases the separation between layers up to about 10 Angstroms and up to less than 20 Angstroms. When the amount of interleaver is on the scale of about 16 percent to less than about 35 weight percent, based on the weight of the dry layer material, the interleaver is sorbed in a bilayer, thereby increasing the separation between layers up to about 10 Angstroms to about 16 Angstroms. In an interlayer filler in the intercalant containing composition of about 35 percent to less than about 55 percent interlayer, based on the dry weight of the contacted layer material, the interlayer spacing increases up to about 20 Angstroms at approximately 25 Angstroms, which corresponds to three layers of intercalant sorbed between the adjacent platelets of the layered material. In an interlayer filler from about 55 percent to about 80 percent interlayer, based on the dry weight of the dissolved or dispersed layer material in the interlayer composition, the interlayer separation will increase from about 30 Angstroms to about 35 Angstroms, corresponding to four and five layers of interspersed sorbido (intercalated) between the adjacent platelets of the material in layers. These interlayer separations have never been achieved by direct intercalation of a monomer, oligomer, or polymer molecule, without pre-sorption between layers of a swelling agent, such as an onium or silane coupling agent, and provides an easier and more complete exfoliation during the incorporation of the platelets in a thermoplastic or thermoplastic matrix polymer. These intercalates are especially useful mixed with thermoplastic or thermosettable matrix polymers in the manufacture of polymeric articles from polymer / platelet composite materials; and for the mixture of the intercalated and the interleaved exfoliated with polar solvents in the rheology modification, for example, of cosmetics, fluids for drilling oil wells, paints, lubricants, especially food grade lubricants in the manufacture of oil and fat, and the like. Once exfoliated, intercalary platelets are predominantly completely separated into individual platelets that have intercalating molecules complexed with the surfaces of the platelets, and the originally adjacent platelets are no longer retained in a separate parallel arrangement, but are free to move as platelets interlayer-coated (continuously or discontinuously) predominantly individual throughout an entire carrier, or through a matrix polymer melt, to act in a manner similar to a nanoscale filler material for the matrix polymer. Predominantly individual phyllosilicate platelets, which have their platelet surfaces complexed with intercalator, e.g., polymer molecules, are dispersed in a random, homogeneous, and uniform manner throughout a carrier, such as water or an organic liquid, or through a polymer melt. Once a composite matrix / platelet polymer material is set and hardened to a desired shape, the predominantly individual phyllosilicate platelets are permanently fixed in position, and are dispersed in a random, homogeneous, and uniform manner, predominantly as Individual platelets, through the entire matrix polymer / platelet composite material. As is recognized, the thickness of the individual exfoliated platelets (approximately 10 Angstroms) is relatively small compared to the size of the flat faces of the platelets. The platelets have an aspect ratio on the scale of about 200 to about 2,000. The dispersion of these finely divided platelet particles in a polymer melt provides a very large area of contact between the polymer and the platelet particles, for a given volume of particles in the compound, and a high degree of homogeneity of the platelets. in the composite material. High strength and modulus platelet particles, dispersed in a submicron size (at the nanoscale), impart greater mechanical reinforcement and a higher glass transition temperature (Tg) to the polymer matrix, than comparable charges of conventional reinforcing fillers of one size in microns, and can impart a lower permeability to matrix polymers than comparable fillers of conventional fillers. Although the nanocomposites disclosed in International Publication Number WO 93/04118 require a swelling / compatibilizing agent, such as a silane coupling agent, or a quaternary ammonium molecule, which has different binding interactions with both the polymer as with the platelet particle, to achieve better properties in the polymer, the intercalators used to form the interleaved and cleaved according to the present invention, do not need to have (but may include) reactivity with the matrix polymer where they are dispersed the interleaved and cleaved of the invention, while improving one or more properties of the matrix polymer.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES In order to form the interleaved materials of the present invention, the phyllosilicate must be swollen or intercalated by sorption of a mixture of an N-alkenyl amide intercalating monomer and an allylic intercalating monomer for on-site copolymerization ( which is sandwiched between adjacent silicate platelets after intercalation); or is intercalated by co-sorption of a co-oligomer or copolymer formed by the polymerization of a mixture of an N-alkenyl amide intercalating monomer and an allylic intercalating monomer. According to a preferred embodiment of the present invention, the phyllosilicate should include at least 4 percent by weight of water, up to about 5,000 percent of water, based on the dry weight of the phyllosilicate, preferably about 7 percent by weight. one hundred to about 100 percent water, more preferably about 25 percent to about 50 percent water by weight, before or during contact with the intercalator to achieve sufficient intercalation for exfoliation . Preferably, the phyllosilicate should include at least about 4 percent by weight of water prior to its contact with the intercalary carrier, for efficient intercalation. The amount of interlayer in contact with the phyllosilicate of the interlayer composition, for efficient exfoliation, 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 intercalating sorption and complexation (intercalation) between the platelets of the layered material, eg, phyllosilicate (preferably about 16 percent a about 70 weight percent interlayer, based on the dry weight of the layered silicate material). The intercalants are introduced in the form of a solid or liquid composition (a clean or aqueous solution or dispersion, and / or with an organic solvent, for example hydroalcoholic), having an intercalant concentration of at least about 2 percent, preferably from at least about 5 weight percent interlayer, more preferably from at least about 50 percent to about 100 weight percent interlayer, in the interlayer / carrier composition that contacts the material in layers for interleaver sorption. 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 of at least about 20 percent water to the layered / interlayer material mixture, for example, from about 20 percent to about 80 percent water, preferably when less than about 30 percent water to about 5,000 percent water, and / or another solvent for the intercalant, based on the dry weight of the more interlayer layer material, preferably from about 30 percent to about 50 percent water or another solvent, such that the interleaving sifts less water or solvent, thus requiring less drying energy after the collation. The interleaver can be introduced into the spaces between each layer, almost each layer, or at least a predominance of the layers of the material in layers, such that the platelet particles subsequently exfoliated are preferably predominantly less than about 5 layers of thickness; more preferably, predominantly about 1 or 2 layers thick; and most preferably, simple platelets. Any material in inflatable layers that sucks sufficiently to the intercalante to increase the separation between layers, between the adjacent phyllosilicate plates to at least about 10 Angstroms, preferably at least about 20 Angstroms (when the phyllosilicate is measured dry - having a maximum of about 5 weight percent water), it can be used in the practice of this invention. Useful inflatable layer materials include phyllosilicates, such as smectite clay minerals, for example montmorillonite, particularly sodium montmorillonite, magnesium montmorillonite, and / or calcium montmorillonite.; nontronite, beidelita; volkonskoite; hectorite; saponite; sauconite; soboquita; Estevensita; Esvinfordite; vermiculite; and similar. Other materials in useful layers include micaceous minerals, such as illites, and illite / smectite minerals in mixed layers, such as lediquita, and mixtures of illites with the clay minerals mentioned above. Other layered materials having little or no load on the layers may be useful in this invention, provided they can be interspersed with the intercalating polymers to expand their interlayer separation by at least about 10 Angstroms, preferably at least for approximately 20 Angstroms. Preferred foamable layer materials are 2: 1 type phyllosilicates, which have a negative charge on the layers of about 0.15 to about 0.9 fillers per unit of the formula, and a commensurate number of exchangeable metal cations in the interlayer spaces . The most preferred layer materials are the smectite clay minerals, such as montmorillonite, nontronite, beidelite, volkonskoite, hectorite, saponite, sauconite, soboquita, stevensite, and svinfordite. As used herein, "interlayer separation" refers to the distance between the internal faces of the adjacent dry silicates layers, as they are assembled in the layered material before any delamination takes place (exfoliation). The separation between layers is measured when the layered material is "air dried", for example, it contains about 3 to 10 weight percent water, preferably about 3 to 6 weight percent water, based on the dry weight of the material in layers. Preferred clay materials generally include inter-layer cations such as Na +, Ca + 2, K +, Mg + 2, NH 4 +, and the like, including mixtures thereof. The amount of intercalating monomer and / or intercalating oligomer and / or intercalating polymer intercalated in the interlayer spaces of the inflatable layer materials useful in this invention, so that the layered material interleaved in the platelets can be exfoliated or delaminated. individual, can vary substantially between about 10 percent and about 100 percent, generally between about 10 percent and about 80 percent, based on the dry weight of the layered silicate material. In the preferred embodiments of the invention, the amounts of intercalants employed, with respect to the dry weight of the layered material being interleaved, will preferably be from at least about 8 grams of interlayer / 100 grams of layered material (dry basis) , more preferably at least about 10 grams of interlayer / 100 grams of layered material, to about 80-90 grams of interlayer / 100 grams of layered material (dry basis). The most preferred amounts are from about 20 grams of interleaver / 100 grams of layered material to about 60 grams of interleaver / 100 grams of layered material (dry basis). The intercalants are introduced into (are sucked into) the spaces between layers of the layered 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 an intercalant / water solution, or an intercalant / organic solvent, for example an ethanol solution. To achieve the best interleaving for the exfoliation, the interlayer / layered material mixture contains at least about 8 weight percent interlayer, preferably at least about 10 percent interlayer, based on the dry weight of the interlayer material. layers. The intercalator carrier (preferably water, with or without an organic solvent, for example ethanol), can be added by splubilizing or dispersing the intercalant in the carrier first.; or the dry intercalant and the relatively dry phyllosilicate (preferably containing at least about 4 weight percent water) can be mixed, and the intercalating carrier is added to the mixture, or to the phyllosilicate, before adding the dry intercalant . In each case, it has been found that surprising sorption and complexation of the intercalant between the platelets is achieved at relatively low charges of intercalary carrier, especially H20, eg, about 4 weight percent water, based on dry weight of the filosilicato. When the phyllosilicate is sandwiched into a paste form (e.g., 408.24 kilograms of water, 45.36 kilograms of phyllosilicate, 11.34 kilograms of intercalant), the amount of water can vary from a preferred minimum of at least about 30 percent by weight of water, without an upper limit, up to the amount of water in the interleaving composition (the interlayer of phyllosilicate is easily separated from the interlayer composition). In an alternative way, the intercalary carrier, for example water, with or without an organic solvent, can be added directly to the phyllosilicate before adding the intercalant, either dry or in solution. Sorption of the intercalant molecules can be accomplished by exposing the layered material to dry or liquid intercalant compositions containing at least about 2 weight percent, preferably at least about 5 weight percent intercalant, more preferably at least about 50 percent interlayer, based on the dry weight of the layered material. Sorption can be aided by exposure of the intercalator composition to heat, pressure, ultrasonic cavitation, or microwaves. In accordance with another method for intercalating the intercalating molecules between the platelets of the layered material, and exfoliating the interleaving, the layered material, containing at least about 4 weight percent water, preferably about 10 percent at about 15 weight percent water, is mixed with a solubilized intercalant (in a carrier of water and / or organic solvent) in a sufficient proportion to provide at least about 8 weight percent, preferably at least about 10 percent by weight intercalant, based on the dry weight of the material in layers. Then the mixture is preferably extruded for a faster intercalation. In addition, the mixture can be heated to at least the melting temperature of the interlayer, and preferably at least about 40-50 ° C above the melting temperature of the interlayer for faster intercalation.

