Surface modified layered silicate material and compositions containing the same

[0001] [Technical field to which the invention belongs] In the present invention, a layered silicate such as a phyllosilicate (such as smectite clay) is positively charged at a plurality of locations (hereinafter referred to as "multicharged"), preferably at two locations. An intercalated layered material prepared by contacting with a coupling agent and thereby intercalating, optionally an exfoliate thereof, and a cointercalant of the layered material. Concerning the synthesis of nanocomposites by co-intercalation with (co-intercalant) (co-intercalant polymerizable reactant). Cointercalant monomers, oligomers or polymers are cointercalants with layers of multicharged onium ions intercalated, for example in a mixing or extrusion device, after or at the same time as the intercalation of the multicharge separation / coupling agent. The co-intercalated layered material and nanocomplex can be produced by intercalation by direct compounding by blending a monomer, a polymer or an oligomer. The intercalation spacing (d-spacing minus the thickness of one platelet of the layered material) between adjacent layers (platelets) of the layered material is the cointercalant polymer reactant, oligomeric cointercalant or polymer. At least 3 Å, preferably at least 15 Å, preferably at least 10 Å, preferably at least 15 Å, and usually at least 3 Å, preferably at least 15 Å, preferably at least 15 Å, by contacting the polycharge separation / coupling agent to intercalate the layers simultaneously or later with the cointercalant. It can be expanded to about 18 Å. The multi-charge separation / coupling agent is at least two charged, Li⁺, Na⁺, K^-, Ca⁺², Mg⁺², Or have atoms that can be ion-exchanged with other inorganic cations (occurring in the interlayer space between adjacent silicate layers or plates of intercalated layered silicates). The association of layered inorganic cations with at least two charged sites in the multicharged separation / coupling agent exchanges substantially a small amount of onium ions into the space of adjacent small plates, similar to monocharged onium ions. Hydrophilic by substantially completing the ion exchange of exchangeable interlayer cations on the surface of the disc with onium ions, leaving more space for oligomeric or polymer cointercalation when compared to the body. Allows conversion from the inner clay disc surface to the hydrophobic disc surface. Thus, a polymer cointercalant, or a polymerizable oligomeric cointercalant molecule, or a polymerizable monomer capable of forming a cointercalant polymer by reaction, is located between adjacent plates of a layered silicate, such as smectite clay plates. Can be easily and more completely intercalated. [0002] In a preferred embodiment of the present invention, a fully polymerized cointercalant polymer having an average molecular weight in the range of about 1-5 million, preferably about 1,000-500,000, is intercalated with a polycharge separating / coupling agent. Dispersing the layered material intercalated with polycharged onium ions into the matrix polymer, i.e., adding an excess of cointercalant oligomer or polymer, between adjacent plates of the layered material. Cointercalation of the multicharge separation / coupling agent by direct complexing with the intercalated layered cointercalant oligomer or polymer, and without separating the resulting intercalate. And the excess cointercalant polymer becomes a matrix polymer, which is exactly the same as the cointercalant polymer. [0003] Multicharge separators / coupling agents and cointercalant oligomers or polymers, or monomer reactants thereof (cointercalant polymerizable monomer reactants, cointercalant oligomers, and cointercalant polymers, hereinafter collectively for brevity. Intercalation of the "intercalant polymer" or "cointercalant polymer") results in a completely uniform dispersion in the matrix polymer of the cointercalated layered material, i.e. a nanocomplex composition. Be done. Optionally, the nanocomplex composition is sheared above the melting temperature or melting temperature of the matrix polymer to exfoliate up to 100% of the tactoids or plaque mass into individual plaques, resulting in 50% by weight or more plaques. It can be in the form of a single disc, for example 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more can be completely peeled off into a single plateau layer. [0004] The intercalated product of the present invention can be used as an organic clay for accommodating organic materials, or can be uniformly dispersed in a solvent to increase the viscosity of the organic liquid, and further such an intercalated product. Sufficient cointercalant oligomers to achieve, for example, clay intercalation sufficient to form concentrates that can be later mixed with matrix polymers and / or additional intercalant polymers, or with different polymer materials. Alternatively, the polymer and the polycharge separation / coupling agent can be dispersed in the matrix polymer to form a polymer / clay intercalated nanocomplex by direct complexing with the intercalated clay. Alternatively, the clay intercalated with the multicharge separation / coupling agent can be cointercalated with a polymerizable monomeric reactant to form a polymer cointercalant. [0005] In another embodiment of the invention, the multicharged separator / coupling agent intercalated layered material can be dispersed in the matrix polymer, and then the matrix polymer is in-situ, eg. It is polymerized by adding a curing agent to form a nanocomplex. Also, the hardener can be directly cointercalated between the clay plates intercalated with the polycharge separation / coupling agent and then intercalated into the clay intercalation caves (gallery). The reaction product intercalant monomer is polymerized. [0006] According to an important feature of the present invention, the intercalant polymer is cointercalated into the multicharged separator / coupling agent intercalated clay caves to form a cointercalated product, and additional polymer is added. Once the nanocomplexes are formed, the cointercalant polymer can be directly composited with the matrix polymer, the nanocomplexes are easily formed, and such cointercalated products are monocharged. The cointercalant polymer can be applied more sufficiently than when the small plates are separated by using an onium ion separation / coupling agent. If a polymerizable cointercalant monomer, or polymerizable oligomeric intercalant, is cointercalated into a clay cave, such cointercalant (1 or more) is polymerized with the desired monomer, oligomer or polymer matrix material. The matrix material can then be polymerized with the copolymer or further polymerized and composited to form nanocomplexes. [0007] [Conventional technology] For example, phyllosilicates such as smectite clay such as sodium montmorillonite and calcium montmorillonite are treated with organic molecules such as organic ammonium ion, phosphonium ion, or sulfonium ion (onium ion) to obtain the organic onium ion molecule. Adjacent to separate (intercalate) adjacent layers or plates of layered silicate enough to exchange ions with exchangeable interlayer cations and intercalate the polymer between separated layers. It is well known that organic molecules can be intercalated between flat plate silicate layers (see US Pat. Nos. 4,739,007, 4,810,734 and 5,164,460). The intercalated phyllosilicate treated in this way has an intercalation spacing increased to at least 3 Å, preferably at least 5 Å, with an intercalation spacing of at least about 10-25 Å up to about 100 Å. Then, for example, the silicate layer can be separated (eg, mechanically, by strong shear mixing) and exfoliated. The individual silicate layers are matrix polymers such as mechanical strength, oxygen permeability, and / or high temperature resistance properties when mixed with the matrix polymer before, after, or during polymerization of the matrix polymer, such as polyamide. It has been found to substantially improve one or more of the properties of (see US Pat. Nos. 4,739,007, 4,810,734, 5,102,948 and 