MXPA01005428A - A polymer/clay nanocomposite comprising a functionalized polymer or oligomer and a process for preparing same - Google Patents

Abstract

The invention is directed to a nanocomposite material and products produced from the nanocomposite material. This invention is also directed to a process for preparing a polymer-clay nanocomposite comprising the steps of (i) forming a concentrate comprising a layered clay material with a matrix polymer-compatible functionalized oligomer or polymer, and (ii) melt compounding the concentrate with a melt-processible matrix polymer to produce a polymer-clay nanocomposite.

Description

A NANOCOMPUESTO OF POLYMER / CLAY COMPRISING A FUNCTIONALIZED POLYMER OR OLIGOMER AND A ROCESO ARA PREPARE THE SAME BRIEF DESCRIPTION OF THE INVENTION This application claims priority to the provisional patent application Series No. 60 / 111,323 filed on December 7, 1998, which is incorporated herein by reference in its entirety. This invention relates generally to a nanocomposite comprising an oligomer or functionalized polymer compatible with polymer matrix and a clay material. This invention also relates to articles produced from the nanocomposite and the processes for producing the nanocomposite. There is much interest in polymer nanocomposites based on material in layers of clay layers due to the improved properties presented by the nanocomposites. It is desirable to maximize the delamination of platelet particles in individual platelets to maximize and improve some properties, including barrier improvements, and to minimize the deleterious effects on some properties including elongation at break. Ideally, the clay is exfoliated into particles smaller than approximately 100 nm to achieve clarity in the i - l. * ^ - ^ - ^^ p - ^^^. ^^^^^^ polymer that is comparable to the clay-free polymer. To date, the only polymer / clay nanocomposites that satisfy this expectation are prepared by incorporation of organically treated clays during the synthesis of the monomer polymer. It is widely known, however, that the amount of clay that can be mixed in a polymer and still exhibit exfoliation of the clay material in layers is limited and some mechanical properties, such as elongation to breakage are often reduced considerably with the addition of the clay . Researchers recognize the value of inventing fusion preparation processes that provide exfoliated polymer / platelet particle compounds, mainly more versatility of polymer selection and clay loading and the potential for cost savings. However, the fusion preparation processes explored to date do not provide sufficient exfoliation of the platelet particles. Polyesters such as poly (ethylene terephthalate) (PET) are widely used in bottles and containers that are used for carbonated drinks, fruit juices, and some foods. Useful polyesters have high inherent viscosities (I.V.s) which allow to form polyesters in parisons and subsequently be molded into containers. Due to the limited barrier properties with respect to oxygen, carbon dioxide and the like, PET containers are not generally used for products that require long shelf life. For example, the transmission in the 5 PET bottles containing beer, wine and some food products cause them to deteriorate. There have been attempts to improve the barrier properties of PET containers by the use of multilayer structures comprising one or more barrier layers and one or more structural PET layers. Without However, multilayer structures have not found wide use and are not suitable for use as a beer container because of the high cost, the large thickness of the required barrier layer, and the poor adhesion of the barrier layer to the structural layer . 15 There are examples in the literature of polymer / clay nanocomposites prepared from treated monomers and clays. For example, U.S. Patent 4,739,007 describes the preparation of Nylon-6 / clay nanocomposites from caprolactam and treated montmorillonite. with alkyl ammonium. U.S. Patent 4,889,885 describes the polymerization of various vinyl monomers such as methyl methacrylate and isoprene in the presence of montmorillonite sodium. Some patents describe the combination of up 60 percent by weight of intercalated clay materials with a wide range of polymers including polyamides, polyesters, polyurethanes, polycarbonates, polyolefins, vinyl polymers, thermosetting resins and the like. Such high loads with modified clays are impractical and useless with most polymers because the melt viscosities of the combinations increase so much that they can not be molded. WO 93/04117 discloses a wide range of molten combination polymers with up to 60 weight percent dispersed platelet particles. WO 93/04118 describes nanocomposite materials of a polymer capable of being processed by melting and up to 60 percent of a clay that is intercalated with organic orne salts. The use of functionalized polymers in the melt combination operation is not contemplated or described. US Patent 5,552,469 describes the preparation of intercalated derivatives from some water-soluble clays and polymers such as polyvinyl pyrrolidone, polyvinyl alcohol, and polyacrylic acid. Although the specification describes a wide range of thermoplastic resins that include polyesters and rubbers that can be used in combinations with these intercalates, there are no examples that teach how to make such combinations. The use of ammonium-containing materials is specifically excluded; Thus, the use of functionalized polymers of • UM "t - - • -" ^ • J * fc- «~ '- --a» ^^ * - ^^^ j ^ .. * t **? .. xk ?. . . k .., > ^ Ammonium is not contemplated or described. The use of a hydroxy-functionalized polypropylene oligomer and an organoclay in the preparation of a polypropylene / clay nanocomposite is described by A. Usuki, M. Kato, T. Kurauchi, J. Appl. Polym. Sci. Letters, 15, 1481 (1996). The use of an oligomer of polypropylene modified by anhydride and a clay intercalated with sterilamium in the preparation of a polypropylene / clay nanocomposite was carried out by M. Kawasumi, N. Hasagawa, M. Kato, A. Usuki, and A. Okada, 10 Macromolecules, 30, 6333 (1997). The use of functionalized ammonium polymers or oligomers is not contemplated or described. The JP Kokai Patent no. 9-176461 describes polyester bottles wherein the polyester contains unmodified sodium montmorillonite 15. The incorporation of the clay into the polyester by fusion preparation is described; however, the use of the functionalized polymer was not contemplated or described. The following references are of interest with respect to chemically modified organoclay materials: U.S. Patent Nos. 4,472,538; 4,546,126 4, 676,929 4,739,007; 4,777,206 4,810,734; 4, 889, 885 4, 894, 411, 5,091,462; 5,102,948 5, 153, 062; 5, 164, 440 5, 164, 460, 5,248,720; 5,382,650 5,385,776; 5,414,042; 5,552,469; Pat. Request No.. WO 93/04117 --- ~ - ~ - "* * rt? Fl * - (* ........ t» a tk ^ ¿hu *** * ák á &? Á * l &l! L ~ tMkM * ~, .t., ... ^ t ^ - ^^ J-Jk- - - - ~~ «*** tk 93/04118; 93/11190; 94/11430; 95/06090; 95/14733; DJ Greenland, J. Colloid Sci. 18,647 (1963); Y. Sugahara et al., J. Ceramic Society of Japan 100, 413 (1992); PB Massersmith et al., J. Polymer Sci .: Polymer Chem. , U 1047 5 (1995), CO Sriakhi et al., J. Mater, Chem. 6, 103 (1996) This invention seeks to satisfy the need in a melt preparation process that provides polymer / clay nanocomposites with sufficient exfoliation for improved clarity and properties for applications commercials, including film, bottle, and containers. The polymeric nanocomposite materials of this invention are useful for forming gaskets having improved gas barrier properties. The containers made from these polymeric composite materials are ideally suitable for protecting consumable products, such as food materials, soft drinks, and medicines. This invention also seeks to provide a cost effective method to produce layers with sufficient oxygen barrier and clarity for widely extended applications. as bottles and multi-layer containers, which include beer bottles. As embodied and broadly described herein, this invention, in one embodiment, refers to a polymer-clay nanocomposite comprising (i) a melt-processable matrix polymer, (ii) a material in ^ fc _ ^^ ". . . i, .. í, ^. > -,. .TO. . ^. ^ A ^. ^ A.j,.,. ^^. ¿, Fat ^ a &J fe..a ^ ^ ¿^. ...- ^ jh ^^^^ IÉaÉÉU,. f,] TÜJÜBÜTE clay layers, and (iii) an oligomer or functionalized polymer compatible with matrix polymer. In another embodiment, this invention relates to a clay-polymer composite nanocomposite comprising 5 (i) a melt processable matrix polymer incorporated therein, (ii) a concentrate comprising a layer material of clay and a oligomer or functionalized polymer compatible with matrix polymer. In another embodiment, this invention comprises a The process comprises the steps of (i) forming a concentrate comprising a material in clay layers and an oligomer or functionalized polymer, and (ii) melt-mixing the concentrate with a polymer or melt-processable matrix to form a nanocomposite of polymer-clay. In yet another embodiment, this invention comprises a process comprising the step of melt-blending a clay-layered material, an oligomer or functionalized polymer, and a melt-processable matrix polymer to form a polymer-clay nanocomposite material. The additional advantages of the invention will be indicated in part in the detailed description, which includes the examples which follow and will be partly obvious from the description, or can be learned by the practice of the invention. The advantages of the invention will be realized and will get by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that the foregoing general description and the following detailed description are for example and explanation of the preferred embodiments of the invention, and are not limiting of the invention, as claimed. The present invention can be understood more readily by reference to the following detailed description of the invention, the examples provided therein. It is to be understood that this invention is not limited to the specific components, articles, processes and / or conditions described, since they may, of course, vary. It should also be understood that the technology used herein is for the purpose of describing particular modalities only and is not intended to be limiting. Definitions It should also be noted that, as will be used in the specification and appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. For example, the reference to an "article", "container" or "bottle" prepared from the nanocomposite and the process of this invention intends to include the processing of a plurality of articles, containers or bottles. The ranges can be expressed in the present as "approximately" or "around" a particular value and / or up to "approximately" or "around" another particular value. When such a range is expressed, another modality includes from the particular value and / or up to the other particular value. Similarly, when the values are expressed as approximations, by the use of the antecedent "approximately", it will be understood that the particular value forms another modality. Whenever used in this specification, the indicated terms will have the following meanings: "Layered clay material," layered clay ", "Layered material" or "clay material" will mean any organic or inorganic material or mixtures thereof, such as a smectite clay mineral, which is in the form of a plurality of layers! adjacent units. Layered clay comprises platelet particles and is typically extensible. "Platelets", "platelet particles" or "particles" means individual or aggregate unbound layers of the layered material. These layers may be in the form of individual platelet particles, small ordered or disordered aggregates of platelet particles (dedoides), and / or small aggregates of dedoids. "Dispersion" or "dispersed" is a general term that refers to a variety of levels or degrees of separation of platelet particles. The high levels of i n i i a - iiM ÉliiÉÉlilllt a ViMn i ii n ili mulí f i 'i iri? ti? dispersion include, but are not limited to "interspersed" and "exfoliated" "Interleaved" or "sandwich" will mean a layered clay material that includes organically modified treated layered clay material that has an increase in interlayer space between the adjacent and / or tactile platelet particles. In the present invention, "intercalated" can refer to a concentrate of a clay material and an oligomer or functionalized polymer. "Exfoliate" or "exfoliate" will mean dispersed platelets primarily in an individual state through a carrier material, such as a matrix polymer.