According to an important embodiment of the present invention, the polymerizable intercalating monomers and / or oligomers can be intercalated between the platelets of the layered material, or simply mixed with the exfoliated layered material, and the polymerizable monomers and / or oligomers they polymerize while they are interspersed between the platelets, or while in contact with the interleaved or with the exfoliated interlayer. To achieve the full advantage of the present invention, the polymerizable monomers, and the copolymers polymerized therefrom, include recurring units of an N-alkenyl amide and one or more allylic monomers selected from the group consisting of allylic alcohols, allyl esters, allyl ethers, and alkoxylated allyl alcohols. Optionally, one or more additional ethylenic monomers may be included. The monomers are copolymerized (before or after intercalation) to provide resins that are easily produced without the need for reaction solvents to control the speed of polymerization, and without the need for chain transfer agents to limit molecular weight. Resin intercalants offer valuable advantages for silicate-filled thermosetting coatings, sealants, elastomers, adhesives, and foams, as well as for composite materials that contain interleaved and delaminated ones that have resins complexed with the surfaces of silicate platelets. In the composites, the resins offer a good performance in a less expensive alternative to obtain commercially available intercalants made by the intercalation of more expensive water-soluble polymers, such as poly (N-vinylpyrrolidone). In coatings and other thermoformable applications, interleaves, their cleaners, and composite materials made by intercalating layered materials with these copolymer resins, offer oil resistance, better hydrophilicity, and a reduced dependence on salt content for water solubility. The N-alkenyl amides useful in the invention are compounds having a substituted or unsubstituted carbon-carbon double bond directly attached to the nitrogen of an amide. The preferred N-alkenyl amides have the general structure: R1- (C = 0) -NR2-C (R3) = C (R4) R5, wherein each of RL, R2, R3, R4, and R5 represents separately a member selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms. R? and R2 can form a ring to give an alkenyl lactam. Suitable alkenyl amides include, for example, N-vinyl formamide, N-vinyl-N-methyl acetamide, N-vinyl-N-methyl propanamide, and the like, and mixtures thereof. Other suitable N-alkenyl amides are described in U.S. Patent Nos. 5,622,533 and 5,625,076, the teachings of which are incorporated herein by reference. Preferred N-alkenyl amides include N-vinyl lactams, which are cyclic amides having a vinyl group (CH2 = CH-) attached to the nitrogen atom of the amide moiety. The lactam preferably has 4 to 10 ring atoms. More preferably, lactam has from 5 to 7 ring atoms. Suitable N-vinyl lactams include, for example, N-vinyl propiolactam, N-vinyl pyrrolidone, N-vinyl valerolactam, N-vinyl caprolactam, and the like, and mixtures thereof. N-vinylpyrrolidone and N-vinyl caprolactam are particularly preferred. In addition to, or in place of, the N-alkenyl amide, the resins of the invention may incorporate recurring units of an acrylate-functionalized pyrrolidone. Suitable acrylate-functionalized pyrrolidones include reaction products of N-2-hydroxyalkylpyrrolidones ester and acrylic or j-methacrylic acid. Suitable acrylate functionalized pyrrolidones also include ester reaction products of N-polyether pyrrolidones and acrylic or methacrylic acid. Examples of these and other useful acrylate-functionalized pyrrolidones appear in U.S. Patent No. 5, 629,359, whose teachings are incorporated herein by reference. The copolymer resin intercalants incorporate one or more allylic monomers. Suitable allylic monomers include allyl alcohols, allyl esters, allyl ethers, and alkoxylated allyl alcohols. The allylic alcohols useful in the manufacture of the intercalators of the present invention preferably have the general structure CH2 = CR-CH2 -OH, wherein R is selected from the group consisting of hydrogen and alkyl of 1 to 5 carbon atoms . Suitable allylic alcohols include, but are not limited to, allyl alcohol, metal alcohol, 2-ethyl-2-propen-1-ol, and the like, and mixtures thereof. Allyl alcohol and metal alcohol are preferred. Suitable allyl esters in the manufacture of the intercalators of the present invention preferably have the general structure: CH2-CR '-CH2-0-CO-R, wherein R is hydrogen or an alkyl group of 1 to 30 carbon atoms , aryl, or aralkyl, saturated or unsaturated, linear, branched or cyclic, and R 'is selected from the group consisting of hydrogen and alkyl of 1 to 5 carbon atoms. Suitable allyl esters include, for example, allyl acetate, allyl acetate, allyl butyrate, allyl benzoate, methallyl acetate, allyl fatty esters, and the like, and mixtures thereof. Allyl esters derived from allyl alcohol and metal alcohol are particularly preferred. Alkyl esters of 1 to 5 carbon atoms of the allyl alcohol and the metal alcohol are more preferred. Preferred allylic ethers have the general structure: CH2-CR '-CH2-0-R, wherein R is an alkyl group of 1 to 30 carbon atoms, aryl, or aralkyl, saturated, linear, branched or cyclic, and R is selected from the group consisting of hydrogen and alkyl of 1 to 5 carbon atoms. Suitable allyl ethers include, for example, allyl methyl ether, allyl ether, allyl tertiary butyl ether, allyl methyl benzyl ether, and the like, and mixtures thereof. The copolymer resin intercalants of the present invention can incorporate recurring units of an alkoxylated allyl alcohol. The preferred alkoxylated allylic alcohols have the general structure CH2 = CH '-CH2- (A) n-OH, where A is an oxyalkylene group, R' is selected from the group consisting of hydrogen and alkyl of 1 to 5 atoms of carbon, and n, which is the average number of oxyalkylene groups in the alkoxylated allyl alcohol, has a value of 1 to 50. Preferred oxyalkylene groups are oxyethylene, oxypropylene, oxybutylenes, and mixtures thereof. More preferred are propoxylated allylic alcohols having an average of 1 to 10 oxypropylene groups. Suitable alkoxylated allyl alcohols can be prepared by the reaction of an allylic alcohol with up to about 50 equivalents of one or more alkylene oxides, in the presence of a basic catalyst, as described, for example, in U.S. Pat. of North America Nos. 3,268,561 and 4,618,703, the teachings of which are incorporated herein by reference. As will be apparent to those skilled in the art, suitable alkoxylated allylic alcohols can also be made by acid catalysis, as described, for example, in J \ Am. Chem. Soc. , 71, (1949) 1152. The relative amounts of N-alkenyl amide and allylic monomer used to make the copolymer resin intercalants of the invention, depend on many factors, including the desired degree of hydrophilicity, the desired hydroxyl content, the nature of the monomers used, the property for the particular end-use application, and other factors. Preferably, the copolymer resin comprises from about 5 to about 95 percent by weight of recurring N-alkenyl amide units, and from about 5 to about 95 percent by weight of recurring allylic monomer units. In a more preferable way, the resin comprises from about 25 to about 75 weight percent recurring N-alkenyl amide units, and from about 25 to about 75 weight percent recurring units of allylic monomer. Most preferred resins comprise from about 30 to about 60 weight percent recurring N-alkenyl amide units, and from about 40 to about 70 weight percent recurring allylic monomer units. Optionally, the copolymer resin intercalators incorporate recurring units derived from one or more ethylenic monomers. The ethylenic monomer is often included to control the solubility of the resin, improve the physical properties, or reduce the cost. Preferably, the ethylenic monomer is used in an amount within the range of about 0.1 to about 50 weight percent, based on the total weight of the copolymerized monomers to form the copolymer. A more preferred scale is from about 1 to about 25 weight percent. Preferred ethylenic monomers include, for example, vinyl aromatic monomers, acrylates and metacrylates, unsaturated nitriles, vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, unsaturated anhydrides, unsaturated dicarboxylic acids, acrylic and methacrylic acids, acrylamide and methacrylamide, fluoroalkyl acrylates and methacrylates, conjugated dienes, and the like, and mixtures thereof. The copolymer resin intercalants of the invention preferably have number average molecular weights within the range of about 500 to about 100,000. A more preferred scale is from about 2,500 'to about 50,000. The copolymer resin intercalants have hydroxyl numbers within the range of 0 to about 400 milligrams of KOH / gram. (In other words, the resins do not need to have any hydroxyl group content, but may incorporate a substantial proportion of hydroxyl groups). A more preferred scale for the hydroxyl number is from about 25 to about 250 milligrams of KOH / gram; more preferred is the scale of about 50 to about 200 milligrams of KOH / gram. The need for hydroxyl groups depends on the application of intended end use. In coatings, for example, it is often important that the resin has a significant hydroxyl group content; in contrast, many compounds can benefit from copolymer resin intercalants of the invention that do not contain hydroxyl groups. The average hydroxyl functionality of the copolymer resin intercalators is generally 0 to about 20. Preferably, the hydroxyl functionality is within the range of about 2 to about 20; the scale from about 3 to about 10 is more preferred. As noted above, the need for the hydroxyl functionality depends on the desired end use. In coating applications, the glass transition temperature of the copolymer resin may be important. The copolymer resins of the invention preferably have a glass transition temperature (Tg) within the range of about -50 ° C to about 100 ° C. A more preferred scale is from about -40 ° C to about 40 ° C. The monomers are preferably copolymerized in the presence of a free radical initiator. The free radical initiator is preferably a peroxide, hydroperoxide, or an azo compound. Preferred initiators have a decomposition temperature greater than about 100 ° C. Examples include tertiary butyl hydroperoxide, tertiary dibutyl peroxide, tertiary butyl perbenzoate, eumenohydroperoxide, and the like.