5,385,776). [0008] Examples of prior art composites, also referred to as "nanocomposites," are disclosed in AlliedSignal Inc.'s published International Patents WO 93/04118 and US Pat. Nos. 5,385,776. More than one or more properties of the matrix polymer by mixing the individual plate particles from the intercalated layered silicate with the polymer and adding at least a portion of the exfoliated intercalated material. It discloses that nanocomposites with improved properties are formed. As disclosed in International Patent No. WO 93/04118 and US Pat. No. 5,554,670, onium cations such as quaternary ammonium compounds having reactive groups compatible with silane coupling agents or matrix polymers. Adsorption forms intercalated material, i.e. increases the interlaminar spacing between adjacent silicate plates. It is well known that such quaternary ammonium cations convert highly hydrophilic clays such as sodium montmorillonite or calcium montmorillonite into lipophilic clays capable of accommodating organic molecules. [0009] [Problems to be Solved by the Invention] The present invention has been made in view of the present situation, and provides an intercalated product which can bring about favorable properties such as a decrease in oxygen permeability to a matrix polymer. The purpose is. [0010] [Means for solving problems] The present invention has been achieved in order to achieve the above object, and the gist thereof is as follows. [0011] In a preferred embodiment of the present invention, the intercalation product is a layered material such as phyllosilicate and a dionium ion separating / coupling agent compound, which comprises at least two carbon atoms and up to about 24 carbon atoms. It is prepared by contacting with a polycharged onium ion separating / coupling agent such as a compound having. Examples of such suitable multicharge separation / coupling agent molecules belong to the V or VI group of quaternary diammonium ions, disulfonium ions, diphosphonium ions, dioxonium ions, or periodic tables of elements. Examples include polycharged ammonium ion compounds with various elements. [0012] The polycharged onium ion separating / coupling agent compound useful in the present invention can become polycharged as anions dissociate from the molecule when dissolved in water and / or an organic solvent, or the molecule is medium. It may then provide an onium ion molecule that is sex and then in solution has a plurality of positively charged atoms that are protonated. [0013] Depending on the cation exchange capacity of the layered silicate, such as smectite clay, the inner plate surface of the silicate plate is between about 4 Å and about 20 Å (between adjacent exchangeable cations in the interlayer space). Includes load center with intervals that vary with interval, or equivalent to distance). [0014] According to the features of the present invention, the polycharged onium ion separating / coupling agents are charged appropriately separated so as to use a smaller amount of separating / coupling agent to separate sufficiently adjacent small plates. Onium ion atoms can be intercalated between adjacent plates so as to balance the charge center within the same silicate plate surface, eg Na.⁺It has been found that it can be ion exchanged with interlayer cations such as ions. In a preferred embodiment, at least two of the charged atoms of the polycharged onium ion separator / coupling agent are intermediate organic molecules, such as -CH.₂-CH₂-;-CH₂-CH₂-CH₂-Equally separated, charged onium ion atoms are separated at a distance of about 5 Å (for high charge density layered material) to about 24 Å (for low charge density layered material) (eg N).⁺-Gap-N⁺). With such a favorable separation between the charged onium ion atoms, ion exchange with the interlayer cations occurs at both charged onium ion atoms, thereby forming a silicate plate sufficient for oligomeric or polymer cointercalation. While separation is achieved and higher quality cointercalation of the cointercalant oligomer or polymer is allowed, less onium ion intercalation is required to achieve complete ion exchange. [0015] As shown in FIGS. 1 (a) and 1 (b), it has a high charge density and a distance between the negatively charged centers on the surface of adjacent interlayer plates in the range of about 6 Å to about 12 Å. The layered material can be ion-exchanged with both adjacent charged atoms of the dicharged onium ion separator / coupling agent, which have charged atoms separated by a distance of about 4 Å to about 14 Å to 16 Å. The spacing between the two closest charged atoms of the polycharged onium ion separation / coupling agent does not have to be exactly the same as the exchangeable cations on the surface of the layered plateau, which is the plateau. This is because each negative charge spreading in and above the surface (corresponding to the position of exchangeable cations) diffuses outward radially about a distance of about 5 Å from the negative charge center. The dashed circles surrounding the adjacent negatively charged centers, shown in FIGS. 1 (a) and 1 (b), are farther away from the negatively charged centers and are weaker, and FIGS. 1 (a) 1 and 1 ( As shown in b), for example, Na⁺Represents a diffuse negative charge located directly on an exchangeable cation such as. Between high-to-medium charge densities (150 milligram equivalents per 100 gram cation exchange capacity (CEC) to 70 milligram equivalents per 100 gram CEC) of the nearest charged atoms of the separation / coupling agent. The preferred spacing is C in the organic demarcation molecule between the charged onium ion atoms.₃To C₁₀It is about 6 Å to about 20 Å, which corresponds to the molecular skeleton of. For layered material with medium to low charge densities (70 eq / 100 eq CEC to 30 eq / 100 gram CEC), the preferred spacing of onium ion spacing / coupling agents is for both charged onium ion atoms. C in organically separated molecules covalently bound to₆To C₁₂It is about 12 Å to about 24 Å, which corresponds to the molecular skeleton of. [0016] According to an important feature of the present invention, the layered material has a concentration of at least about 0.25 mol, preferably at least about 0.25 mol, of positively polycharged cation moieties of the onium ion compound per mol of exchangeable interlayer cations. Multicharged onium ion exchange with a molar ratio of at least 0.5: 1, more preferably 1: 1: Best results achieved by mixing with a polycharge separation / coupling agent with interchangeable interlayer cations. Be done. When less than all of the interlayer cations are ion-exchanged with polycharged onium ions, the residue of the interlayer cations can remain in place, or at least some of the residual interlayer cations are single. It may be exchanged for charged onium ions. A polycharged separator / coupling agent compound of at least about 2% by weight, preferably at least about 5% by weight, based on the dry weight of the layered material in the intercalation composition, relative to most of the layered material, such as montmorillonite clay. The molar ratio is achieved by intercalating at least about 10% by weight, and most preferably at least about 30% to about 200% by weight of the polycharge separation / coupling agent cations. Regardless of the concentration of the polycharge separation / coupling agent compound in the intercalation composition, such as oligomers or polymers (or monomer reactants thereof) between adjacent inner surfaces of adjacent flakes of the layered material. To achieve sufficient intercalation of one or more cointercalants, the weight ratio of the multicharge separator / coupling agent intercalant: layered material is at least 1:20, preferably at least 1:10, more preferably at least. 