Typically, "exfoliated" is used to denote the highest degree of separation of the platelet particles. "Exfoliation" will mean a process to form an exfoliate from an interleaving or a state of separation of another less dispersed form. "Nanocomposite (s)" or "nanocomposite compositions (s)" shall mean a polymer or copolymer having dispersed therein a plurality of individual platelets obtained from a layered clay material. "Matrix polymer", "polymer in bulk" or "Bulk matrix polymer will mean a thermoplastic or thermoset polymer in which the material of k ,,?, *,. *, * ^. * ... ^. ^ * ^ .. - .A-. tík ^? k * Mm ^ * k3L? ^? itoM? JU ± ¿k * ^ ak ^^. . , ... ^ - jfc clay is dispersed to form a nanocomposite. In this invention, however, the platelet particles are predominantly exfoliated in the matrix polymer to form a nanocomposite. This invention relates to a polymer / clay nanocomposite and to melt preparation processes for preparing a polymer / clay nanocomposite composition by combining a clay, a melt-processable matrix polymer, or a functionalized oligomer or polymer. More specifically, this invention relates to a polymer / clay nanocomposite or process for preparing a polymer / clay nanocomposite composition comprising an oligomer or polymer containing an onium group, preferably an ammonium group. Without being limited by a particular theory, it is believed that the ammonium group on the oligomer or polymer provides a driving force for intercalation of the oligomer or polymer within the clay gallery, which disrupts the tactile structure and dilates the clay to allow the intercalation of the polymer of bulk matrix. The prior art has defined the degree of separation of the clay (platelet particles) based on the peak intensity and the baseline spacing value, or gives a lack of predominant basal spacing, as determined by X-ray analysis of particulate compound platelets polymer. Even when the X-ray analysis only ^ .. - ^ - - ^; It frequently does not predict unambiguously whether the platelet particles are individually dispersed in the polymer, it can often allow quantification of the level of dispersion achieved. The basal diffraction spacing of 5 X-rays indicates the separation distance of a plate in a tactile rather than a simple platelet. The X-ray diffraction intensity (peak height of basal spacing) can be correlated to the barrier in an article that results from a nanocomposite that includes a clay material.