The amount of free radical initiator required varies, but in general it is within the range of about 0.1 to about 10 weight percent, based on the amount of monomers. Preferably, the amount of free radical initiator used is within the range of about 1 to about 5 weight percent; the scale from about 2 to about 4 weight percent is more preferred. In general, it is preferred to add the free radical initiator to the reactor gradually during the course of the polymerization. When preparing resins for coating, it is also desirable to add the N-alkenyl amide gradually to the reactor, and to match the rate of addition of the free radical initiator with the polymerization rate of the N-alkenyl amide. When an ethylenic monomer is included, it is preferred to add it in proportion to the N-alkenyl amide. For example, if half of the N-alkenyl amide is gradually added, then it is preferred to charge half of the ethylenic monomer initially, and add the remaining portion with the N-alkenyl amide. As with N-alkenyl amide, all ethylene monomer can be added gradually. These techniques produce a polymer having a uniformly distributed hydroxyl functionality, which is relatively independent of molecular weight. A batch process, wherein all monomers are initially charged to the reactor, is suitable when the goal is to make copolymer resins for applications where the distribution of hydroxyl functionality in the resin is less important. In the preferred batch process, the N-alkenyl amide and the allylic monomer are initially charged, and the free radical initiator is added gradually as the reaction proceeds. The process for manufacturing the copolymer intercalators can be carried out over a wide temperature range. In general, the reaction temperature will be within the range of about 60 ° C to about 300 ° C. A more preferred scale is from about 90 ° C to about 200 ° C; the scale from about 100 ° C to about 180 ° C is more preferred. The process for making the copolymer intercalators is conveniently carried out in the absence of any reaction solvent, but a solvent may be included if desired. Useful solvents include those which do not interfere with the free radical polymerization reaction, or which do not otherwise react with the monomers. Suitable solvents include, for example, ethers, esters, ketones, aromatic and aliphatic hydrocarbons, alcohols, glycol ethers, glycol ether-esters, and the like, and mixtures thereof. One advantage of the process for making the copolymer intercalants is that no solvent is needed to polymerize the reactive monomers at a low polymerization rate. This obviates the need to remove a solvent later from the resin, and saves the expense of using and recovering a solvent. The process also gives low molecular weight polymer intercalants useful as polymeric interlayer intermediates, without the need to include a chain transfer agent. Chain transfer agents often impart undesirable odors, and decrease the final physical properties of a polymer. The invention includes intercalators and cleaners made using copolymer resins for use as fillers in thermoplastic and thermosetting polymers, including thermosetting coatings, sealants, elastomers, adhesives, and foams made using hydroxyl functional copolymer resin intercalants. Thermosetting agents include, for example, melamines, polyurethanes, epoxies, polyesters, alkyds, and uraniums. For example, interlayers based on melamine can be prepared by reacting the above-described copolymer resin intercalators with melamine resins. Suitable melamine resins include commercial grade hexametoxymethylmelamines, such as, for example, the crosslinking agent CYMEL 303, a product of Cytec. A polyurethane nanocomposite intercalant is made by reacting a hydroxyl functional copolymer interlayer with a di- or polyisocyanate, or with an isocyanate-terminated prepolymer, either on site (while interleaving), or before interleaving. The prepolymer intercalants derived from the copolymer resin intercalants can also be used to sandwich the materials. Optionally, a low molecular weight chain extender (diol, diamine, or the like) may be included with the monomers used to form the copolymer intercalators. Suitable di- or polyisocyanates are those well known in the polyurethanes industry, and include, for example, toluene diisocyanate, MDI, polymeric MDIs, carbodiimide-modified MDIs, hydrogenated MDIs, isophorone diisocyanate, 1-6. hexandiisocyanate, and the like. The isocyanate-terminated prepolymer intercalants are made in the usual manner from a polyisocyanate and a polyol ether polyol, polyester polyol, or the like. The polyurethane is formulated at any desired NCO index, but it is preferred to use an NCO index close to 1. If desired, all available NCO groups are treated with hydroxy groups of the copolymer resin and any chain extenders. The invention includes epoxie-filled thermosetting fillers with interleaving and / or fillers with exfoliation, and interleaves and delaminations intercalated with the copolymer intercalators which are the reaction products of the functional hydroxyl copolymer resins described above, and an epoxy resin. Suitable epoxy resins generally have two or more epoxide groups available to react with the hydroxyl groups of the copolymer resin. Particularly preferred epoxy resins are diglycidyl ether of bisphenol -A and the like. Other suitable methods for making epoxy thermoformable intercalators are described in U.S. Patent No. 4,609,717, the teachings of which are incorporated herein by reference. The intercalants also include thermosetting polyesters which are the reaction products of the above-described functional hydroxyl copolymer resins, and an anhydride or a di- or polycarboxylic acid. Suitable anhydrides and carboxylic acids are those commonly used in the polyester industry. Examples include phthalic anhydride, phthalic acid, maleic anhydride, maleic acid, adipic acid, isophthalic acid, terephthalic acids, sebasic acid, succinic acid, trimellitic anhydride, and the like, and mixtures thereof. Other suitable methods for making thermosetting polyester intercalators are described in U.S. Patent No. 3,457,324, incorporated herein by reference. The invention includes alkyd intercalators prepared by the reaction of the above-described functional hydroxyl copolymer intercalators with an unsaturated fatty acid. Suitable unsaturated fatty acids are those known in the art as useful for the alkyd resins, and include, for example, oleic acid, ricinoleic acid, linoleic acid, licánic acid, and the like, and mixtures thereof. Mixtures of unsaturated acids and saturated fatty acids, such as lauric acid or palmitic acid, can also be used. Alkyd resins are particularly useful for making alkyd coatings. For example, a functional hydroxyl copolymer resin, or a mixture of the resin and glycerin or other low molecular weight polyol, is first partially esterified with an unsaturated fatty acid, to give an alkyd resin. Then the resin is combined with an organic solvent, and the resin solution is stored until needed. A drying agent, such as cobalt acetate, is added to the alkyd resin solution, the solution is spread over a surface, the solvent is evaporated, and the resin is cured leaving an alkyd intercalant. Other suitable methods for making the alkyd resin intercalants are described in U.S. Patent Number 3, 423, 341, incorporated herein by reference. Instead of combining the alkyd resin with an organic solvent for the intercalation of the layered material, the resin intercalants can be dispersed in water to make a water-based alkyd intercalating composition. To improve the water dispersibility of alkyd resin intercalants, a free hydroxyl group of the alkyd resin can be converted into a salt. For example, the resin, alkyd can be reacted with phthalic anhydride to give a resin intercalant containing residues of phthalic acid; the action of sodium hydroxide makes the sodium phthalate salt, and provides a water-dispersible alkyd resin intercalant derived from the allyl ester copolymer. See, for example, United States Patent Number 3,483,152. The invention includes polyurethane-modified (polyurethane) alkyd intercalates prepared from the hydroxyl functional copolymer resin intercalants of the invention. These uralkyd resin intercalants and their exfoliates are especially valuable as fillers in the uralkide coatings. The functional hydroxyl copolymer resin is first partially esterified with an unsaturated fatty acid (described above), to give an alkyd resin. The alkyd resin, which contains some free hydroxyl groups, is reacted with a di- or polyisocyanate (described above), to give a prepolymer. The prepolymer is then reacted with a chain extender, in atmospheric humidity, or with additional alkyd resin, to give a urea-based interlayer. Other suitable methods for making the uralkyd resin intercalants are described in U.S. Patent No. 3,267,058, incorporated herein by reference. In the composites, the resins offer a good performance in a less expensive alternative for commercially available intercalators, such as poly (N-vinylpyrrolidone). The incorporation of allylic monomers makes it possible to make formulations to control the operation of the intercalating polymer, including bonding efficiency, while minimizing the cost. The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and the scope of the claims.