1: 5, and most preferably at least about 1: Should be 4. Multicharged demultiplexing / coupling agent compounds that are converged between silicate plates and ion-exchanged via ion exchange at polycharged atoms are of higher amounts of cointercalant oligomers or polymers than previously possible. It induces surprisingly easy intercalation or allows the intercalation of large amounts of monomeric reactants for polymerization at that location. [0017] According to an important feature of the present invention, phyllosilicates such as smectite clay intercalated with polycharged separators / coupling agents can be easily cointercalated with cointercalant polymers, thus in matrix polymers. It is possible to form an intercalation product with unexpectedly good intercalation material dispersibility and, unexpectedly, be co-intercalated with a large amount of cointercalating polymer molecules. The intercalation can also be added to any matrix polymer to enhance a number of properties of the matrix polymer, including tensile strength, thermal strain temperature, glass transition temperature, gas permeability, elongation and the like. [0018] Multicharge separation to increase the viscosity of the organic compound or to provide a matrix polymer / intercalated and / or matrix polymer / stripped composition to enhance one or more of the above properties of the matrix polymer. / Layers intercalated with coupling agents, cointercalated with polymer cointercalants, and / or strips thereof, matrix polymers or other organic monomer compounds (s) or compositions. Can be mixed with. [0019] Known organic clays that contain more (wider) intercalation spacing for adsorption of organic liquids and gases by intercalated layers and intercalation methods with the multicharge separation / coupling agents of the present invention. A unique organic clay that is useful for all purposes is provided. Also, according to a preferred embodiment of the invention, the intercalation is a direct composite of the intercalation, especially with various matrix polymers (either thermoplastic or thermosetting) (intercalating into the matrix polymer melt). It can be added by directly mixing the calated material). Examples of commercially available resin systems for use as cointercalant polymers and / or matrix polymers of nanocomplexes include bisphenol A-derived resins, epoxy cresol novolac resins, epoxyphenol novolac resins, bisphenol F resins, polycyclic phenol-glycidyl. Ether-derived resins, alicyclic epoxy resins, aromatic and heterocyclic glycidylamine resins, tetraglycidylmethylenediamine-derived resins, nylon-6 and nylon 66, and especially MXD6 nylon (polymers polymerized with meta-xylene diamine and adipic acid). Nylons such as. [0020] BEST MODE FOR CARRYING OUT THE INVENTION First, the meanings of the terms in the present specification will be described below. [0021] [0021] A "layered material" is an inorganic substance such as a smectite clay mineral, which is a combination of a plurality of adjacent layers, and each layer has a thickness of about 3 Å to about 50 Å, preferably about 10 Å. Is. [0022] "Plate" means each layer of a layered material. [0023] The "intercalated material" or "intercalated material" includes a polycharged onium ion separating / coupling agent molecule arranged between adjacent plates of a layered material, and of the separating / coupling agent. Ion exchange with cations on the inner plateau surface at multiple (at least two) charged atoms so that the intercalation between adjacent plates is at least 3 Å, preferably at least 5 Å, for example at least about 10 Å, preferably at least about 10 Å. Means a layered material that has been increased to at least about 15 Å, eg 18 Å, and after intercalation of the cointercalant polymer, the d-intercalation of the cointercalated material has been increased to at least about 20 Å, preferably 25 Å to 35 Å. .. [0024] "Intercalation" means the process for forming an intercalated material. [0025] A "multicharged separator / coupling agent" is two or more protons separated by at least two substituted or unsubstituted carbon atoms, preferably separated by 3-4, more preferably 3-6 carbon atoms. Nitrogen (ammonium or quaternary ammonium) atom (N)⁺); Two or more positively charged phosphorus (phosphonium) atoms (P)⁺); Two or more positively charged sulfur (sulfonium) atoms (S)⁺); Two or more positively charged oxygen (oxonium) atoms (O)⁺); Or N⁺, P⁺, S⁺And / or O⁺Means a monomeric organic compound containing at least two positively charged atoms, such as various combinations of. Preferred is N⁺, P⁺, S⁺, O⁺Alternatively, it is a quaternary ammonium compound containing two separated positively charged atoms, selected from one or more combinations of these. When dissolved in water and / or an organic solvent, anions dissociate from the polycharged separator / coupling agent compound, leaving at least two positively charged atoms selected from nitrogen, phosphorus, sulfur, and / or oxygen. The positively charged atoms are separated by two or more carbon atoms, leaving the polycharged cation molecules that they have, and such polycharged onium ions are preferably oniums that are positively charged at two locations. Ion Separation / Coupling Agent It has a positively charged atom located at the opposite end of the intercalant molecule. [0026] "Cointercalation" refers to intercalation by multicharge separation / coupling agent intercalation, and simultaneous or separate oligomer or polymer cointercalation, or reaction or polymerization to form a polymer. Cointercalant means a process for forming an intercalation of polymerizable monomers. [0027] "Concentrate" means an intercalation formed by intercalation of a polycharged separator / coupling agent and a cointercalant polymer, such intercalation being one or more of the matrix polymers. It is incorporated into the matrix polymer at a higher intercalation concentration than required to improve properties, and the concentrate is mixed with additional matrix polymer to create a nanocomplex composition. It is possible to form a product or a commercial product. [0028] An "intercalation carrier" is an intercalation of a polycharged onium ion demultiplexer / coupling agent and, simultaneously or separately, an intercalation of a cointercalant polymer or a cointercalant polymerizable monomer or oligomer between the platelets of a layered material. Water used with a polycharged onium ion demultiplexer / coupling agent and / or with a cointercalant polymer or cointercalant polymerizable monomer or oligomer to form an intercalation composition capable of achieving intercalation. And / or a carrier comprising an organic solvent. [0029] "Intercalation composition" or "intercalant composition" is a polycharged onium ion separating / coupling agent containing or not containing an intercalation carrier, and / or an intercalant polymer or an intercalant polymerizable monomer. Alternatively, it means a composition containing an oligomer and a layered material. [0030] "Peeled material" or "peeled material" is an individual plaque of an intercalated layered material, or an agglomerate of tactoids or individual plaques, which has a smaller total thickness than a non-peeled layered material. (For example, 2 to 10 plates, preferably 2 to 5 plates), individual small plates across carriers such as water, polymers, alcohols or glycols or various other organic solvents, or across matrix polymers. It is dispersed as a plate or tactoid. [0031] "Peeling" means the process for forming a strip from an intercalated product. [0032] A "matrix polymer" is a thermoplastic or thermosetting polymer in which an intercalated or exfoliated material is dispersed to improve the mechanical strength of such a matrix polymer and tolerate heat (eg, glass transition). Increase temperature (Tg)) and / or gas (O)₂) Means something that reduces transparency. [0033] Hereinafter, embodiments of the present invention will be described. [0034] First outlined, the present invention is an organic clay or intercalated layered material prepared by intercalating a polycharge separation / coupling agent between adjacent silicate platelets of a swellable layered material. Monomer, oligomers or polymer molecules as well as between the flat silicate layers or plates of swellable layered material such as phyllosilicates such as smectite clays intercalated with isolation / coupling agents, preferably montmorillonite sodium clay. It relates to a cointercalated product and a nanocomplex formed by co-intercalation. The spacing between adjacent layers