For example, a peak height of low basal spacing indicates few tactile; therefore, the rest can be individual or tactile platelets that are disordered. In addition, in polymeric nanocomposites, X-ray analysis alone does not predict precisely the dispersion of platelet particles in the polymer or the improvement in the resulting gas barrier. TEM images of platelet polymer compounds show that platelet particles that are incorporated within at least one polymer exist in a variety of forms, including, but not limited to individual platelets (the exfoliated state), disordered agglomerates of platelets, platelet aggregates well ordered or stacked (tactile), dilated aggregates of stacked platelets (tactile interspersed), and aggregates of tactoids. 25 Without being limited by a particular theory, it is believed that the degree of gas barrier improvement, (decreased permeability) depends on the rate of incorporation, of the resulting particle platelets and aggregates, the degree! to which they are uniformly dispersed or distributed, and the degree, to which they are ordered perpendicular to the flow of the permeant, to obtain the improvements in gas permeability according to the present invention, it is preferred that the platelet particles representative of the package bulk exfoliate, and preferably highly exfoliate, in the matrix polymer such that most, preferably at least about 75 percent and perhaps as much as at least 90 percent or more of the platelet particles, are dispersed in the form of individual platelets and small aggregates having a thickness in the shortest dimension of less than about 30 nm and preferably less than about 10 nm, as estimated from TEM images. The platelet polymer nanocomposite containing more individual platelets and few aggregates, ordered or unordered, are more preferred. Significant levels of incomplete dispersion (ie, the presence of large agglomerates and tactiles greater than about 30 nm) not only lead to an exponential reduction in the barrier enhancement potential attributable to platelet particles, but can also lead to effects harmful to others properties inherent to polymer resins such as strength, toughness, resistance to calpr, and processability. Again, without being limited by a particular theory, 5 it is believed that delamination of platelet particles in the processing or mixing of fusion with a polymer requires favorable free mixing energy, which has contributions of enthalpy of mixing and entropy of mixing. The processing clay melted with polymers results in a negative entropy of mixing due to the reduced number of conformations, which are accessible to a polymer chain when it resides in the region between two layers of clay. It is believed that poor dispersion is obtained using melt-processable polyesters, because the enthalpy of mixing is not enough to ovee the negative entropy of mixing. In contrast, generally good dispersions are obtained with polyamides due to their hydrogen bonding character. However, the degree of this dispersion is often decreased due to the negative entropy of mixed. With respect to the present invention, it has been found that processing a polymer or matrix, a functionalized oligomer or polymer and a layered clay material gives a good dispersion of platelet particles, in a resulting polymer nanocomposite, creating mainly individual platelet particles. The resulting nanocomposite forms a gas barrier when formed within a wall or article as compared to a net polymer formed within the same structure or the like. Polymers Any polymer or melt-processable oligomer can be used in this invention. Illustrative of melt processable polymers are polyesters, polyethers, polyamides, polyesteramides, polyurethanes, polyimides, polyetherimides, polyureas, polyamideimides, polyphenylene oxides, phenoxy resins, epoxy resins, polyolefins, polyacrylates, polystyrenes, co-vinyl polyethylene (EVOH) alcohols. , and the like or their combinations and compositions. Although the preferred polymers are linear or quasi-linear, polymers with other architectures, including branched, star, cross-linked and dendritic structures, may be used if desired. Preferred polymers include those materials that are suitable for use in the formation of monolayer and / or multilayer structures with polyesters, and include polyesters, polyamides, co-vinyl polyethylene alcohols (such as EVOH), and similar polymers and / or copolymers or related The preferred polyester is polyethylene terephthalate (PET), or a copolymer thereof. The preferred polyamide is polya (m-xylylene adipamide) or a copolymer thereof. Suitable polyesters include at least one basic acid and at least one glycol. A polyester of this invention may comprise the reaction product polycondensation, polymerization (or residue) of the glycol component and the dicarboxylic acid component. "Residue" when used in reference to the polyester components of this invention, refers to the portion that is the product that results from the chemical species in a particular reaction scheme, or subsequent formulation or chemical product, regardless of whether the portion is currently of the chemical species. The main dibasic acids are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. The various isomers of naphthalenedicarboxylic acid or mixtures of isomers may be given, but the 1,4-, 1,5-, 2,6- and 2,7-isomers are preferred. The 1,4-c-chlorhexandicarboxylic acid may be in the form of cis, trans, or cis / trans mixtures. In addition to the acid forms, lower alkyl esters or acid chlorides can also be used. A polyester of this invention can be prepared from one or more of the following dicarboxylic acids and one or more of the following glycols. The dicarboxylic acid component of polyester it can be optionally modified with up to about 50 mole percent of one or more different dicarboxylic acids. Such additional dicarboxylic acids include dicarboxylic acids having from 6 to about 40 carbon atoms, and more preferably dicarboxylic acids selected from aromatic dicarboxylic acids having preferably 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 4 carbon atoms. to 12 carbon atoms, d acids cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms. Examples of suitable dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, acid Diphenyl-4,4'-dicarboxylic acid, phenylendi (oxyacetic acid), succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like. The polyesters can also be prepared from two or more of the above dicarboxylic acids. Typical glycols used in polyester include those containing from two to about ten carbon atoms. Preferred glycols include ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, and the like. He glycol component can optionally be modified with up about 50 mole percent, preferably up to 25 mole percent, and more preferably up to about 15 mole percent of one or more different diols1. Such additional diols include cycloaliphatic diols having preferably 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms. Examples of such diols include: diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propan-1,3-diol, butan-1,4-diol, pentan-1,5-diol, hexane-1,6-diol, 3-methylpentanediol- (2, 4), 2-methylpentanediol- (1, 4), 2, 2, 4-tpmethylpentan-d? Ol- (1, 3), 2-ethylhexandiol- (1, 3), 2, 2-diethylpropan-diol- (1, 3), hejcandiol- (1,3), 1,4-di- (2-hydroxyethoxy) -benzene, 2,2-bis- (44-hydroxynylohexyl) -propane, 2 , 4-d-hydroxy-1,3,3-tetramethylcyclobutane, 2,2-bis- (3-hydroxyethoxyphenyl) -propane, 2,2-bis- (4-hydroxypropoxyphenyl) -propane and the like. The polyesters can also be prepared from two or more of the above diols. Small amounts of multifunctional polyols such as trimethylolpropane, pentaerythritol, glycerol and the like can be used, if desired. When 1,4-cyclohexanedimethanol is used, it may be the cis, trans or cis / trans mixtures. When phenylenendi (oxyacetic acid) is used, it can be used as 1,2 isomers; 1.3; 1.4, or mixtures thereof. The polymer may also contain small amounts of trifunctional or tetrafunctional comonomers to provide controlled branching in the polymers. Such comonomers include trimellitic anhydride, tpmethylolpropane, pyromellitic dianhydride, pentaerythritol, trimellitic acid, pyromellitic acid, and other polyester-forming polyacids or polyols generally known in the art. The polyesters of the present invention exhibit an I.V. from about 0.25 to about 1.5 dL / g, preferably about 0.4 to about 1.2 dL / g, and more preferably from about 0.7 to about 0.9 dL / g. The I.V. is measured at 25 ° C in a 60/40 by weight mixture in phenol / tetrachloroethane at a concentration of 0.5 grams per 100 ml. Polyesters that have an I.V. within the ranges specified above are of sufficiently high molecular weight to be used in the formation of the articles of the present invention. Suitable polyamides include partially aromatic polyamides, aliphatic polyamides, fully aromatic polyamides and / or mixtures thereof. By "partially aromatic polyamide", it means that the amide bond of the partially aromatic polyamide contains at least one aromatic ring and one non-aromatic species. Suitable polyamides have a molecular weight that forms an article and preferably an I.V. of more than 0.4.