EXAMPLE 1 Copolymer Resin Intercalates from N-vinylpyrrolidone and Propoxylated Allyl Alcohol Allyl alcohol propoxylate (an average of 1.6 units of oxypropylene, 350 grams) is charged in a 1-liter reaction tank equipped with stirrer, heating mantle, temperature controller, nitrogen purge device, condenser, and addition pump. The N-vinylpyrrolidone (350 grams) and tertiary butyl perbenzoate (10 grams) are mixed at 5 ° C in a freezer, deoxygenated with nitrogen, and charged to the addition pump. After purging the reactor three times with nitrogen, the contents of the reactor are heated to 145 ° C. The N-vinylpyrrolidone / initiator mixture is gradually added at a uniform rate to the reactor for 4 hours at 145 ° C. The mixture is heated for another 45 minutes after the monomer addition is complete. Unreacted monomers are removed by vacuum separation of the mixture at 160 ° C. The copolymer resin product has an Mw = 12,600; Mn = 3260; and Tg = 21 ° C.

EXAMPLE 2 Copolymer Resin Intercalates from N-vinylpyrrolidone and Propoxylated Allyl Alcohol The procedure of Example 1 is followed, but allyl alcohol propoxylate with an average of 10 oxypropylene units (350 grams) is used. The polymer has a Tg = -28 ° C.

EXAMPLE 3 Copolymerisate Resin Intercalates from N-vinylpyrrolidone and Propoxylated Allyl Alcohol The procedure of Example 1 is followed, using 525 grams of allyl alcohol propoxylate (an average of 1.6 oxypropylene units), and 175 grams of N-vinylpyrrolidone. The copolymer resin has an Mw = 8660; Mn = 1570; and a hydroxyl number = 172 milligrams of KOH / gram.

EXAMPLE 4 Copolymer Resin Intercalates from N-vinylpyrrolidone and Allyl Alcohol Allyl alcohol (750 grams) and N-vinylpyrrolidone (750 grams) are charged in a 5 liter reaction tank equipped with stirrer, heating mantle, temperature controller , inputs for nitrogen and vacuum, condenser, and addition pump. Tertiary dibutyl peroxide (25 grams) is charged into the reactor. Additional tertiary dibutyl peroxide (50 grams) is added to the addition pump. After purging the reactor three times with nitrogen, the reactor contents are heated to 135 ° C. The initiator is added gradually at a decreasing speed to the reactor for 4 hours at 135 ° C. The addition of initiator is carried out as follows: first, 20 grams; second hour, 15 grams; third hour, 10 grams; fourth hour, 5 grams. The mixture is heated for another 60 minutes after the addition of the monomer is completed. Unreacted monomers are removed by vacuum separation of the mixture at 160 ° C.