of the layered material is widened by at least 3 Å, preferably at least about 5 Å to at least about 10 Å, preferably at least about 15 Å, usually about 15 to about 30 Å with the polycharged onium ion separator / coupling agent. , Forming a new organic clay. Monomers, oligomers or polymers (hereinafter collectively abbreviated as "polymers") by cointercalation of coincarants, then for use in augmenting organic liquid clays, and in preferred embodiments nano For mixtures with matrix polymers forming complexes or compositions, increase the d-spacing of adjacent layers by at least 20 Å, preferably up to about 25 Å to about 35 Å, and up to 300 Å. [0035] The present invention relates to a method for preparing an intercalated layered material prepared by intercalation of a polycharged onium ion separating / coupling agent, and in a preferred embodiment, an oligomer into a cave of the layered material. Cointercalation of sex or polymeric cointercalants to form intercalations or intercalation concentrated compositions for incorporation into one or more matrix polymers, such as by direct composite with matrix polymer melts. [0036] The present invention also relates to a strip prepared from the intercalation or intercalation concentrated composition. The exfoliate can be prepared by diluting the concentrate with a matrix polymer (or additional matrix polymer) and then curing. The presence of a polymerizable monomer or oligomer or polymer in the cave of the layered material causes the layered material to become a matrix polymer when the intercalating material is added to the same additional matrix polymer as the cointercalated monomer, oligomer or polymer. It becomes compatible with. When a polymer hardener is added, the layered material can expand and be stripped by the intercalating monomers or oligomers that are polymerizing, and the resulting polymer molecules are platelets, depending on the degree of polymerization achieved. Distributed between layers. The stripped individual layers or tactoids of the intercalated and / or layered material act as polymer tougheners and molecular (gas) barriers in the matrix polymer, providing the mechanical and barrier properties of the matrix polymer. It improves (eg, reduces gas permeability) and raises the gas transition temperature (Tg). The strips can also be prepared by adding a curing agent directly to the monomer / oligomer / or polymer intercalated concentrate. The curing agent penetrates into the cave region of the intercalated material and reacts with the polymerizable monomer or oligomer or polymer that has been cointercalated in the interlayer cave in advance, and the intercalated material and / or its exfoliated product. , And form plate or multilayer intercalated or tactoids uniformly dispersed in the nanocomplex containing the matrix polymer. [0037] In another aspect of the invention, an intercalation is added to the composition carrier or a polar organic compound containing an organic solvent or a carrier containing a polar organic compound to transport the carrier or solvent, or to transport the carrier or solvent. A carrier composition having an unpredictable viscosity can be provided for administration of the active ingredient dissolved or dispersed therein. Such compositions, which are particularly high viscosity gels, provide extremely high viscosity for the transport of active ingredients such as lubricants for hair wave lotions and drugs for topical administration; and for example cosmetics, petroleum. Especially for mixing rheological modifications of mining liquids, paints, lubricants (especially food grade lubricants), and in the production of lubricants, greases, etc. with intercalated products or strips thereof and organic solvents. It is useful. Such intercalated and / or stripped products are also particularly useful as mixtures with matrix thermoplastic or thermosetting polymers in the production of nanocomplexes for forming polymer commodities. [0038] Organic liquid compositions containing intercalated and / or strips are difficult to phase separate and can be used to deliver a variety of active ingredients in the cosmetics, hair care and pharmaceutical industries and the like. The shape of the rock-modified gel can be stable. The layered material is intercalated by contact with the multicharge separation / coupling agent to form a new organic clay. Onium ions are generated by co-intercalating an oligomer or polymer between adjacent separated phyllosilicate discs and directly compounding them with an extruder to optionally separate (peeling) the layered material into individual discs. Cointercalant oligomers or polymers are added to the intercalated layers simultaneously or later to provide cointercalated layers for mixing with matrix polymers to provide nanocomplex compositions. Form. [0039] The addition of the cointercalation to the matrix polymer melt enhances one or more properties of the matrix polymer melt, such as strength or heat resistance, and especially gas permeability; or an intercalation with a carrier or solvent. Alternatively, by mixing the cointercalation, the viscosity and rocking denaturation of the carrier material is maintained and / or increased. The intercalated and cointercalated products of the present invention are easily dispersed homogeneously and uniformly throughout the carrier or solvent, and thus the carrier / plate composition even after the addition of active organic components such as cosmetic ingredients or pharmaceuticals. It gives the product a new and unexpected viscosity, which is beneficial for the administration of active organic compounds from the composition. The cointercalated products of the present invention are also easily dispersed uniformly and uniformly in the matrix polymer to provide the matrix polymer with new, unexpected gas barriers and strength properties. [0040] The features and advantages described above, and yet yet another of the present invention, should be more clearly understood from the following description, along with the drawings. [0041] In order to form the intercalated and stripped products of the present invention, the layered material (eg, phyllosilicate) should be swollen or intercalated by the sorption of the multicharge separation / coupling agent. In order to form a cointercalated product of the nanocomplex according to a preferred embodiment of the present invention, the layered material intercalated with polycharged onium ions may be composed of a cointercalant polymerizable monomer, a polymerizable oligomer or a polymer. Co-intercalated at the same time or later. [0042] Useful polycharge separation / coupling agents include, for example, aliphatic, aromatic or aryl aliphatic amines, phosphines, esters, alcohols and sulfides tetra-ammonium, tri-ammonium, and di-ammonium (primary, 2). Classes, tertiary, and quaternary), tetra-, tri-, and di-onium species such as -phosphonium, -oxonium, or -sulfonium derivatives are included. Examples of such substances include compounds having the following formulas. [0043] [Chemical 2]<img file="JP4646352B2_D0001.tif" />[0044] [In the formula, X⁺And Y⁺Can be the same or different,-⁺NH₃、-⁺NH₂、-⁺N (CH₃)₃、-⁺N (CH₃)₂-、-⁺N (CH₃)₂(CH₂CH₃)、-⁺N (CH₃) (CH₂CH₃)-、-⁺S (CH₃)₃、-⁺S (CH₃)₂、-⁺P (CH₃)₃、-⁺P (CH₃)₂、-⁺NH₄、-⁺NH₃-Ammonium, sulfonium, phosphonium, or oxonium groups such as, etc .; R is an organic separated scaffold group preferably having 2 to 24, more preferably 3 to 10 carbon atoms, linear or branched chain. May be, organically separated molecules in the skeleton are charged N⁺, P⁺, S⁺And / or O⁺It is covalently attached to a cation at its end, and R¹Is a hydrogen atom, or a linear or branched alkyl group having 1-22, preferably at least 6 carbon atoms]. Examples of R include amino, alkylamino, dialkylamino, nitro, azide, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkyl, aryloxy, arylalkylamino, alkylamino, arylamino, dialkylamino, Diarylamino, aryl, alkylsulfonyl, aryloxy, alkylsulfinyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, or alkylsilane substituted or unsubstituted alkylene, cycloalkenylene, cycloalkylene, arylene, alkyl Arylen is included. R¹May not be present, for