Preferred fully aromatic polyamides comprise in the molecule chain at least 70 mol% of structural units derived from m-xylylene diamine or a mixture of xylylene diamine comprising m-xylylene diamine and up to 30% p-xylylene diamine and a dicarboxylic acid aliphatic having 6 to 10 carbon atoms, which are further described in Japanese Patent Publications No. 1156/75, No. 5751/75 and No. 5735/75 and No. 10196/75 and Patent Application Japanese Specification Open to the Public No. 29697/75. The polyamides formed from isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, meta- or para-xylene diamine, 1,3- or 1X-cyclohexane (bis) methylamine, aliphatic diacids with 6 to 12 carbon atoms, aliphatic amino acids or lactams with 6 to 12 carbon atoms, aliphatic diamines with 4 to 12 carbon atoms, and other generally known polyamide forming diacids and diamines can be used. The low molecular weight polyamides may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamides and polyamides that form polyamide known in the art. Preferred partially aromatic polyamides include, but are not limited to poly (m-xylylene adipamide), poly (j -xylylene adipamide-co-isophthalamide), poly (hexamethylene isophthalamide), poly (hexamethylene isophthalamide-co-terephthalamide), poly (hexamethylene adipamide-co-isophthalamide), poly (hexamethylene adipamide-co-terephthalamide), poly (hexamethylene isophthalamide-co-terephthalamide) and the like or mixtures thereof. More preferred partial-polyamide polyamides include, but are not limited to poly (m-xylylene adipamide), poly (hexamethylene isophthalamide-co-terephthalamide), poly (jn-xylylene adipamide-co-isophthalamide), and / or mixtures thereof . The partially aromatic polyamide is poly (m-xylylene adipamide). Preferred aliphatic polyamides include, but are not limited to poly (hexamethylene adipamide) and poly (caprolactam). The most preferred aliphatic polyamide is poly (hexymethylene adipamide). Partially aromatic polyamides are preferred over aliphatic polyamides where good thermal properties are crucial. Preferred aliphatic polyamides include, but are not limited to polycapramide (Nylon 6), polyaminoheptanoic acid (Nylon 7), poly-aminonanoic acid (Nylon 9), polyundecane-amide (Nylon 11), polyaurilactam (Nylon 12), poly (ethylene-adipamide) (Nylon 2,6), poly (tetramethylene-adipamide) (Nylon 4,6), poly (hexamethylene-adipamide) (Nylon 6,6), poly (hexamethylene-sebacamide) (Nylon 6,10) ), poly (hexamethylene-dodecamide) (Nylon 6.12), poly (octamethylene- adipamide) (Nylon 8.6), poly (decamethylene-adipamide) (Nylon 10.6), poly (dodecamethylene-adipamide) (Nylon 12.6) and poly (dodecamethylene sebacamide) (Nylon 12.8). More preferred polyamides include poly (m-xylylene adipamide), polycapramide (Nylon 6) and poly (hexamethylene adipamide) (Nylon 6,6). Poly (m-xylylene adipamide) is a preferred polyamide due to its availability, high barrier, and processability. Polyamides are generally prepared by processes that are well known in the art. A polyamide of the present invention may comprise the polycondensation reaction product (or residue) of a diamine component and a dicarboxylic acid component, and / or those prepared by ring opening polymerization of lactams. "Residue" when used in reference to the components of the polyamide of this invention refers to the portion that is the product that results from the chemical species in a particular ration scheme, or subsequent formulation or chemical product, regardless of whether the portion is currently obtained from the chemical species. The polyamides of the present invention have an I.V. from about 0.25 to about 1.5 dL / g, preferably about 0.4 < up to about 1.2 dL / g, and more preferably from about 0.7 to about 1.0 dL / g. The I.V. is measured at 25 ° C in a 60/40 by weight mixture in phenol / tetrachloroethane at a concentration of 0.5 grams per 100 ml. Polyamides that have an I.V. within the 5 ranges specified above are of sufficiently high molecular weight to be used in the formation i of the articles of the present invention. The nanocomposite of the present invention also comprises a functionalized oligomer or polymer. By "functionalized", what is meant is that the oligomer or polymer preferably contains a functional group that provides increased intercalation of a clay material. Preferably, the functional group of the oligomer or functionalized polymer is an onium group, more preferably an ammonium group. It is preferred, but not required, that the onium group be located at or near the end of the polymer or oligomer chain. As stated above and not limited by a particular theory, it is believed that the ammonium group on the oligomer or polymer provides a force promoter for intercalation of the oligomer or polymer within the clay gallery, which disrupts the tactile structure and dilates the clay to allow intercalation by the bulk matrix polymer. Although any oligomer or polymer functionalized is contemplated by this invention, Preferred functionalized oligomers and polymers include, but are not limited to, oligomeric or polymeric polyesters such as polycaprolactone, beta-butyrolactane, poly (ethylene adipate), poly (ethylene terephthalate), poly (ethylene-naphthalate) and / or their copolymers; oligomeric or polymeric polyamides such as Nylon-6, nylon-6, 6, nylon-6,12, poly (in-xylylene adipamide) and / or their copolymers; oligomeric or polymeric polyolefins such as polystyrene, polyethylene, polypropylene, polybutadiene, polyisopropylene, polyvinyl alcohol, polyvinyl acetate and / or their copolymers; oligomeric or polymeric polysiloxanes such as polydimethyl siloxane; and oligomeric or polymeric polyacrylates such as poly (methyl methacrylate), poly (2-ethylhexyl acrylate), poly (butyl acrylate) and / or their copolymers. More preferred are oligomeric or polymeric polyesters, polyamide and polyolefins with the most preferred functionalized oligomers or polymers being polycaprolactone, poly (ethylene terephthalate), poly (iii-xylylene adipamide), polystyrene, and / or polypropylene. The IV of a functionalized oligomeric polyester before melt mixing is preferably about 0.05 and 0.5 dL / g, and more preferably 0.1 dL / g, at 0.3 dL / g as measured in a mixture of 60 weight percent in phenol and 40 weight percent 1,1,2,2-tetrachloroethane in a concentration of 0.5 g / 100 ml (solvent) at 25 ° C. In addition, the oligomeric polyester has a number average molecular weight of from about 200 to about 30,000 g / mol, more preferably about 200 to about 12,000 g / mol, and 5 can be a homo or co-oligomer. The I.V. of an oligomeric polyamide functionalized before melt mixing is preferably about 0.1 and 0.5 dL / g, and more preferably 0.3 dL / g, at 0.5 dL / g as measured in a mixture of 60 percent. by weight in phenol and 40 weight percent of 1,1,2,2-tetrachloroethane in a concentration of 0.5 g / 100 ml (solvent) at 25 ° C. In addition, the oligomeric polyester has a number average molecular weight of from about 200 to about 30,000 g / mol, more preferably About 200 to about 12,000 g / mol, and can be a homo or co-oligomer. It is preferred, but not required, that an ammonium-functionalized polymer or oligomer have an average viscosity average molecular weight number that is less than that of the matrix polymer. The ammonium-functionalized polymer or oligomer can comprise the same or different repeating units from those of the matrix polymer with the proviso that it is the ammonium-functionalized polymer or oligomer sufficiently compatible with the polymer or matrix to allow the achievement of desired properties. One or more ammonium groups may be present on the polymer or oligomer functionalized with ammonium. It is preferred, but not required, that the ammonium group be located at or near the end of the oligomer or polymer chain. Although not necessarily preferred, the oligomers and / or polymers of the present invention may also include suitable additives normally used in polymers1. Such additives can be used in conventional amounts and can be added directly to the reaction that fprma the functionalized polymer or oligomer or matrix polymer. Illustrative of such additives known in the art are dyes, pigments, carbon blacks, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, reheating aids, crystallization aids, acetaldehyde reducing compounds, recirculation release aids, oxygen scavengers, plasticizers, nucleators, mold release agents, compatibilizers, and the like, or combinations thereof. All these additives and many others and their use are known in the art and do not require extensive discussion. Therefore, only a limited number will be mentioned, it being understood that any of these compounds can be used in any combination as long as they do not impede present invention to achieve its purposes. Clay Materials (Platelet Particles) The nanocomposite composition of the present invention comprises less than about 25 percent by weight, preferably from about 0.5 to about 20 percent by weight, more preferably from about 0.5 to about 15 percent by weight, and more preferably from about 0.5 to about 10 weight percent clay material in ca.pas. He Layered clay material comprises platelet particles. The amount of platelet particles is determined by measuring the amount of silicate residue in the ash of the polymer / platelet composition when casting according to ASTM D5630-94. 15 Useful clay materials include natural, synthetic and modified phyllosilicates. Natural clays include smectite clays, such as montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, beidelite, volkonskoite, magadite, kenyaite and similar. Synthetic clays include synthetic mica, synthetic hectorite synthetic saponite and the like. The modified clays include fluoronated montmorillonite, fluorinated mica and the like. Suitable clays1 are available from various companies including Nanocor, Inc., Southern Clay Products, Kunimine Industries, Ltd., and Rheox.

Generally, the clay materials in layers useful in this invention are an agglomeration of individual platelet particles that are tightly stacked together like charts, in domains called tactile. The 5 individual platelet particles of the clays preferably have a thickness of about 2 nm and a diameter in the range of about 10 to about 3000 nm. Preferably, the clays are dispersed in the polymers so that most of the clay material exists as particles of individual platelets, small tactile, and small aggregates of tactoids. Preferably, a majority of the dedoids and aggregates in the polymer / clay nanocomposites of the present The invention will have thickness in its smallest dimension of less than about 20 nm. Polymer / clay nanocomposite compositions with the highest concentration of individual platelet particles and few tactile or aggregate are preferred. In addition, layered clay materials are typically freely flowing, expandable powders having a cation exchange capacity of from about 0.3 to about 3.0 milliequivalents per gram of ore (meq / g), Preferably from about 0.90 to about 1. 5 meq / g, and more preferably from about 0.95 to about 1.25 meq / g. The clay may have a wide variety of interchangeable cations present in the galleries between the layers of the clay, including, but not limited to, cations comprising the alkali metals (group IA), the ferrous alkali metals1 (group IIA), and its mixtures The most preferred cation is sodium; however, any cation or combination of cations can be used with the proviso that most cations can be exchanged for organic cations (onium ions). The exchange can occur when treating an individual clay or a mixture of clays with organic cations. Preferred clay materials are type 2: 1 phyllosilicates having a cation exchange capacity of 0.5 to 2.0 meq / g. The most preferred clay materials are smectite clay minerals, particularly bentonite or montmorillonite, more particularly Wyoming-type sodium montmorillonite or Wyoming-type sodium bentonite having a cation exchange capacity of about 0.95 'to about 1.25 meq / g. Other non-clay materials having the ion exchange capacity described above and size, such as chalcogens, can also be used as a source of platelet particles under the present invention.