The amount of interleaved and / or delaminated layer material included in a liquid carrier or in a matrix polymer to form viscous carriers or a composite polymer material, can vary widely, depending on the intended use of the material. When interleaving or exfoliation is added to a solvent to form viscous compositions suitable for delivering the carrier or some active material dissolved in the carrier or dispersed in the carrier, such as a pharmaceutical product, relatively higher amounts of intercalates are used, that is, from about 10 percent to about 30 percent by weight of the total composition, in the formation of solvent gels having extremely high viscosities, for example, from 5,000 to 5,000,000 centipoises. However, extremely high viscosities can also be achieved with a relatively low concentration of interleaves and / or cleaved thereof, for example, from 0.1 percent to 5 percent by weight, adjusting the pH of the composition on the scale of approximately 0 to 6 or from about 10 to 14, and / or heating the composition above room temperature, for example, in the range from about 25 ° C to about 200 ° C, preferably from about 75 ° C to about 100 ° C. Relatively larger amounts of platelet particles are used (excluding the intercalating polymer, since the content of intercalating polymer in the layered material can vary), i.e. from about 15 percent to about 30 percent by weight of the mixing, in applications where interleaving and / or delamination is added to a matrix polymer, and the composite material is used to form patterned polymer articles. Substantially improved barrier properties and heat resistance (deviation temperature under load, DTUL) are imparted by platelet particle concentrations greater than about 2.5 percent in a matrix polymer. In a similar manner, substantially improved strength is imparted by platelet particle concentrations greater than about 1.5 percent, including the nanoscale layer materials of this invention. It is preferred that the platelet load be less than about 10 percent. The platelet particle loads within the range of about 0.05 percent to about 40 percent by weight, preferably from about 0.5 percent to about 20 percent, more preferably from about 1 percent to about 10 percent of the composite material significantly improves the modulus, dimensional stability, and wet strength. In general, the amount of platelet particles incorporated in the matrix polymer is less than about 90 percent by weight of the mixture, and preferably from about 0.01 percent to about 80 percent by weight of the mixture. composite material, more preferably from about 0.05 percent to about 40 percent by weight of the polymer / particle mixture, and most preferably from about 0.05 percent to about 20 percent, or from 0.05 percent to about 10 percent by weight, with some matrix polymers. In accordance with an important feature of the present invention, the interleaved phyllosilicate can be manufactured in a concentrated form, for example, from 10 to 90 percent, preferably 20 to 80 percent intercalating polymer, and from 10 to 90 percent by weight. percent, preferably 20 to 80 percent interleaved phyllosilicate that can be dispersed in a solvent or matrix polymer, and can be exfoliated before or after addition to the solvent or polymer melt, to a desired platelet load. The interleaves are exfoliated and dispersed in a host material, such as an organic solvent, or one or more thermoplastic and / or melt-processable thermoplastic or meltable matrix polymers or oligomers, or mixtures thereof. In accordance with an important feature of the present invention, a wide variety of locally active compounds can be incorporated into a stable composition of the present invention. These locally active compositions include cosmetic, industrial, and medicinal compounds, which act upon contact with the skin or hair, or which are used to adjust the rheology of industrial greases and the like. In accordance with another important feature of the present invention, a locally active compound can be solubilized in the composition of the present invention, or it can be dispersed homogeneously throughout the composition as an insoluble particulate material. In any case, the locally effective compositions of the present invention are resistant to separation of the composition, and effectively apply the locally active compound to the skin or hair. If required for stability, a surfactant may be included in the composition, such as any disclosed in Laughlin et al., U.S. Patent Number 3,929,678, incorporated herein by reference. In general, the locally effective compositions of the present invention do not demonstrate essentially phase separation, if the locally active compound is solubilized in the compositions. In addition, if the locally active compound is insoluble in the composition, the composition essentially does not demonstrate phase separation. Compounds locally active may be a cosmetically active compound, a medically active, "or any other compound that is useful upon application to the skin or hair. These compounds locally active include, for example, antiperspirants, antidandruff agents, antibacterial compounds, antifungal compounds, anti-inflammatory compounds, local anesthetics, sunscreens, and other locally effective cosmetic and medical compounds.Therefore, in accordance with an important feature of the present invention, the locally effective stable composition can include any of the generally known antiperspirant compounds, such as finely divided solid astringent salts, for example, aluminum chlorohydrate, chlorohydroxyaluminium, zirconium hydrochloride, and complexes of aluminum chlorohydrate with zirconyl chloride or zirconyl hydroxychloride In general, the amount of the antipe compound Respirator, such as aluminum and zirconium tetrachlorohydrexglycine in the composition, may be from about 0.01 percent to about 50 percent, and preferably from about 0.1 percent to about 30 percent by weight of the total composition. Other locally active compounds can be included in the compositions of the present invention, in an amount sufficient to perform their intended function. For example, zinc oxide, titanium dioxide, or similar compounds may be included, if the composition is intended as a sunscreen. In a similar way, locally active drugs, such as antifungal compounds, can be included; antibacterial compounds; anti-inflammatory compounds; local anesthetics; medications for skin itching, skin disease, and dermatitis; and anti-itch compounds and irritation reducers, in the compositions of the present invention. For example, analgesics, such as benzocaine, dichlonine hydrochloride, aloe vera and the like; anesthetics such as butambene picrate, lidocaine hydrochloride, zylocaine, and the like, antibacterials and antiseptics, such as povidone-iodine, polymyxin sulphate b-bacitracin, zinc-neomycin sulfate-hydrocortisone, chloramphenicol, methylbenzethonium chloride, and erythromycin and the like; antiparasitic, such as lindane; deodorants, such as chlorophyllin-copper complex, aluminum chloride, aluminum chloride hexahydrate, and methylbenzethonium chloride; essentially all dermatological ones, such as preparations for acne, such as benzoyl peroxide, erythromycin-benzoyl peroxide, clindamycin phosphate, 5,7-dichloro-8-hydroxyquinoline, and the like; anti-inflammatory agents, such as alclometasone dipropionate, betamethasone valerate, and the like; ointments for the relief of burns, such as o-amino-p-toluenesulfonamide monoacetate and the like; depigmenting agents, such as monobenzone; agents for the relief of dermatitis, such as the active steroids amcinodine, diflorasone diacetate, hydrocortisone, and the like; agents for the relief of diaper itching, such as methylbenzethonium chloride and the like; emollients and humectants, such as mineral oil, PEG-4 dilaurate, lanolin oil, petrolatum, mineral wax and the like; fungicides, such as butocouazole nitrate, haloprogin, clotrimazole, and the like; drugs for the treatment of herpes, such as 9- [(2-hydroxyethoxy) methyl] guanine; pruritic drugs, such as alclometasone dipropionate, betamethasone valerate, isopropyl myristate MSD, and the like; agents for psoriasis, seborrhea, and scabicide, such as anthralin, methoxsalen, coal tar, and the like; sunscreens, such as octyl p- (dimethylamino) benzoate, octyl methoxycinnamate, oxybenzone and the like; steroids, such as 2- (acetyloxy) -9-fluoro-1 ', 2', 3 ',' -tetrahydro-ll-hydroxypregna-l, 4-diene [16, 17-b] -naphthalen-3, 20- dione, and 21-chloro-9-fluoro-1 ', 2', 3 ', 4' -tetrahydro-l, 1-hydroxy-dipne-1,4-diene [16z, 17-b] naphthalene-3, 20-dione. Any other drug that can be administered locally, in the composition of the present invention, in an amount sufficient to perform its intended function can also be incorporated. The matrix polymers for use in the process of this invention can vary widely, and the only requirement is that they can be processed by melting. The resin intercalants described herein, of course, are fully compatible with the matrix polymers, which are the same as the resin intercalants. Additionally, the matrix polymers can be altered in percentages of monomer, or they can contain an ethylenic monomer, wherein the copolymer intercalants contain only the N-alkenyl amide and / or the pyrrolidone functionality with acrylate, and an allylic monomer. In the preferred embodiments of the invention, the matrix polymer includes at least 10, preferably at least 30 recurring monomer units. The upper limit for the number of recurring monomer units is not critical, provided that the melt index of the matrix polymer under the conditions of use is such that the matrix polymer forms a flowable mixture. More preferably, the matrix polymer includes from at least about 10 to about 100 recurring monomer units. In the most preferred embodiments of this invention, the number of recurring units is such that the matrix polymer has a melt index of about 0.01 to about 12 grams per 10 minutes at the processing temperature. Thermoplastic resins and rubbers for use as matrix polymers in the practice of this