example hydrogen atoms; amino, alkylamino, dialkylamino, nitro, azide, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkyl, aryloxy, arylalkylamino. , Alkylamino, arylamino, dialkylamino, diarylamino, aryl, alkylsulfonyl, aryloxy, alkylsulfinyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, or alkylsilane substituted or unsubstituted. Includes linear or branched alkyl, cycloalkenyl, cycloalkyl, aryl, and alkylaryl having 1-22 carbon atoms. Examples of useful R groups are alkylenes such as methylene, ethylene, octylene, nonylene, tert-butylene, neopentylene, isopropylene, sec-butylene, dodecylene; 1-propenylene, 1-butenylene, 1-pentenylene, 1-hexenylene. Alkenylene such as 1-heptenylene and 1-octenylene, cycloalkenylene such as cyclohexenylene and cyclopentenylene; butanoyl octadecylene, pentannoyl nonadesilene, octanoyl pentadecylene, etanoyl undecylene, propanoyl hexa Alkanoylalkylenes such as decylene; alkylaminoalkylenes such as methylaminooctadecylene, ethylaminopentadecylene, butylaminononadecilene; dialkylaminoalkylenes such as dimethylaminooctadecylene, methylethylaminononadecilene; phenylamino Arylaminoalkylenes such as octadecylene, p-methylphenylaminononadecilene; diarylaminoalkylenes such as diphenylaminopentadecylene, p-nitrophenyl-p'-methylphenylaminooctadecilene; 2-phenyl-4- Alkylarylaminoalkylenes such as methylaminopentadecylene;₃H₆COO-, -C₅H₁₀COO-, -C₇H₁₀COO-, -C₇H₁₄COO-, -C₈H₁₈COO-, -C₁₁H₂₂COO-, -C₁₃H₂₆COO-, -C₁₅H₃₀COO- and -C₁₇H₃₄COO- and -C = C (CH)₃) COOCH₂CH₂-Examples include polypropylene glycol and polyethylene glycol substituents according to the part represented by the formula such as. Such tetra-, tri-, and di-ammonium, -sulfonium, -phosphonium, -oxonium; ammonium / sulfonium; ammonium / phosphonium; ammonium / oxonium; phosphonium / oxonium; sulfonium / oxonium; and sulfonium / phosphonium groups are relevant. It is well known in the art and may be derived from the corresponding amines, phosphines, alcohols or ethers, and sulfides. [0045] The sorption of the multicharge separation / coupling agent should be sufficient to widen the intercalation between adjacent plates of the layered material to at least about 10 Å, preferably at least about 15 Å when measured in the dry state. So that the intercalation of both the multicharged separator / coupling agent and the cointercalant polymer usually achieves an interlayer spacing of at least about 20 Å, preferably at least about 25 Å, up to about 300 Å. Should. [0046] Multicharged Onium Ion Separation / Coupling agent sorption and ion exchange, based on the dry weight of the layered material, at least about 2%, preferably at least about 5% by weight, of the polycharged separation in the intercalation composition. / Coupling agent, more preferably at least about 50% to about 200% by weight of polycharge separation / polycharge separation at a concentration of coupling agent / layered material with coupling agent (progenitor, or many if necessary) Multicharged separation / coupling in an intercalation composition containing or not containing an organic solvent (eg, an aliphatic hydrocarbon such as heptane) to assist in the dissolution of the charged onium ion compound. The agent is introduced into the cave of the layered material in solid or liquid form. [0047] In a preferred embodiment, a layered material, such as smectite clay, is slurried in water and a multicharged separator / coupling agent (multicharged cation) is placed in the clay slurry water, preferably between polycharged onium ions vs. clay. The cations are dissolved at a molar ratio of at least about 0.25: 1, more preferably at least about 0.5: 1, and even more preferably at least about 1: 1. The clay intercalated with the polycharge desorber / coupling agent is then easily separated from the water because the layered material (clay) is no longer hydrophobic, and before being combined with the cointercalant polymer. And preferably prior to compounding with the matrix polymer, which is the same as the cointercalant polymer, it is dried in the oven to a moisture content of less than 5% based on the dry weight of the layered material, preferably until completely dry. [0048] Multicharge separation / coupling agent compounds are used in layered / multicharge separation / coupling agent compound blends in which at least about 20% water, preferably at least about 30% or more water, is present based on the dry weight of the layered material. By adding it, it can be added as a solid. Based on the dry weight of the layered material, preferably about 30% to about 50% water, more preferably about 30% to about 40% water is incorporated into the multicharge separation / coupling agent intercalation composition. Thus, the intercalation allows only a small amount of water to be accumulated, thereby reducing the energy required for drying after the intercalation of the polycharged demultiplexing / coupling agent compound. [0049] Preferred polycharge separation / coupling agent compounds are each selected from primary, secondary, tertiary or quaternary ammonium, phosphonium, sulfonium, and / or oxonium ions and may be the same or different, at least two. It is a multi-onium ion compound containing two positively charged atoms and is represented by the following formula. [0050] [Chemical 3]<img file="JP4646352B2_D0002.tif" />[0051] [In the formula, R is an alkylene, aralkylene or substituted alkylene charged atom separating moiety, preferably C.₃From C₂₄More preferably C for layers with a range of, and relatively high charge densities (150 mg equivalent / 100 gram CEC to 70 mg equivalent / 100 gram CEC).₃From C₆For layers with moderate to low charge densities (70 mg equivalent / 100 gram CEC to 30 mg equivalent / 100 gram CEC), preferably C₆From C₁₂Is the range of. R may be linear or branched, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂, C₂₃And C₂₄Parts may be alone or in combination; R₁, R₂, R₃And R₄May be the same or different, hydrogen atom, alkyl, aralkyl, benzyl, substituted benzyl (either linear or branched chain alkyl substitution or halogen substitution); ethoxylated or propoxylated benzyl (For example, 1 to 10 mol of ethoxylation or 1 to 10 mol of propoxylation). It is a component selected from the group consisting of. Z¹And Z²May be the same or different, may not exist, or R₁, R₂And R₃And R₄It may be any of the parts similar to those defined for. Also, Z¹And Z²One or both may contain one or more positively charged atoms or onium ions. ] Only single charged ammonium or phosphonium ions are used in the prior art organic clays used to intercalate the clay. The present invention discloses a first organic clay composition in which an organic clay is prepared using polycharged, preferably bicharged cationic onium ions. In particular, the compositions of the present invention are more suitable for polymer-clay nanocomposite preparations, such as in-reactor and direct composite pathways. Multicharged cationic surfactant (at least C₆From about C₂₄Onium ions having at least one group attached to one of the charged atoms having a chain length of up to) are preferred, are commercially available at very affordable prices, and use less onium ion agents. Therefore, complete ion exchange for interlayer cations can be performed so as to leave more room for polymer cointercalation as shown in Table 1 below. [0052] [table 1]<img file="JP4646352B2_D0003.tif" />[0053] The organic clay of the present invention in which the above-mentioned dicharged onium ions are intercalated is prepared by a dicharged onium ion exchange reaction process. Surprisingly, both charged atoms of the Taro diamine intercalant ion-exchanged with the same plate surface of smectite clay and did not form crosslinks with the adjacent plate surface. To achieve the full advantage of the present invention, the distance between at least two separated charged atoms of a polycharged onium ion is the average distance between two exchangeable cations or adjacent negative charges on the clay plate surface. Should be in the range of (within about 6 Å). For example, the average area occupied by the negative charge of 140 mg equivalent / 100 g of CEC montmorillonite clay is 70-80 Å.