The chalcogens are salts of a heavy metal and the group VIA (O, S, Se and Te). These materials are known in the art and do not need to be described in detail here. Improvements in the gas barrier result in increases in the concentration of platelet particles in the polymer. While amounts of platelet particles as low as 0.01 percent provide improved barrier (especially when well dispersed and ordered), compositions having at least about 0.5 percent by weight of platelet particles are preferred due to which show the desired improvements in gas permeability. Prior to incorporation into the oligomers or polymers, the particle size of the clay material is reduced in size by methods known in the art, including, but not limited to, grinding, pulverizing, hammer milling, jet milling. , and their combinations. It is preferred that the average particle size be reduced to less than 100 microns in diameter, more preferably less than 50 microns in diameter, and more preferably less than 20 microns in diameter. The clay material of this invention may comprise refined but unmodified clays, modified clays or mixtures of modified and unmodified clays. Generally, it is desirable to treat the material of selected clay to facilitate the separation of the agglomerates of platelet particles into individual platelets and small tactile particles. By removing the platelet particles before incorporation into the polymer, the polymer / platelet interface also improves. Any treatment that achieves the above goals can be used. Many clay treatments used to modify clay for the purpose of improving the dispersion of clay materials are known and can be used in the practice of this invention. The clay treatments can be conducted before, during, or after mixing the clay material with the polymer. Organic Cations In one embodiment of this invention, a material of The modified or treated layer clay is prepared by reacting a stretchable clay with an organic cation (to effect partial or complete cation exchange), preferably an ammonium compound. If desired, two or more organic cations can be used to treat the clay. In addition, mixtures of organic cations can also be used to prepare a treated, layered clay material. The process for preparing organoclays (modified or treated clays) can be conducted in a batch, semi-batch, or continuous form. 25 The organic cations used to modify a Clay material or a mixture of clay materials of a nanocomposite of this invention are derived from organic cationic salts, preferably onium salt compounds. The organic cationic salts useful for the nanocomposite and process of this invention can generally be represented by the following formula (I): (I) wherein M is nitrogen or phosphorus; X ~ is a halide anion, hydroxide, or acetate, preferably chloride and bromide; and Ri, R2, R3 and R4 are independently organic and / or oligomeric ligands or can be hydrogens. Examples of useful organic ligands include, but are not limited to, linear or branched alkyl groups having 1 to 22 carbon atoms, aralkyl groups which are benzyl and benzyl substituted portions including fused ring portions having straight or branched chains of 1 at 100 carbon atoms in the alkyl portion of the structure, aryl groups such as phenyl and substituted phenyl including aromatic substituents of fused rings, beta, gamma, unsaturated groups having 6 or less carbon atoms, and alkylene oxide groups that have units which are repeated comprising 2 to 6 carbon atoms. Examples of useful oligomeric ligands include, but are not limited to poly (alkylene oxide), polystyrene, polyacrylate, polycaprolactone and the like. Examples of useful organic cations include, but are not limited to, alkyl ammonium ions, such as tetramethyl ammonium, hexyl ammonium, butyl ammonium, bis (2-hydroxyethyl) dimethyl ammonium, hexyl benzyl dimethyl ammonium, becil trimethyl ammonium, butyl benzyl dimethyl. ammonium, tetrabutyl ammonium, di (2-hydroxyethyl) ammonium, and the like, and alkyl phosphonium ions such as tetrabutyl fpsphonium, trioctyl octadecyl phosphonium, tetraoctyl phosphonium, octadecyl triphenyl phosphonium, and the like or mixtures thereof. Other organic cations particularly useful for this invention include, but are not limited to, alkyl ammonium ions such as dodecyl ammonium, octadecyl trimethyl ammonium, bis (2-hydroxyethyl) octadecyl methyl ammonium, octadecyl benzyl dimethyl ammonium, and the like or mixtures thereof. same. Illustrative examples of suitable polyalkoxylated ammonium compounds include the hydrochloride salts of polyalkoxylated amines such as JEFFAMINE (ex Huntsman Chemical), mainly, JEFFAMINE-506 and JEFFAMINE 505, and an amine available under the trade name ETHOMEEN (ex Akzo Chemie America), mainly, ETHOMEEN 18/25, which is octadecyl 25 bis (polyoxyethylene [15]) amine, where the numbers in bracket ir'r-'iiinir '' - T f ^ T. J '* •' f 'fi Ti' 'füfiHtf r i ifíiiiii? Itfiiinjitiiíi if íi? The total number of units of ethylene oxide is calculated in terms of the total number of units of ethylene oxide. A further illustrative example of a suitable polyalkoxylated ammonium compound is ETHOQUAD 18/25, (from Akzo Chemie America), which is octadecyl methyl bis (polyoxyethylene [15]), where the numbers in bracket refer to the total number of ethylene oxide units. Numerous methods are known for modifying clays in organic cation layers, and any of these can be used in the practice of this invention. One embodiment of this invention is the organic modification of a layered clay with an organic cationic salt by the process of dispersing a layered clay or clay mixture in hot water, more preferably 50 to 80 ° C, by adding the organic cationic salt separately or by adding a mixture of the organic cationic salts (net or dissolved in water or alcohol) with stirring, then combining for a period of time sufficient for the organic cations to exchange the majority of the metal cations present in the galleries between the layers 1 of the clay materials. Then, the organically modified clay materials are isolated by methods known in the art including, but not limited to, filtration, centrifugation, spray drying and combinations thereof. It is desirable to use a sufficient amount of the organic cationic salts to allow the exchange of most of the metal cations in the galleries i of the particles in layers by the organic cations; therefore, at least 0.5 equivalents of total organic cationic salt are used and up to about 3 equivalents of organic cationic salt can be used. It is preferred that about 0.5 to 2 equivalents of organic cationic salt be used, more preferably about 1.0 to 1.5 equivalents. It is desirable, but it is not required to remove most of the metal cationic salts and most of the excess organic cationic salts by washing and other techniques known in the art. Other Clay Treatments The clay may be further treated for the purposes of aiding the exfoliation in the composite and / or improving the strength of the polymer / clay inferium. Any treatment that achieves the above goals can be used. Examples of useful treatments include intercalation with water-soluble or water-insoluble polymers, organic reagents or monomers, silane, metal or organometallic compounds, and / or combinations thereof. The treatment of the clay can be achieved before the addition of a polymer to the clay material, during the dispersion of the clay with the polymer or during a combination by subsequent melting or melt fabrication step.

Examples of useful pretreatment with polymers or oligomers include those described in U.S. Patent Nos. 5,552,469 and 5,578,672, incorporated herein by reference. Examples of polymers useful for treating the clay material include polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polytetrahydrofuran, polystyrene, polycaprolactone, some water dispersible polyesters, Nylon1 6, and the like. Examples of useful pretreatment with reagents and organic monomers include those described in EP 780,340 A1, incorporated herein by reference. Examples of organic reagents and monomers useful for interlaying the clay in expandable layers include dodecyl pyrrolidone, caprolactone, caprolactam, ethylene carbonate, ethylene glycol, bishydroxyethyl terephthalate, dimethyl terephthalate and the like or mixtures thereof. Examples of useful pretreatment silane compounds include those pretreatments described in WO 93/11190, incorporated herein by reference. Examples of useful silane compounds include (3-glycidoxypropyl) trimethoxysilane, 2-methoxy (polyethyleneoxy) propyl heptamethyl trisiloxane, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride and similar.