invention can vary widely. Illustrating useful thermoplastic resins, which may be used alone or in admixture, are polylactones, such as poly (pivalolactone), poly (caprolactone), and the like; polyurethanes derived from the reaction of diisocyanates, such as 1,5-naphthalene diisocyanate; p-phenylene diisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4-diisocyanate '-diphenylisopropylidene, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-, 4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-, 4'-biphenyl diisocyanate, dianisidine diisocyanate, toluidine diisocyanate, hexamethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane, and the like, and linear long chain hydroxyl terminated polyesters; polyethers based on diols, such as poly (tetramethylene adipate), poly (ethylene adipate), poly (1,4-butylene adipate), poly (ethylene succinate), poly (2,3-butylene succinate), polyether diols, and the like; polycarbonates, such as poly [metan-bis (4-phenyl) carbonate], poly [1,1-ether-bis (4-phenyl)] carbonate, poly [diphenylmethane-bis (4-phenyl) carbonate], poly [1,1-cyclohexane-bis [4-phenyl] carbonate], and the like; polysulfones; polyethers; polyketones; polyamides such as poly (4-aminobutyric acid), poly (hexamethylene adipamide), poly (6-aminohexanoic acid), poly (m-xylylene adipamide), poly (p-xylylene sebacamide), poly (2-terephthalamide), 2,2-trimethylhexamethylene), poly (metaphenylene isophthalamide) (NOMEX), poly (p-phenylene terephthalamide) (KEVLAR), and the like; polyesters, such as poly (ethylene azelate), poly (1, 5-ethylene naphthalate), poly (1,4-cyclohexanedimethylene terephthalate), poly (ethylene oxybenzoate) (A-TELL), poly (para-hydroxybenzoate) (EKONOL), poly (1,4-cyclohexylidenedimethylene terephthalate) (KODEL) (cis), poly (1,4-cyclohexylidenedimethylene terephthalate) (KODEL) (trans), polyethylene terephthalate, polybutylene terephthalate, and the like; poly (arylene oxides), such as poly (2,6-dimethyl-1,4-phenylene oxide), poly (2,6-diphenyl-1,4-phenylene oxide), and the like; poly (arylene sulfides), such as poly (phenylene sulfide), and the like; polyetherimides; vinyl polymers and their copolymers, such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride; polyvinyl butyral, polyvinylidene chloride, ethylene-vinyl acetate copolymers, and the like; polyacrylics, polyacrylate and their copolymers such as polyethyl acrylate, poly (normal butyl acrylate), polymethylmethacrylate, polyethylmethacrylate, poly (normal butyl methacrylate), poly (normal propyl methacrylate), polyacrylamide, polyacrylonitrile, polyacrylic acid, copolymers ethylene-acrylic acid, ethylene-vinyl alcohol copolymers, acrylonitrile copolymers, methyl methacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers, butadiene-methacrylate-styrene copolymers, and the like; polyolefins, such as low density poly (ethylene), poly (propylene), chlorinated low density poly (ethylene), poly (4-methyl-1-pentene), poly (ethylene), poly (styrene), and the like; ionomers; poly (epichlorohydrins); poly (urethane), such as the polymerization product of diols, such as ethylene glycol, propylene glycol, and / or a polydiol, such as diethylene glycol, triethylene glycol, and / or tetraethylene glycol, and the like, with a polyisocyanate, such as a diisocyanate of 2, 4-toluene, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like; and polysulfones, such as the reaction product of the sodium salt of 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dichlorodiphenylsulfone; furan resins, such as poly (furan); cellulose ester plastics, such as cellulose acetate, cellulose acetate butyrate,. cellulose propionate, and the like; silicones, such as poly (dimethylsiloxane), poly (dimethylsiloxane-co-phenylmethylsiloxane), and the like; protein plastics; and mixtures of two or more of the above. The vulcanizable and thermoplastic rubbers useful in the practice of this invention can also vary widely. Illustrating these rubbers are brominated butyl rubber, chlorinated butyl rubber, polyurethane elastomers, fluoroelastomers, polyester elastomers, polyvinyl chloride, butadiene / acrylonitrile elastomers, silicone elastomers, poly (butadiene), poly (isobutylene), copolymers ethylene-propylene, ethylene-propylene-diene terpolymers, sulfonated-ethylene-propylene-diene terpolymers, poly (chloroprene), poly (-2, 3-dimethylbutadiene), poly (butadiene-pentadiene), poly (ethylenes) chlorosulfonated, poly (sulfide) elastomers, block copolymers, made of glazed or crystalline block segments, such as poly (styrene), poly (vinyl toluene), poly (tertiary butyl-styrene), polyesters and the like, and elastomeric blocks, such such as poly (butadiene), poly (isoprene), ethylene-propylene copolymers, ethylene-butylene copolymers, polyether, and the like, such as, for example, copolymers in the poly block copolymer (styrene) -poly (butadiene) -poly (styrene) manufactured by Shell Chemical Company under the tradename KRATONR. Useful thermosetting resins include, for example, polyamides, polyalkylamides; polyesters, polyurethanes; polycarbonates; polyepoxides; and mixtures thereof. Thermosetting resins based on water soluble prepolymers include formaldehyde-based prepolymers: phenols (phenol, cresol, and the like); urea; melamine and phenol; urea and phenol. The polyurethanes based on: toluene diisocyanate (TDI), and monomeric and polymeric phenyl meta-diisocyanates (MDI); hydroxy-terminated polyethers (polyethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene oxide, and the like); amino-terminated polyethers, polyamines (tetramethylenediamine, ethylenediamine, hexamethylenediamine, 2,2-dimethyl-1,3-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, glycols and aromatic polyglycols; unsaturated polyesters based on vinyl, allyl, and acryl monomers; epoxides, based on bisphenol A (2,2'-bis (4-hydroxyphenyl) propane), and epichlorohydrin; epoxy prepolymers based on monoepoxide and polyepoxy compounds and a, ß-unsaturated compounds (styrene, vinyl, allyl, acrylic monomers); polyamides, 4-tetramethylenediamine, hexamethylenediamine, melamine, 1,3-propanediamine, diaminobenzene, triaminobenzene, 3,3 ', 4,4'-bitriaminobenzene; 3, 3 ', 4, 4' -biphenyltetramine, and the like. Polyethyleneimines; amides and polyamides (di-, tri-, and tetra-acid amides); hydroxyphenols (pyrogallol, 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; polybenzimidazoles based on 3, 3 ', 4,4'-biphenyltetramine and isophthalic acid; polyamide based on unsaturated dibasic acids and anhydrides (maleic, fumaric) and aromatic polyamides; alkyd resins based on dibasic aromatic acids or anhydrides, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and unsaturated fatty long chain carboxylic acids (the latter being derived from vegetable oils); and prepolymers based on acrylic (hydroxy- or carboxy-functional) monomers. The most preferred thermoplastic polymers are thermoplastic polymers such as polyamides, polyesters, and polymers of 0.-3-unsaturated monomers and copolymers. The polyamides which can be used in the process of the present invention are synthetic linear polycarbonyamides, characterized by the presence of recurring carbonamide groups as an integral part of the polymer chain, which are separated from each other by at least 2 carbon atoms. Polyamides of this type include polymers, generally known in the art as nylon, obtained from diamines and dibasic acid having the recurring unit represented by the general formula: -NHCOR13COHNR14 - wherein R13 is an alkylene group of at least 2 carbon atoms, preferably from about 2 to about 11, or arylene having at least about 6 carbon atoms, preferably from about 6 to about 17 carbon atoms; and R14 is selected from R13 and aryl groups. Also included are the copolyamides and terpolyamides obtained by known methods, for example, by the condensation of hexamethylenediamine and a mixture of dibasic acids consisting of terephthalic acid and adipic acid. The polyamides of the above description are well known in the art, and include, for example, the copolyamide of 30 percent hexamethylenediammonium isophthalate, and 70 percent hexamethylene diammonium adipate, poly (hexamethylene-nadipamide) (nylon 6, 6), poly (hexamethylene sebacamide) (nylon 6.10), poly (hexamethylene phosphthalamide), poly (hexamethyleneterephthalamide), poly (hexamethylene-dimethylamide) (nylon 7.7), poly (octamethylene sebacamide) (nylon 8, 8), poly ( nonamethylene-lamide) (nylon 9.9), poly (decamethylene azelamide) (nylon 10.9), poly (decamethylene sebacamide) (nylon 10.10), poly [bis (4-aminocilohexyl) methan-1, 10-decancarboxamide)] , poly (m-xylylenadipamide), poly (p-xylylene sebacamide), poly (2,2,2-trimethylhexamethyleneterephthalamide), poly (piperazinesebacamide), poly (p-phenyleneterephthalamide), poly (metaphenyleneisophthalamide), and the like. Other useful polyamides are those formed by the polymerization of amino acids and derivatives thereof, such as, for example, lactams. Illustrative of these useful polyamides are poly (4-aminobutyric acid) (nylon 4), poly (6-aminohexanoic acid) (nylon 6), poly (7-aminoheptanoic) (nylon 7), poly (8-aminooctanoic acid) (nylon 8). ), poly (9-aminononanoic acid) (nylon 9), poly (10-aminodecanoic acid) (nylon 10), poly (ll-aminounde-canoic acid) (nylon 11), poly (12-aminododecanoic acid) (nylon 12) ), and the like. Preferred polyamides are poly (caprolactam), poly (12-aminododecanoic acid), and poly (hexamethylene di-pamida). Other matrix polymers or hosts that can be used mixed with the cleaved to form nanocomposites, are linear polyesters. The type of polyester is not critical, and the particular polyesters selected for use in any particular situation will depend essentially on the physical properties and characteristics, i.e., the tensile strength, the modulus, and the like, desired in the form final. Accordingly, a multiplicity of linear thermoplastic polyesters having wide variations in their physical properties are suitable for use in admixture with the platelets of the exfoliated layer material in the manufacture of the nanocomposites in accordance with this invention.