²Is. Therefore, the average distance of adjacent charges is 8-9 Å. In Taro diamine, two charged ammonium groups (two charged nitrogen atoms N)⁺Is separated by three carbon atoms) The distance is about 8 Å. [0054] [Chemical 4]<img file="JP4646352B2_D0004.tif" />[0055] Figure 1 (a) shows the negative charge center and the corresponding associated cation (Na).⁺) Is schematically shown as a layered small plate having a cation charge density so as to be separated by a distance L. As shown in Figures 1 (b), 1 (c) and 1 (d), polycharged onium ions have different chain lengths due to the negative charge occupying a substantial radiation distance of about 5 Å from the negative charge center. Carbon-separated molecule R₁, R₂And R₃While having (R₁&lt;R₃= L &lt;R₂), Both adjacent Na⁺Na at the ion⁺It can exchange ions with cations. Therefore, it can be considered that the distance between two positively charged atoms of a polycharged onium ion may differ depending on the charge density of the layered material. [0056] Therefore, as shown in FIGS. 2 (a), 2 (b), 3 (a) and 3 (b), the Taro (R) group extending upward from the plate surface and the adjacent exchange on the same silicate plate surface. The possible cations and the two charged amino groups of the tallow diamine molecule are therefore, upon substitution, each located within approximately 6 Å of the negative charge center (in this case, each N).⁺Ions are within about 1 Å of the negative charge center). [0057] Figures 3 (a) and 3 (b) outline the differences between organic clays prepared using single-charged onium ions and double-charged onium ions. The hydrophobic (taro) tail of the bicharged surfactant intercalates just like organic clay exchanged with a single charged onium ion, intercalating oligomers and polymer guest molecules into the cave of the clay. Tolerate. The degree of intercalation of cointercalant polymer molecules into the caves of mono-onium or two-onium ion organic clay is the fact that the chain lengths of both intercalants are the same (a regulator in intercalation). ) Can be considered to be the same. However, due to the fact that the number of long (taro) tails of dicharged onium ions has been reduced to 50%, cointercalants, as schematically shown in Figures 3 (a) and 3 (b). The capacity occupied by the polymer molecule should be substantially increased. [0058] [0058] Preferred examples of commercially available polycharged onium surfactants include: [0059] [Chemical 5]<img file="JP4646352B2_D0005.tif" />[0060] [Chemical 6]<img file="JP4646352B2_D0006.tif" />[0061] [Chemical 7]<img file="JP4646352B2_D0007.tif" />[0062] [Chemical 8]<img file="JP4646352B2_D0008.tif" />[0063] [Chemical 9]<img file="JP4646352B2_D0009.tif" />[0064] [Chemical 10]<img file="JP4646352B2_D0010.tif" />[0065] [In the formula, R is C₁₄~ C₁₈It is an alkyl chain of. ] Intercalation of monomers and polymers into polycharged onium ion-exchanged organic clay suggests that there is no locking of adjacent clay silicate layers by the use of polycharged onium ion intercalants. .. [0066] A swellable capable of sufficiently accommodating the multicharge separation / coupling agent to increase the interlayer spacing between adjacent phyllosilicate discs, at least 3 Å, preferably at least 5 Å, preferably at least about 10 Å. Any layered material can be used for the practice of the present invention. Useful swellable layers include, for example, montmorillonite, especially sodium montmorillonite, magnesium montmorillonite and / or calcium montmorillonite, non-lonite, vermiculite, volkonskoite, hectorite, saponite, saponite, sobockite, stephensite. , Svinfordite, smectite clay minerals such as vermiculite, and other phyllosilicates. Other useful layers include mica stone minerals such as illite and layered illite / smectite mineral mixtures (such as lectrite, tarosovite, ledikite and mixtures of said clay minerals and illite). To. [0067] A preferred swellable layer has a negative charge on the layer in the range of about 0.15 to about 0.9 charge per structural unit and in the interlayer space a number of exchangeable metal cations commensurate with the negative charge. It is a 2: 1 type phyllosilicate with ions. The most preferred layered material is smectite clay minerals such as montmorillonite, non-lonite, byderite, volconscoite, hectorite, saponite, saponite, sobokite, stepvensite and subfoldite. [0068] [0068] As used herein, the term "interlayer spacing" refers to the distance between the inner surfaces of adjacent layers in a state where they are assembled before delamination (peeling) occurs in the layered material. Will be mentioned. [0069] The surface of the intercalated layered platen is sufficiently multicharged so that the adjacent plates of the intercalant layered material are sufficiently spaced apart to facilitate cointercalation of the polymeric or polymerizable cointercalant. / Coupling agent The amount of multicharged separation / coupling agent intercalated into a swellable layered material to allow ion exchange with the molecule is substantially about 2 based on the dry weight of the layered material. It may vary from% by weight, preferably at least about 10% by weight, and the upper limit in the range of 200% by weight. [0070] Multicharged Onium Ion Separation / Coupling Agents Intercalants and cointercalant polymers can be introduced into the interlayer space of layers in a number of ways (can be accommodated in space). In a preferred method for intercalating a polycharged onium ion separator / coupling agent between adjacent plates of a layered material, the layered material is, for example, 5 to 20% by weight of the layered material and 80 to 95% by weight of the layered material. It is slurried in water in proportion to water, and the multicharge separation / coupling agent compound is dissolved or dispersed in the water in which the layered material is slurried. If desired, the multicharge separation / coupling agent compound may first be dissolved in an organic solvent (eg, propanol). The layered material is then separated from the slurry water and dried prior to compositing with the cointercalant polymer for intercalating the cointercalant, and preferably in a matrix polymer which is the same matrix polymer as the cointercalant polymer. A nanocomposite is formed in. In a preferred method of intercalating a cointercalant as an oligomer or polymer, the layered material intercalated with the multicharge separation / coupling agent is the cointercalant oligomer or polymer, for example by extrusion or mixing mill (Pagmill). Homogeneously mixed with the melt. [0071] The resulting layered material intercalated with the multicharge separation / coupling agent is sufficiently hydrophobic and sufficiently separated for intercalation of the cointercalant polymer. The carrier of the multicharge separation / coupling agent (preferably water, or water containing an organic solvent) can be added by first solubilizing or dispersing the multicharge separation / coupling agent compound in the carrier. .. Alternatively, the dry multicharged separator / coupling agent compound is mixed with a relatively dry layered material (preferably containing at least about 4% by weight of water) and an intercalation carrier is added to the mixture. Alternatively, an intercalation carrier may be added to the layered material before adding the dry multicharged separator / coupling agent. When intercalating layers with a multicharge separation / coupling agent in the form of a slurry (eg, about 408 kg (900 lbs) of water, about 45.4 kg (100 lbs) of layers and about 45.4 kg (100 lbs). ), The amount of water in the intercalation composition is, for example, from about 4% by weight, from a preferable minimum value of at least about 30% by weight, to an upper limit without particular limitation. , Can be changed as appropriate. After intercalation of the multicharged decoupling / coupling agent compound, the intercalated material is easily separated from the intercalation composition due to its hydrophobicity. [0072] Alternatively, a multicharge separation / coupling agent intercalation carrier, such as water, or an organic solvent, is