If desired, a dispersing aid may be present during or before the formation of the compounds for the purposes of aiding the exfoliation of the particles in treated or untreated stretchable layers within the polymer. Many such dispersion aids are known and meet a wide range of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents and the like or combinations thereof. It should be appreciated that on a total composition basis, the dispersion aids and / or pretreatment compounds can account for a significant amount of the total composition, in some cases up to 30 weight percent. While it is preferred to use Alternatively, the dispersant aid / treatment compound can not be used, the amounts of dispersing aids and / or pretreatment compounds can be as much as about 8 times the amount of the platelet particles. 20 Articles The clay polymer nanocomposite of this invention can be formed into articles by conventional plastic processing techniques. Molded articles can be made from the polymers described above by molding or compression, blow molding, or | ^^ g ^ j & ^^^ | riMHMM | tf | iA j || íi | ^ "dbj - * > * • '< * > other such molding techniques, all of which are known in the art Monolayer and / or multilayer articles prepared from the nanocomposite material of this invention include, but are not limited to, film, sheet, pipe, tubes, profiles, molded articles, preforms, films and blow-molded containers, blow molded containers, blow-molded films and containers, thermoformed articles and the like The containers are preferably bottles The bottles and containers of this invention provide increased shelf life for the contents, including beverages and foods, which are sensitive to gas permeation The articles, more preferably containers, of the present invention often show a gas transmission rate or permeability (oxygen, carbon dioxide, water vapor) of at least 10% lower (depending on the concentration of clay) than that of similar containers made of clay-free polymers, which result in shelf life of the correspondingly longer product provided! for the container. The desirable values for the sidewall module and tensile strength can also be maintained. The articles also show unexpected resistance to fog formation, crystallization, and other defects of training. Articles can also be multi-layered. Preferably, the multilayer articles have a nanocomposite material disposed intermediate to other layers, although the nanocomposite can also be a one layer or two layer article. In the modalities where the nanocomposite and its components are approved for contact with food, the nanocomposite can form the contact layer with the food of the desired articles. In other embodiments, it is preferred that the nanocomposite be in a layer other than the food contact layer. The multilayer articles may also contain one or more layers of the nanocomposite composition of this invention and one or more layers of a structural polymer. A wide variety of structural polymers can be used. Illustrative of structural polymers are polyesters, polyethers, polyamides, polyesteramides, polyurethanes, polyimides, polyetherimides, polyureas, polyamideimides, polyphenylene oxides, phenoxy resins, epoxy resins, polyolefins, polyacrylates, polystyrenes, co-vinyl polyethylene alcohols (EVOH), and similar or their combinations and mixtures. Preferred structural polymers are polyesters, such as poly (ethylene terephthalate)! and its copolymers. In another modality, extrude a layer of Polymer clay nanocomposite specified above with some other suitable thermoplastic resin can form articles. The clay polymer nanocomposite and the molded article and / or extruded sheet can also be formed at the same time by co-injection or co-extrusion molding. Another embodiment of this invention is the combined use of uniformly dispersed silicate layers in the matrix of a high barrier thermoplastic together with the multilayer proposal for packaging materials. When using a Layered clay to decrease the gas permeability in the high barrier layer, the amount of this material that is needed to generate a specified barrier level in the final application is greatly reduced. Since the high barrier material is As the most expensive component in multi-layer packaging, a reduction in the amount of this material used can be quite beneficial. With the nanocomposite aapa of clay polymer being sandwiched between the two outer polymeric layers. The superficial roughness is often considerably smaller for a monolayer nanocomposite material. Thus, with a multilayer proposal, the fog level can be further reduced. Processes The polymer / clay nanocomposites of this invention can be prepared with the matrix polymer, oligomer or functionalized polymer and clay material in layers in different forms. In one embodiment of this invention, a polymer or oligomer comprising an ammonium group is prepared. A concentrate is then prepared by melt preparation, by methods known in the art, 20-99.5 weight percent, preferably 40-95 weight percent, of the ammonium functionalized polymer or oligomer with 0.5-80 percent by weight. weight, preferably 0.5-60 weight percent, of the desired clay. Then, the final nanocomposite is prepared by melt preparation, by methods known in the art, 1-50 weight percent of the concentrate with 50-99 weight percent of a matrix polymer. The steps of fusion preparation can be carried out separately or sequentially. That is, the concentrate can be used immediately while in the molten form, or it can be solidified and used at a later time. In another embodiment of this invention, a concentrate of 0.5-80 weight percent clay interspersed with 20-99.5 weight percent of an ammonium-functionalized polymer or oligomer is prepared in water or a mixture of water and one or more solvents. organic miscible in water, which include alcohols, ethers, acids and nitriles. Illustrative of organic solvents miscible in water are dioxane, tetrahydrofuran, methanol, ethanol, isopropanol, acetic acid, acetonitrile and the like or mixtures thereof. Then, the final nanocomposite is prepared by melt preparation 1-50 weight percent of the concentrate with 50-99 weight percent of a polymer by methods known in the art. The steps of fusion preparation can be carried out separately or sequentially. That is, the concentrate can be used immediately while in the molten form or can be requested and used at a later time. In another embodiment of this invention, the nanocomposite is prepared in a single extrusion, by methods known in the art, using up to 0.5 ^ 25 weight percent of the ammonium functionalized polymer or oligomer, 50-99 weight percent of the desired polymer , and 0.5-25 weight percent of the desired clay. In yet another embodiment of this invention, a polymer is prepared or modified such that a minor amount of the polymer chains comprise an ammonium group. Then, 75-99.5 weight percent of this polymer material partially functionalized with ammonium is prepared by melting, by methods known in the art, with 0.5-25 weight percent of the desired clay material. In yet another embodiment of this invention, an ammonium-functionalized polymer or oligomer is melt-bonded with a matrix polymer, and then the combination is prepared by melting clay.

Fusion processing or mixing includes melt preparation and extrusion. The use of extrusion preparation to mix clay and a polymer has advantages. Primarily, the extruder is capable of handling the high viscosity presented by the nanocomposite material. In addition, in a proposal of fusion mixing to produce nanocomposite materials, the use of solvents can be avoided. Low molecular weight liquids can often be expensive to remove from the resin nanocomposite. A low molecular weight oligomer, for example, is very effective in dispersing a modified or other organoclay, preferably smectite clay, as a concentrate when melt blending. The values desirable for I.V. or molecular weight of the functionalized oligomer or polymer depends on factors including the selected oligomer and clay and is readily determined by those skilled in the art. If desired, a dispersion aid may be present during or before the formation of the compound by melt mixing for the purposes of aiding the exfoliation of the particles in treated or untreated stretchable layers within the polymer. Many such dispersion aids are known that cover a wide range of materials including water, ketone alcohols, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents and the like or combinations thereof. The molecular weight of the polymeric material can be increased by any of a number of known proposals or by any combination of these proposed, for example chain extension, reactive extrusion, extrusion by extrusion, polymerization in solid or hardened state, tempering ba or a flow of inert gas, vacuum tempering, tempering in a fusion reactor, etc. Although any fusion mixing device can be used, typically, the melt mixing is conducted by a batch mixing process or by a melt preparation extrusion process during which the clay particles in treated or untreated layers are introduced. inside an oligomeric or polymer resin. Prior to melt mixing, the particles in treated or untreated layers can exist in various forms, including pellets, flakes, chips and powders. It is preferred that the particles in treated or untreated layers be reduced in size by methods known in the art such as hammer milling, and jet milling. Prior to melt mixing, the oligomeric or polymeric resin can exist in a wide variety of forms including pellets, ground chips, powder or its molten state. The melt blending can also be achieved by dry blends of an oligomeric resin functionalized with treated or untreated particles in layers then passing the mixture through a preparation extruder under conditions sufficient to melt the oligomeric ream. Additionally, the melt blending can be conducted by feeding the functionalized oligomeric resin and the particles into treated or untreated layers separately into a preparation extruder. When the particles in treated layers are used in this process, it is preferred that the oligomeric resin be added first to minimize the degradation of the particles in treated layers. In yet another embodiment involving the melt blending of a functionalized oligomer, a high concentration of layered particles is mixed by melting with oligomeric resin by mixing in a reactor. The resulting composite material is then chain lengthened, polymerized to high molecular weight, or lowered in the extruder into a high molecular weight polymer to obtain the final nanocomposite material. As exemplified above, the clay, the ammonium functionalized polymer or oligomer, and the matrix polymer components of the nanocomposite of this invention can be combined in a wide variety of ways that are known to those skilled in the art. Therefore, it will be apparent to those experts in the 'technical ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ «^^^^^^^^ ^^ * ^^ MA-L- that various modifications and variations can be made to the processes incorporated above without departing from the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention described herein. It is tried that the description of the previous modalities is not limiting. The functionalized oligomer or polymer and the high molecular weight matrix polymer may have the same or different repeat unit structure, ie they may be comprised of the same or different monomer units. Preferably, the oligomer or functionalized polymer has the same monomeric unit to 'improve compatibility or miscibility with the high molecular weight matrix polymer. The resulting nanocomposite can then be processed into the desired barrier article, film or container with methods forming articles well known in the art. For example, the nanocomposite can then be processed as an injection molded article, for example, a container preform or an extruded sheet or film. The further processing of extrusion tempering for a container or extrusion as a barrier film produces high-barrier transparent articles. Polymeric nanocomposites and articles produced according to the present invention show gas permeability, which is at least 10% lower than that of the unmodified polymer. EXAMPLES The following examples and experimental results include to provide those of ordinary skill in the art with a complete description and presentation of the particular forms in which the present invention can be practiced and evaluated, and are intended to be merely examples of the invention and not intended limit the scope of what the inventors consider to be their invention. Efforts have been made to ensure accuracy with respect to numbers (eg, amounts, temperature, etc.); however, some errpres and deviations may have occurred. Unless otherwise indicated, the parts are parts by weight, the temperature is in ° C or is at room temperature, and the pressure is or is close to atmospheric. Example 1 This Example illustrates the preparation of amine-functionalized polyesters by aminolysis of an oligomeric poly (caprolactone). 200 grams (approximately 0.1 moles) of polycaprolactoma, with an average molecular weight number of about 2000 available from Aldrich and 30 grams (0.30 moles) of 2,2-dimet? Ll, 3-propanediamine were heated with stirring at 200 ° C. 90 minutes and at 220 ° C for 30 minutes in a 500 mL 3-necked round bottom flask equipped with stirrer, condenser, and nitrogen inlet. The resulting liquid resin was poured into one liter. The titration of a small sample indicates that the amine content in the sample is 2.08 meq / g, and the analysis of molecular weight indicates a significant decrease in molecular weight. 20 grams of product were stirred in 160 ml of water at 60 ° C, and the ammonium form was prepared by adding 10 meq of hydrochloric acid in 10 ml of water. 6.36 g (6.14 meq of exchangeable sodium) were dispersed from Wyoming-type sodium montmorillonite with cation exchange capacity of 0.95 meq / g available from Southern Clay Products in 500 ml of water at 60 ° C in a Vitamix mixer. Then 3.07 g (6.14 meq ammonium) of the ammonium-functionalised polycaprolactone in 150 ml of water was added. The mixture was then combined, filtered, washed with 500 ml of water twice in the Vitamix mixer, then dried in an oven at 60 ° C. The average particle size volume of the clay material was reduced to less than 10 microns by hammer milling, then jetting. The resulting mud concentrate and ammonium-functionalized polycaprolactone was determined to have a WAXS basal spacing of 1.4 nm. ^^^^ i s lr? Zi (.i.i ?? i? Ji.? * T ~ í -. ,,. S ^ Z.Á.