The particular polyester selected for use may be a homo-polyester or a co-polyester, or mixtures thereof, as desired. The polyesters are usually prepared by the condensation of an organic dicarboxylic acid and an organic diol, and the reactants can be added to the interleaves, or the exfoliated interlayers, for polymerization at the polyester site while in contact with the layered material , before or after the exfoliation of the intercalated ones. Polyesters which are suitable for use in this invention are those which are derived from the condensation of aromatic, cycloaliphatic, and aliphatic diols, with aliphatic, aromatic, and cycloaliphatic dicarboxylic acids, and may be cycloaliphatic, aliphatic, or aromatic polyesters. Examples of the useful cycloaliphatic, aliphatic, and aromatic polyesters that can be used in the practice of this invention are polyethylene terephthalate, poly (cyclohexylenedimethylene terephthalate), poly (ethylene dodecate), polybutylene terephthalate. ), poly [(2,7-naphthalate) of ethylene], poly (metaphenylene isophthalate), poly (glycolic acid), poly (ethylene succinate), poly (ethylene adipate), poly (decamethylene azelate), poly (ethylene sebacate), poly (decamethylene adipate), poly (decamethylene sebacate), poly (dimethylpropiolactone), poly (para-hydroxybenzoate) (EKONOL), poly (ethylene oxybenzoate) (A-tell), poly (isophthalate) ethylene), poly (tetramethylene terephthalate), poly (hexamethylene terephthalate) poly (decamethylene terephthalate), poly (1,4-cyclohexanedimethylene terephthalate) (trans), poly (1, 5-ethylene naphthalate), poly (2,6-ethylene naphthalate), poly (1,4-cyclohexylidenedimethylene terephthalate) (KODEL) (cis), and poly (1,4-cyclohexylidenedimethylene terephthalate) (KODEL) (trans). The polyester compounds prepared from the condensation of a diol and an aromatic dicarboxylic acid are especially suitable according to the present invention. Illustrative of these useful aromatic carboxylic acids are terephthalic acid, isophthalic acid, and o-phthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4 '-diphenyldicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid, 1,3-trimethyl-5-carboxy-3- (p-carboxyphenyl) -indane, diphenyl ether, 4,4'-dicarboxylic acid , bis-p (carboxyphenyl) ethane, and the like. Of the aforementioned aromatic dicarboxylic acids, those based on a benzene ring (such as terephthalic acid, isophthalic acid, orthophthalic acid) are preferred for use in the practice of this invention. Among these preferred acid precursors, the particularly preferred acid precursor is terephthalic acid. The most preferred embodiments of this invention incorporate intercalating a polymer selected from the group consisting of poly (ethylene terephthalate), poly (butylene terephthalate), poly (1-cyclohexanedimethylene terephthalate), a polyvinylimine, and mixtures thereof. thereof. Among these polyesters of choice, poly (ethylene terephthalate) and poly (butylene terephthalate) are more preferred. Still other matrix polymers of thermoplastic homopolymers and copolymers useful for forming nanocomposites, are the polymers formed by the polymerization of alpha-beta-unsaturated monomers of the formula: R15R16C = CH2 wherein: R15 and R16 are the same or different, and are cyano , phenyl, carboxy, alkyl ester, halogen, alkyl, alkyl substituted by one or more of chloro or fluoro, or hydrogen. Illustrative of these preferred homopolymers and copolymers are the homopolymers and copolymers of ethylene, propylene, vinyl alcohol, acrylonitrile, vinylidene chloride, acrylic acid esters, methacrylic acid esters, chlorotrifluoroethylene, vinyl chloride, and the like. Poly (propylene), propylene copolymers, poly (ethylene) copolymers and ethylene are preferred. More poly (ethylene) and poly (propylene) are preferred. In the preferred embodiments of the invention, the matrix polymers of choice in the manufacture of nanocomposites are the polymers and copolymers of olefins, polyesters, polyamides, polyvinylimines, and mixtures thereof containing polyesters. In the particularly preferred embodiments of the invention, polymers and copolymers of ethylene, polyamides (preferably nylon 6 and nylon 66, and more preferably nylon 6), and mixtures thereof are used. The blend may include different optional components that are additives commonly employed with the polymers. These optional components include nucleating agents, fillers, plasticizers, impact modifiers, chain extenders, plasticizers, colorants, mold release lubricants, antistatic agents, pigments, fire retardants, and the like. These optional components and the appropriate amounts are well known to those skilled in the art. Exfoliation of the interlayer layer material should provide the delamination of at least about 90 weight percent of the interleaved material, to provide a composition comprising a polymer matrix having platelet particles dispersed in a substantially homogeneous manner therein. Some interleaves require a shear rate greater than about 10 sec. "1 for this relatively complete exfoliation, others interspersed naturally or exfoliating by heating at the melting temperature of the intercalating polymer, or by applying pressure, for example, 0.5 to 60 atmospheres above the ambient, with or without heating The upper limit for the shear rate is not critical, provided that the shear rate is not so high as to physically degrade the polymer. Particularly preferred embodiments of the invention, when a shear stress is employed for exfoliation, the shear rate is from more than about 10 sec. "1 to about 20,000 sec.", and in the most preferred embodiments of the invention, the index of shear stress is approximately 100 sec "1 to approximately 10,000 sec" 1. When short effort is employed For exfoliation, any method that can be used to apply shear stress to a flowable mixture or to any polymer melt can be used. The shearing action can be provided by any suitable method, such as, for example, by mechanical elements, by thermal shock, by pressure alteration, or by ultrasound, all of which are known in the art. In particularly useful processes, the flowable polymer mixture is torn by mechanical methods, where portions of the melt are made to flow into other portions of the mixture, by the use of mechanical elements, such as stirrers, Banbury type mixers. *, Brabender® type mixers, long continuous mixers, and extruders. Another method employs thermal shock, where tearing is achieved by alternately raising or lowering the temperature of the mixture, causing thermal expansions, and resulting in internal stresses that cause tearing. In still other procedures, tearing is achieved by sudden pressure changes in pressure alteration methods; by ultrasonic techniques, wherein cavitation or resonant vibrations cause portions of the mixture to vibrate or be excited in different phases, and thus undergo tearing. These methods of tearing the flowable polymer blends and polymer melts are merely representative of the useful methods, and any method known in the art can be used to tear the flowable polymer blends and polymer melts. Mechanical shear methods, such as by extrusion, injection molding machines, Banbury.RTM. Type mixers, Brabender.RTM. Type mixers, and the like, can be employed. The tear can also be achieved by introducing the polymer melt at one end of the extruder (single screw or twin screw), and receiving the polymer torn at the other 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, double screw, number of blades per unit length, depth of channel, tolerance of blades, mixing zone, etc.), are several variables that control the amount of shear that is going to be applied. The exfoliation must be sufficiently complete to provide at least about 80 weight percent, preferably at least about 85 weight percent, more preferably at least about 90 weight percent, and most preferably at least about 95 weight percent, and most preferably at least about 95 weight percent, and most preferably at least about 95 weight percent. percent by weight of delamination of the layers, to form the platelet particles dispersed in a substantially homogeneous manner in the polymer matrix. Already formed by this process, the platelet particles dispersed in the matrix polymers have the thickness of the individual layers, or small multiples less than about 10, preferably less than about 5, and more preferably less than about three of the layers , and still more preferably "of one or two layers In the preferred embodiments of this invention, the intercalation and delamination of each interlayer space is completed, such that all or substantially all of the individual layers are delaminated from each other to forming separate platelet particles In cases where intercalation is incomplete between some layers, these layers will not delaminate in the polymer melt, and will form platelet particles that comprise these layers in a coplanar aggregate. matrix polymer platelet particles dispersed in nanoscale particles, derived from As a result of the interleaves formed in accordance with the present invention, it is usually an increase in the tensile modulus and in the ultimate tensile strength, or an increase in the ultimate impact strength or the glass transition temperature. (Tg) Molding compositions comprising a thermoplastic or thermosetting polymer containing a desired load of platelets obtained from the exfoliation of the interleaves manufactured in accordance with the invention are outstandingly suitable for the production of sheets and panels having valuable properties. These sheets and panels can be configured by conventional processes, such as vacuum processing, or by hot press, to form useful objects. The sheets and panels according to the invention are also suitable as coating materials for other materials comprising, for example, wood, glass, ceramic, metal, or other plastics, and outstanding forces can be achieved using conventional adhesion promoters, for example, those based on vinyl resins. The sheets and panels can also be laminated with other plastic films, and this is preferably done by coextrusion, linking the leaves in the molten state. The surfaces of the sheets and panels, including those in the embossed form, can be improved or finished by conventional methods, for example, by applying lacquer, or by applying protective films. Polymer / platelet composites are especially useful for the manufacture of extruded films and film laminates, such as films for use in food packaging. These films can be manufactured using conventional film extrusion techniques. The films preferably are from about 10 to about 100 microns, more preferably from about 20 to about 100 microns, and most preferably from about 25 to about 75 microns in thickness. The homogeneously distributed platelet particles and the matrix polymer, which form the nanocomposites, are formed into a film by suitable film-forming methods. Typically, the composition is melted and forced through a film former die. The nanocomposite film can pass through passages to cause the platelets to be further oriented, so that the larger planes through the platelets are substantially parallel to the larger plane through the film. One method to do this is to stretch the film biaxially. For example, the film is stretched in the axial or machine direction by tension rollers, pulling the film as it is extruded from the die. The film is stretched simultaneously in the transverse direction, holding the edges of the film, and stretching them to separate them. Alternatively, the film is stretched in the transverse direction, using a die of tubular film, and blowing the film as it passes from the tubular film die. Movies can exhibit one or more of the following benefits: greater module; greater resistance to humidity; greater dimensional stability; lower humidity adsorption; lower permeability to gases such as oxygen, and to liquids, such as water, alcohols, and other solvents. Those skilled in the art, in view of the foregoing description, will be able to think of numerous modifications and alternative embodiments of the invention. In accordance with the foregoing, this description should be construed as illustrative only, and is for the purpose of teaching the experts in this field the best mode of carrying out the invention. The details of the structure can be varied substantially without departing from the spirit of the invention, and the exclusive use of all modifications falling within the scope of the appended claims is reserved.