added prior to the addition of the multicharge separation / coupling agent compound (which may be dry or in solution). The contained water can be added directly to the layered material (ie, the phyllosilicate). Multicharge Separation / Coupling Agent Compound Molecules are exposed to a dry or liquid multicharge separation / coupling agent compound in a multicharge separation / coupling agent intercalation composition. May be carried out by. [0073] According to another method of the invention for intercalating a polycharged separator / coupling agent and cointercalant between layered plates, preferably at least about 4% by weight of water, eg, about 10 to about 15 weight. The layer containing% water is mixed with the water and / or organic solvent solution of the polycharged intercalation / coupling agent compound. The multicharge separation / coupling agent compound can be intercalated into layers at the same time as the intercalation of the cointercalant polymer, or the cointercalant polymer can be used after the intercalation of the multicharge separation / coupling agent. It may be intercalated. Then, in order to intercalate the cointercalant polymer to the layered material intercalated with the multicharged separating / coupling agent, the layered material intercalated with the multicharged separating / coupling agent is directly composited. Extruded with a cointercalant oligomer or polymer melt. [0074] Multicharge separation / coupling agents have an affinity for phyllosilicates at appropriately separated charged atoms on both sides that crosslink adjacent negatively charged sites on the surface of the plate, thus multicharge separation. The coupling agent is encapsulated on a single plate surface and remains bound to the inner surface of the plate after delamination in the interlayer space. [0075] For the purpose of increasing the viscosity of the organic liquid carrier, it is preferable that the load amount of the intercalated material is less than about 10%. Viscosity is significant by setting the intercalation load to about 0.05% to about 40% by weight, preferably from about 0.5% to about 20% by weight, more preferably from about 1% to about 10% by weight. Is enhanced to. Generally, the amount of intercalation and / or exfoliated particles thereof introduced into a liquid carrier (eg, polar solvent such as glycol such as glycerol) is less than about 90% by weight of the mixture, preferably about about the complex mixture. From 0.01% to about 80%, more preferably from about 0.05% to about 40% by weight of the mixture, and most preferably from about 0.05% to about 20% by weight, or from about 0.05% to about 10% by weight. is there. [0076] In a preferred embodiment of the invention, the cointercalated layered material is cointercalated with various oligomers or polymers by direct composite and then melt-processable one or more thermoplastic and / or thermosetting oligomers or polymers. , Or can be dispersed in a mixture of these. As the matrix polymer used in this embodiment in the method of the present invention, a wide variety of matrix polymers are possible as long as melt processing is possible as the sole requirement. In such embodiments of the invention, the polymer comprises at least 10, preferably at least 30 repeating monomer units. The upper limit of the repeating monomeric units is not definitive as long as the matrix polymer has a melt index that forms a flowable mixture. Most preferably, the cointercalant polymer is uniformly dispersed in the matrix, while the matrix polymer is intercalated into a layered material intercalated with a dicharge separation / coupling agent. The matrix polymer preferably comprises at least about 10 to at least about 100 repeating monomeric units, and is preferably the same oligomer or polymer as the cointercalant. In the most preferred embodiment of the invention, the number of repeating units is such that at processing temperature the matrix polymer has a melt index of about 0.01 to about 12 grams per 10 minutes. [0077] MXD6 nylon (Mitsubishi Gas Chemical Company, Tokyo, Japan) is a polymer having the following chemical formula. [0078] [Chemical 11]<img file="JP4646352B2_D0011.tif" />[0079] [In the formula, n = 1 for monomers, n = 2-10 for oligomers, and n = 11-200,000, preferably 11-1,000, more preferably 11-500 for polymers]. In practicing the present invention, many thermoplastic resins and rubbers for use as matrix monomers, oligomers or polymers can be selected from a very wide range. Examples of useful thermoplastic resins that can be used alone or as a mixture are polylactones such as poly (pivalolactone), poly (caprolactone); 1,5-naphthalenediocyanates, p-phenylenediocyanates, m-phenylenediocyanates. , 2,4-Toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropyridene diisocyanate, 3,3'-dimethyl-4, 4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4,4 Polyurethanes derived from the reaction of diisocyanates such as'-diisocyanato diphenylmethane with linear long-chain polyesters having hydroxyl terminal terminals; poly (tetramethylene adipate), poly (ethylene adipate), poly (1,4- Diol-based polyethers such as butylene adipate), poly (ethylene succinate), poly (2,3-butythylene succinate), polyether diols, etc.; poly [methanebis (4-phenyl) carbonate ], Poly [1,1-etherbis (4-phenyl) carbonate], poly [diphenylmethanebis (4-phenyl) carbonate], poly [1,1-cyclohexanebis (4-phenyl) carbonate] and other polycarbonates Polysulphons; Polyethers; Polyketones; [0080] [0080] A wide range of vulcanizable and thermoplastic rubbers, which are useful as matrix polymers in carrying out embodiments of the present invention, are also available. Examples of such rubbers include butyl bromide rubber, butyl rubber chloride, polyurethane elastomers, fluoroelastomers, polyester elastomers, butadiene / acrylonitrile elastomers, silicon elastomers, poly (butadiene), poly (isobutadiene), ethylene-propylene. Copolymers, ethylene-propylene-dienter polymers, sulphonized ethylene-propylene-dienter polymers, poly (chloroprene), poly (2,3-dimethylbutadiene), poly (butadiene-pentadiene), chlorosulphonized poly ( Vitreous or crystalline block copolymers such as ethylene), poly (sulfide) elastomers, poly (styrene), poly (vinyl-toluene), poly (t-butylstyrene), polyesters, and poly Manufactured by Shell Chemical Company under elastomeric blocks such as (butadiene), poly (isoprene), ethylene-propylene copolymers, propylene copolymers, ethylene-butylene copolymers, polyethers, etc., for example KRATON (brand name). , Poly (styrene) -poly (butadiene) -poly (styrene) block copolymers. [0081] Thermosetting resins useful as matrix polymers include, for example, polyamides; polyalkylamides; polyesters; polyurethanes; polycarbonates; polyepoxides; and mixtures thereof. [0082] The most preferred thermoplastic polymers for use as matrix polymers are polyamides, especially nylon, especially MXD6 nylon. Polyamides that can be used as matrix polymers in the methods of the invention are synthetic linear polys characterized by the presence of repeating carbon amide groups as complete parts of the polymer chains separated from each other by at least two carbon atoms. It is a carbon amide. This type of polyamide includes polymers commonly known in the art as nylon, which is a general formula. [0083] [Chemical 12]<img file="JP4646352B2_D0012.tif" />[0084] [In the formula, R¹³Is an alkylene group having at least 2, preferably about 2 to about 11 carbon atoms, or an arylene having at least about 6, preferably about 6 to about 17 carbon atoms.¹⁴Is R¹³And represents a group selected from aryl groups], and is obtained from diamines and dibasic acids. Also included in the preferred polyamides are copolyamides and terpolyamides obtained by known methods, for example by concentration of a mixture of dibasic acids consisting of terephthalic acid and adipic acid with hexamethylenediamine or m-xylylenediamine. Will be done. The above-mentioned polyamides are well known in the art, for example, 30% hexamethylene diammonium isophthalate and 70% hexamethylene diammonium adipate copolyamide, poly (hexamethylene adipamide) (nylon). 