EXAMPLE 2 The procedure of Example 1 was repeated, except that PETG6763, which is poly (fillene terephthalate, co-1,4-cyclohexane dimethylene, with IV Roman of 0.75 dL / g, was used. available from Eastman Chemical Company, in polycaprolactone form, and the temperature was increased to 225 ° C. Example 3 The procedure of Example 2 was repeated except that AQ 55, which is a water dispersible processable polyester available from Eastman < Hemical Company, instead of PETG 6763. Example 4 The procedure of Example 2 was repeated except that oligomeric poly (ethylene adipate) was used in place of polycaprolactone Example 5-18 The above procedure was repeated using the following polyesters of amines in the molar ratio indicated in Table 1 below.

Table 1 Example 19 An oligomeric polystyrene terminated in dimethylamine was prepared by anionic styrene polymerization using 3- (dimethylamino) propyl lithium as the initiator, using vacuum line conditions with a complex solvent mixture of cyclohexane, benzene and tetrahydrofuran. The average molecular weight number of the polystyrene terminated in dimethylamine was determined to be approximately 700 x MALDI-T0F. 6.6 grams of the above material was dissolved in 290 ml of dioxane then 10 g of 0.97 N of hydrochloric acid was added to give the oligomeric polystyrene ammonium form. 10 g of refined Wyoming type montmorillonite sodium with cation exchange capacity of 0.95 meq / g available from Southern Clay Products were dispersed in a ^ t fr kt & k & M mix at 70 ° C 90 ml water and 110 ml dioxanp in a mixer. The ammonium functionalized polystyrene solution was added to the mixer. The mixture was then combined, filtered, washed once with dioxane and once with water. Then it was dried in an oven at 60 ° C. The volume of the average particle size of the clay material was reduced to less than 10 microns milled by hammers and then jet grinded. The resulting concentrate of mud and polystyrene functionalized with ammonium was determined to have a WAXS vane spacing of 1.8 nm. Example 20 The concentrates prepared in Examples 1-19 are dry blended with PET 9921, dried overnight, then extruded in a Leistritz Micro-18 twin screw extruder at 280 ° C. The extruded strand is cooled by air and chopped into pellets. The pellets are dried in a vacuum oven overnight and then extruded on film using a single inch Kiliol single screw extruder with a 4 inch film tint. Oxygen permeability measurements of films in a mucus? Oxtran 1000 shows a significant reduction compared to PET film 9921. EXAMPLE 21 An oligomeric polystyrene terminated in dimethylamine was prepared by anionic styrene polymerization using 3- (dimethylamino) propyl lithium as the initiator 'using vacuum line conditions with a complex compound mixture of cyclohexane, benzene and tetrahydrofuran. The average molecular weight number of the polystyrene in dimethyl amine was determined to be about 1200 by MALDI TOF the oligomeric polystyrene terminated in dimethyl ammo was prepared by treating the oligomeric polystyrene terminated in dimethylamine with one equivalent of hydrochloric acid in a mixture of dioxane and water , concentrating the solvent, and then precipitating the product by adding a large amount of isopropanol. 120 g of oligomeric polystyrene functionalized with above ammonium, 8 g? of a montmorillonite intercalated with octadecyltrimethylammonium with average particle size volume of approximately 10-15 microns of Nanocor, and 872 g of polystyrene, dried in a vacuum oven at 100 ° C overnight, then extruded from an extruder of Twin screws Leistritz Micro-18 at 200 ° C. The extruded strand is cooled by air and placed in pellets. 700 g of the above pellets are dried i in a vacuum oven overnight at 100 ° C, then they are extruded into films. Oxygen permeability measurements in a Mocon Oxtran 1000 show a significant reaction compared to a free burlap control. ^^^ & ^^? ¡^^^^^^^^ &? ^^^^ # »^^^ j ti ^^ EXAMPLE 22 An amine functionalized polyvinylene acetate copolymer is prepared using a initiator functionalized with amine. Next, ammonium-functionalized co-vinyl polyethylene alcohol is prepared with hydrolysis of co-vinyl polyethylene acetate functionalized with Andean. 120 g of the ammonium-functionalized co-vinyl polyethylene alcohol are mixed dry, 7 g of a refined sodium montmorillonite with an average particle size of about 10-15 microns available from Nanocor, and 873 g of Eval F101A, which is a co-vinyl polyethylene alcohol available from Eval Company USA, dried in a vacuum oven at 100 ° C overnight, then extruded in a Leistritz Micro-18 twin screw extruder at 200 ° C. the extruded strand is cooled by air and it is pelleted. 700 g of the above pellets are dried in a vacuum oven overnight and then extruded in a three-layer film with two outer layers of PET-9921. Samples of two square inches of the film are oriented 4x4 on a T.M. Long. Oxygen permeability measurements in a Mocon Oxatran 2/20 shows a significant reduction compared to a mud free control. EXAMPLE 23 An amine-functionalized terpolymer comprising 33 mol% of ethylene, 62 mol% of vinyl acetate and 5 mol% of 6- (N, N-dimethylamino) hexyl vinyl ether is prepared. Then, this material is converted into a co-vinyl polyethylene alcohol functionalized with ammonium by hydrolysis of the terpolymer. 120 g of the polyethylene co-vinyl alcohol functionalized with above ammonium, 7 g, of a refined sodium montmorillonite with an average particle size volume of about 10-15 microns available from Nanocor, and 873 g of Eval F101A, are mixed dry. which is a polyethylene-co-vinyl alcohol available from Eval 'Company USA, dried in a vacuum oven at 100 ° C overnight, then extruded on a Leistritz Micro-18 twin screw extruder at 200 ° C. The extruded strand is cooled by air and chopped into pellets. 700 g of the above pellets are dried in a vacuum oven overnight and then extruded in a three-layer film with two outer layers of PET-9921. Two-inch square samples of the film are oriented! 4x4 on a T.M. Long. Oxygen permeability measurements in a Mocon Oxatran 2/20 show a significant reduction compared to a clay-free control. Example 24 An ammonium-functionalized poly (meta-xylylene adipamide) is prepared from 6- (trimethylammonium) hexanoic acid, adipicp acid, and metaxylylenediamine. 120 g of the ammonium-functionalized poly (methaxylylylene amipamide), 8 g of a montmorillonite intercalated with octadecylamine or Nacor, Inc., and 872 g of polyamide MxD6 6007 of Mitsubishi iGas are dry blended, dried in a vacuum oven at 110 ° C overnight, then it is extruded in a twin screw extruder Leistritz Micro-18 at 280 ° C. The extruded strand is cooled by air and chopped into pellets. 700 g of the above pellets are crystallized, then dried in a vacuum oven overnight, then extruded in three-layer film with two outer layers of PET-9921. Samples of two square inches of the film are oriented 4x4 on a T.M. Long. Oxygen permeability measurements in a Mocon 'Oxtran 2/20 show a significant reduction compared to a clay free control. Through this application, reference is made to various publications. The descriptions of these publications in their entirety are hereby incorporated by reference in this application to more fully describe the state of the art to which this invention pertains. It will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from the consideration of practical specification of the invention described herein. It is intended that the specification and examples be considered as examples only, with a true scope and spirit of the invention indicated by the following claims.