Claims

NOVELTY OF THE INVENTION Having described the above invention, it is considered as a novelty, and therefore, the content of the following is claimed as property: CLAIMS

1. A composite material comprising a host material in an amount of about 40 percent to about 99.95 percent by weight of the composite material, and from about 0.05 percent to about 60 percent by weight of exfoliated platelets of a material of phyllosilicate, these platelets being derived from an interlayer formed by the contact of a phyllosilicate with a composition containing intercalant, this composition having a intercalant concentration of at least about 2 weight percent intercalant, to achieve sorption of the intercalating between the adjacent layers separated from the phyllosilicate, to expand the spacing between a predominance of the adjacent phyllosilicate plates at a distance of at least about 10 Angstroms, when measured after the sorption of the intercalary, this intercalant being selected from the group consisting of in: (1) a monom N-alkenyl amide and an allylic monomer; (2) an oligomer formed by the copolymerization of an N-alkenyl amide monomer and an allylic monomer; (3) a polymer formed by the copolymerization of an N-alkenyl amide monomer and an allylic monomer; and (4) mixtures thereof.

2. A composite material according to claim 1, characterized in that the concentration of the intercalant in the composition contacting the phyllosilicate is at least about 5 weight percent, based on the dry weight. of the filosilicato with which he makes contact.

3. A compliant composite material as claimed in claim 2, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is at least about 15 weight percent.

4. A composite material according to claim 3, characterized in that the concentration of the intercalant in the composition contacting the phyllosilicate is at least about 20 weight percent.

5. A composite material according to claim 4, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is at least about 30 weight percent.

6. A composite material as claimed in claim 5, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is in the range of about 50 percent to about 80 percent by weight.

7. A composite material according to claim 5, characterized in that the intercalant concentration in the composition contacting the phyllosilicate is in the range of about 50 percent to about 100 percent 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 weight percent, based on the dry weight of the composition. filosilicato with which he makes contact.

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 percent to about 70 percent, based on in the dry weight of the phyllosilicate with which it makes contact.

10. A composite material according to claim 9, characterized in that the intercalant concentration in the composition that makes contact with the phyllosilicate, is initially on the scale of about 16 percent to less than about 35 weight percent, based on the dry weight of the phyllosilicate with which it makes contact.

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 percent to less than about 55 percent. by weight, based on the dry weight of the phyllosilicate with which it makes contact.

12. A composite material according to claim 9, characterized in that the concentration of the intercalant in the composition making contact with the phyllosilicate is 70 weight percent, based on the dry weight of the phyllosilicate. makes contact.

13. A composite material according to claim 1, characterized in that the interlayer is a copolymer of an N-alkenyl amide monomer and an allylic monomer.

14. A composite material according to claim 13, characterized in that the intercalant is a mixture of an N-alkenyl amide monomer and an allylic monomer.

15. A composite material according to claim 1, characterized in that the intercalant polymer has a weight average molecular weight in the range from about 225 to about 1,000,000.

16. A composite material as claimed in claim 15, characterized in that the intercalant polymer has a weight average molecular weight in the range from about 225 to about 10,000.

17. A composite material according to claim 1, characterized in that the host material is a matrix polymer selected from the group consisting of a polyamide, polyvinylimine; polyethylene terephthalate; polybutylene terephthalate; a polymer polymerized from a monomer selected from the group consisting of dihydroxyethyl terephthalate; hydroxyethyl terephthalate; dihydroxybutyl terephthalate; and mixtures thereof.

18. A method for manufacturing the composite material as claimed in any of claims 1 to 17, which contains from about 40 percent to about 99.95 percent by weight of a thermoplastic or thermoformable matrix polymer, and from about 0.05 percent to about 60 weight percent of exfoliated platelets of a phyllosilicate material, these platelets being derived from an interleaved phyllosilicate having an intercalator interspersed between the adjacent phyllosilicate platelets, which comprises: contacting the phyllosilicate with a composition containing intercalant, comprising at least about 5 percent by weight of the intercalant polymer, based on the dry weight of the phyllosilicate with which it contacts, to achieve intercalation of the polymer between the adjacent phyllosilicate platelets , in an amount sufficient to separate the platelets from the adjacent osilicate by a distance of at least about 10 Angstroms; combining the interleaved platelets with the thermoplastic or thermoplastic polymer, and heating the thermoplastic or thermosetting polymer sufficiently to provide the flow of the thermoplastic or thermosetting polymer, and the delamination of the platelets of the phyllosilicate; and dispersing the delaminated platelets throughout the matrix polymer, wherein the intercalant is selected from the group consisting of: (1) an N-alkenyl amide monomer and an allylic monomer; (2) an oligomer formed by the copolymerization of an N-alkenyl amide monomer and an allylic monomer; (3) a polymer formed by the copolymerization of an N-alkenyl amide monomer and an allylic monomer; (4) mixtures thereof.

19. The method according to claim 18, characterized in that the intercalant polymer-containing composition includes a dissolved polymer carrier comprising from about 5 percent to about 95 percent by weight of organic solvent, based on in the total weight of the composition that makes contact with the phyllosilicate.

20. The method according to claim 19, characterized in that the carrier comprises from about 5 percent to about 95 percent of an alcohol-aliphatic.

21. The method according to claim 20, characterized in that the alcohol is selected from the group consisting of methanol, ethanol, and mixtures thereof.

22. A method for exfoliating a phyllosilicate, which comprises: contacting the phyllosilicate, which has a moisture content of at least about 4 weight percent, with an interlayer composition comprising at least about 2 percent by weight. weight of an interlayer in a liquid carrier, to achieve intercalation of the interlayer between the adjacent phyllosilicate plates, in an amount sufficient to separate the adjacent phyllosilicate platelets by a distance of at least about 10 Angstroms; and separating the platelets from the interspersed phyllosilicate; wherein the intercalant is selected from the group consisting of: (1) an N-alkenyl amide monomer and an allylic monomer; (2) an oligomer formed by the copolymerization of an N-alkenyl amide monomer and an allylic monomer; (3) a polymer formed by the copolymerization of an N-alkenyl amide monomer and an allylic monomer; and (4) mixtures thereof.

23. The method according to claim 22, characterized in that the intercalant-containing composition includes a liquid carrier that can solubilize the intercalant., in an amount of about 5 percent to about 95 percent by weight, based on the total weight of the interleaver composition.

24. The method according to claim 22, characterized in that the carrier comprises from about 30 percent to about 40 percent by weight of water.

25. The method according to claim 24, characterized in that the liquid carrier comprises from about 35 percent to about 40 percent by weight of water.

26. The method according to claim 23, characterized in that the carrier comprises from about 5 percent to about 50 percent by weight of water, based on the total weight of the intercalant in the composition that contacts the the phyllosilicate, which contains intercalary.

27. A composition comprising an interlayer, together with an organic solvent, this interleaving being formed by contacting a layered material, having a moisture content of at least about 4 weight percent, with an intercalating polymer, for forming an interlayer composition, this interleaving having a weight ratio of the polymer to the layered material of at least 1:20, to achieve sorption and polymer complex formation between the adjacent separated layers of the layered silicate material, to expand the separation between a predominance of adjacent platelets of the layered silicate material to at least about 10 Angstroms, measured after sorption of the intercalating polymer, and drying to a maximum of 5 weight percent water; wherein the intercalating polymer is a copolymer of an N-alkenyl amide and an allylic monomer.