Claims (50)

1. CLAIMS 1. A clay polymer nanocomposite comprising: (i) a melt processable matrix polymer, (ii) a layered clay material, and (iii) an oligomer or functionalized polymer compatible with matrix polymer. The nanocomposite according to claim 1, characterized in that the melt processable matrix polymer comprises a polyester, polyether ester, polyamide, polyesteramide, polyurethane, polyimide, polyetherimide, polyurea, polyamideimide, polyphenylene oxide, phenoxy resin, polyolefin, polyacrylate, polystyrene. , polyethylene-co-vinyl alcohol, or polymers thereof or a mixture thereof. The nanocomposite according to claim 1, characterized in that the melt processable matrix polymer comprises a partially aromatic polyamide, aliphatic polyamide, fully aromatic polyamide or a mixture thereof. 4. The nanocomposite according to claim 1, characterized in that the melt-processable matrix polymer comprises poly (m-xylylene adipamide) or a copolymer thereof, poly (m-xylylene adipamide) modified by isophthalic acid, nylon- 6, nylon-6,6, or a ^^ i ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^ ^^^^^^^ ^^^^^^^^^^^^ t e ^^^^^^^^^ copolymer thereof, EVOH or a mixture miamos. 5. The nanocomposite according to claim 1, characterized in that the melt-processable matrix polymer comprises poly (methylene terephthalate) or a copolymer thereof, or a mixture thereof., 6. The nanocomposite according to claim 1, characterized in that it comprises more than zero up to about 25 weight percent of the layered clay material. 7. The compliance nanocomposite bon according to claim 1, characterized in that it comprises from about 0.5 to about 15 weight percent of the layered clay material. The nanocomposite according to claim 1, characterized in that the layered clay material comprises montmorilomta, hectorite, mica, vermiculite, bentonite, nontronite, beidelite, volconscoite, saponite, magadite, kenyaite, or a mixture thereof. 9. The nanocomposite according to claim 1, wherein the layered clay material comprises sodium montmorilomta Wypmmg type sodium bentonite or Wyoming type. 10. The nanocomposite according to claim 1, characterized in that the layered clay material is a free flowing powder having a cation exchange capacity of about 0.9 to about 1.5 meq / g. The nanocomposite according to claim 1, characterized in that at least 50 percent of the layered clay material is dispersed in the form of individual and tactile platelet particles i in the matrix polymer and the individual platelet particles have a thickness of less than about 2 nm and a diameter of from about 10 to about 3000 nm. 12. The compliance nanocomposite according to claim 1, characterized in that the functionalized oligomer or polymer and the melt processable matrix polymer have the same monomer unit. 13. The nanocomposite according to claim 1, characterized in that the layered clay material is treated with an organic cation. 14. The nanocomposite according to claim 13, characterized in that the organic cation is derived from an onium salt compound. 15. The nanocomposite according to claim 14, characterized in that the onium salt compound comprises an ammonium or phosphonium salt compound. 16. The nanocomposite according to claim 14, characterized in that the organic cation comprises an alkylammonium ion, alkyl phosphonium ion, polyalkoxylated ammonium ion, or a mixture thereof. 17. The nanocomposite according to claim 1, characterized in that the melt-processable matrix polymer comprises poly (ethylene terephthalate) or a copolymer thereof, the layered clay material comprises Wyoming-type sodium montmorillonite or Wyoming-type sodium bentonite. 18. The article prepared from the nanocomposite according to claim 1. 19. The article of conformity of claim 18 in the form of film, sheet, pipe, an extruded article, a molded article or a molded container. 20. The article according to claim 18 in the form of a bottle. 21. The article according to claim 18, characterized in that it has a gas permeability that is at least 10 percent lower than that of an article formed from a clay-free polymer. 22. The article having a plurality of layers, characterized in that at least one layer is formed of the nanocomposite according to claim 1. The article according to claim 22, characterized in that the nanocomposite is disposed intermediate to the other two layers. 24. The article of claim 22, characterized in that it has one or more layers of a structural polymer. 25. A clay polymer nanocomposite characterized in that it comprises: (i) a melt processable matrix polymer, and incorporated therein. (n) a concentrate comprising a layered clay material and an oligomer or functionalized polymer compatible with the matrix polymer. The compliant nanocomposite according to claim 25, characterized in that the melt processable matrix polymer comprises a polyester, polyether ester, polyamide, polyesteramide, polyurethane, polyimide, polyetherimide, polyurea, polyamideimide, polyphenylene oxide, phenoxy resin, polyolefin, polyacrylate, polystyrene. , polyethylene-co-vinyl alcohol, or polymers thereof or a mixture thereof. 27. The nanocomposite according to claim 25, characterized in that the melt processable matrix polymer comprises a partially aromatic polyamide, aliphatic polyamide, fully aromatic polyamide or a mixture thereof. The nanocomposite according to claim 25, characterized in that the melt-processable matrix polymer comprises poly (m-xylylene adipamide) or a copolymer thereof, poly (m-xylylene adipamide) modified by isophthalic acid, nylon-6 , nylon-6, 6, or a copolymer thereof, EVOH or a mixture thereof. 29. The nanocomposite according to claim 25, characterized in that the melt-processable matrix polymer comprises poly (ethylene terephthalate) or a copolymer thereof, or a mixture thereof., 30. The nanocomposite according to claim 25, characterized in that it comprises more than zero up to about 25 weight percent of the layered clay material. 31. The nanocomposite according to claim 25, characterized in that the layered clay material comprises montmorillonite, hectorite, mica, vermiculite, bentonite, nontronite, beidelite, volconscoite, saponite, magadite, kenyaite, or a mixture thereof. 32. The nanocomposite according to claim 25, characterized in that the layered clay material comprises sodium montmorillonite type, yoming or Wyoming-type sodium bentonite. The nanocomposite according to claim 25, characterized in that the layered clay material is a free flowing powder that has The amount of cation exchange capacity is from about 0.9 to about 1.5 meq / g. 34. The nanocomposite according to claim 25, characterized in that at least 50 5 percent of the layered clay material is dispersed in the form of individual platelet and tachyroid particles in the matrix polymer and the individual platelet particles have a thickness of less than about 2 nm and a diameter of about 10 to about 10 3000 nm. 35. The nanocomposite according to claim 25, characterized in that the functionalized oligomer or polymer and the melt processable matrix polymer have the same monomer unit. 36. The nanocomposite according to claim 25, characterized in that the layered clay material is treated with an organic cation. 37. A process for preparing a clay polymer nanocomposite characterized in that it comprises the steps of: (i) forming a concentrate comprising a layered clay material and an oligomer or functionalized polymer, and (ii) melting the concentrate with a melt processable matrix polymer to form a ^^^^^^^^ ß ^ J ^ H ^^^ - ^^^^ * ai¿B ^^^^^^^^^^ ß ^? ^^ ßA ^ iß¿ ^ H ^ BH ^ ^^ ß ^ _ ^^ i ^ * í ^^^ J¡ ^^^ nanocomposite polymer clay. 38. The process according to claim 39, characterized in that steps (i) and (ii) are conducted by an extrusion process of fusion preparation or a 5 mixed by batch. 39. The process according to claim 37, characterized in that the concentrate is prepared in water or a mixture of water and one or more organic solvents miscible in water comprising alcohols, ethers, acids, and nitriles. 40. The process according to claim 39, characterized in that the water-miscible organic solvents comprise dioxane, tetrahydrofuran, methanol, ethanol, isopropanol, acetic acid, acetonitrile, or mixtures thereof. 41. The process according to claim 37, characterized in that the functionalized oligomer or polymer and the melt processable matrix polymer have the same monomer unit. 42. The process in accordance with the claim 20 37, characterized in that the concentrate of step (i) comprises from about 20 to about 99.5 weight percent of the functionalized polymer or oligomer and from about 0.5 to about 80 weight percent of the layered clay material. 25 43. A nanocomposite material produced by the The process of claim 37. 44. An article prepared from the nanocomposite material according to claim 43. The article according to claim 44 in the form of film, sheet, fiber, an extruded article, an article. molded, or a molded container. 46. The article according to claim 44 in the form of a bottle. 47. The article according to claim 44, characterized in that it has a gas permeability that is at least 10 percent lower than that of the unmodified polymer. 48. A process to prepare a nanocomposite Polymer clay characterized in that it comprises: melt-blending a layered clay material, an oligomer or functionalized polymer, and a melt-processable matrix polymer to form a nano-composite clay polymer material. 49. The process according to claim 48, characterized in that the nanocomposite material comprises from about 0.5 to about 25 weight percent of the functionalized polymer or oligomer, from about 50 to about 99 percent by weight. 25 weight of the matrix polymer, and from about 0.5 to ^^^^^^^ ^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ About 25 percent by weight of the layered clay material. 50. The nanocomposite material produced by the process according to claim 48. 51. An article prepared from the nanocomposite material according to claim 50. ^^^ b ^ ¡^^ ¿^ ¡^ ^ ¿h ^^ ¡h¡¿ ^^^^^^^^^^^^^