6,6), Poly (Hexamethylene sebacamide) (Nylon 6,10), Poly (Hexamethylene isophthalamide), Poly (Hexamethylene terephthalamide), Poly (Heptamethylene pimmelamide) (Nylon 7, 7), Poly (Octamethylenesveramide) (Nylon 8,8), Poly (Nonamethylene Azelamide) (Nylon 9,9), Poly (Decamethylene Azelamide) (Nylon 10,9), Poly (Decamethylenese) Bacamide) (nylon 10,10), poly [bis (4-aminocyclohexyl) methane-1,10-decanecarboxamide)], poly (m-adipamide), poly (p-xylenesebacamide), poly (2) , 2,2, -trimethylhexamethylene terephthalamide), poly (piperazin sebacamide), poly (p-phenylene terephthalamide), poly (metaphenylene isophthalamide) and the like. [0085] Other polyamides for use as matrix polymers are those formed by the polymerization of amino acids and their derivatives, such as lactams. Examples of these useful polyamides are poly (4-aminobutyric acid) (nylon 4), poly (6-aminohexanoic acid) (nylon 6), poly (7-aminoheptanoic acid) (nylon 7), poly ( 8-Aminooctanoic acid) (Nylon 8), Poly (9-Aminononanoic acid) (Nylon 9), Poly (10-Aminodecanoic acid) (Nylon 10), Poly (11-Aminoundecanoic acid) (Nylon 11) and Poly (Nylon 11) 12-Aminododecanoic acid) (nylon 12) and the like. [0086] Other matrix or host polymers that can be used in mixtures with the bicharge separation / coupling agent intercalants and intercalant polymers of the present invention to form nanocomposites are linear polyesters. The type of polyester does not affect the present invention, and the particular polyesters selected for use in a particular situation have the physical properties and properties desired for their final form, i.e., tensile strength. , Tensile stress, etc. are essentially dependent. As described above, the existence of a large number of linear thermoplastic polyesters having a wide variety of physical properties is a mixture with the stripped layered small plates in producing the nanocomposite of the present invention. Suitable for use in. [0087] The polyester specifically selected for use as the matrix polymer in the present invention can be homopolyester, copolyester, or a mixture thereof, if desired. Polyesters are usually prepared by concentration of an organic dicarboxylic acid with an organic diol, and are used to carry out in situ polymerization of the polyester before or after exfoliation of the intercalated material while in contact with the layered material. The reaction product can be added to the intercalated product or the peeled intercalated product. [0088] Polyesters suitable for use as a matrix polymer in such embodiments of the present invention are obtained by enriching aromatic, cyclic aliphatic and aliphatic diols with aliphatic, aromatic and cyclic aliphatic dicarboxylic acids. It can be a cyclic aliphatic, aliphatic or aromatic polyester. [0089] Examples of useful cyclic aliphatic, aliphatic and aromatic polyesters that can be used as matrix polymers in carrying out such embodiments of the present invention include poly (ethylene terephthalate), poly (cyclohexylene methylene terephthalate), and the like. Poly (ethylene dodecate), poly (butylene terephthalate), poly [ethylene (2,7-naphthalate)], poly (metaphenylene isophthalate), poly (glycolic acid), poly (ethylene succinate), poly ( Polyethylene adipate), poly (ethylene sebacate), poly (decamethylene azelate), poly (decamethylene adipate), poly (decamethylene sebacate), poly (dimethylpropiolactone), poly (para-hydroxybenzoate) ( EKONOL), poly (ethyleneoxybenzoate) (A-tell), poly (ethyleneisophthalate), poly (tetramethylene terephthalate), poly (hexamethylene terephthalate), poly (decamethylene terephthalate), poly (1,4-cyclohexane) Dimethylene terephthalate) (trans), poly (ethylene-1,5-naphthalate), poly (ethylene-2,6-naphthalate), poly (1,4-cyclohexylidene dimethylene terephthalate) (KODEL) (cis), and Examples thereof include poly (1,4-cyclohexylidene dimethylene terephthalate) (KODEL) (trans). [0090] Polyester compounds prepared by concentration of diols and aromatic dicarboxylic acids are particularly suitable as matrix polymers in said embodiments of the present invention. Examples of aromatic carboxylic acids having such usefulness are terephthalic acid, isophthalic acid and o-phthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylsulphondicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) -idane, diphenyl ether Examples thereof include 4,4'-dicarboxylic acid and bis-p- (carboxyphenyl) methane. Among the above aromatic dicarboxylic acids, those having a benzene ring (terephthalic acid, isophthalic acid, orthophthalic acid, etc.) are preferable for use in carrying out the present invention. Of these preferred acid precursors, terephthalic acid is a particularly preferred acid precursor. [0091] Yet another useful thermoplastic homopolymers and copolymer matrix polymers for forming nanocomposites using the cointercalated layered material of the present invention include α, β unsaturated monomers, or: Formula [0092] [Chemical 13]<img file="JP4646352B2_D0013.tif" />[0093] [In the formula, R¹⁵And R¹⁶Represents the same or different from each other and represents a cyano, phenyl, carboxy, alkyl ester, halo, alkyl or alkyl substituted with one or more chlorine or fluorine, or a hydrogen atom] Examples include polymers. Examples of such preferred homopolymers and copolymers are homopolymers such as ethylene, propylene, vinyl alcohol, acrylonitrile, vinylidene chloride, acrylic acid esters, methacrylic acid esters, chlorotrifluoroethylene and vinyl chloride. And copolymers. Preferred are poly (propylene), propylene copolymers, poly (ethylene), and ethylene copolymers. More preferred are poly (ethylene) and poly (propylene). [0094] Mixtures of the present invention can contain a variety of optionally blendable ingredients, additives commonly used in polar organic liquids. Such optional components include nucleating Agent), fillers, plasticizers, impact modifiers, chain extenders, plasticizers, colorants, mold desorption lubricants, antistatic agents, dyes, flame suppressants, etc. are included. These optional components, and appropriate addition amounts thereof, are well known in the art. [0095] Intercalated, contained in a liquid carrier or solvent composition to form a carrier or a viscous composition suitable for transporting an active ingredient dissolved or dispersed in a carrier such as a pharmaceutical. The amount of layered material can vary widely depending on the intended use of the composition and the desired viscosity. For example, when forming a solvent gel with an extremely high viscosity of 5,000 to 5,000,000 cps, a relatively large amount of intercalation is used, such as about 10 to about 30% by weight of the total weight of the composition. However, even if a relatively low concentration intercalated product and / or a stripped product thereof is used, for example, about 0.1 to 5% by weight, the pH of the composition is adjusted to the range of about 0 to 6 or about 10 to 14. And / or those having an extremely high viscosity by heating the composition to a temperature higher than room temperature, for example in the range of about 25 ° C to about 200 ° C, preferably about 75 ° C to about 100 ° C. It can also be. [0096] The loading of the platelets is preferably less than about 10% of the composition. Intercalated or small in the range of about 0.01% to about 40% by weight, preferably about 0.05% to about 20% by weight, more preferably about 0.5% to about 10% by weight of the total weight of the composition. By loading the plate particles, the viscosity of the composition is significantly increased. Generally, the amount of intercalation and / or disc particles introduced into the carrier / solvent is less than about 20% by weight, preferably from about 0.05% to about 20% by weight, based on the total weight of the composition. It is preferably from about 0.01% to about 10% by weight, and most preferably from about 0.01% to about 5% by weight. [0097] According to the important features of the present invention, the intercalated product and / or the plate / carrier composition of the present invention is, for example, about 10 to 90%, preferably about 20 to 80% of the intercalated product and /. Alternatively, it can be produced in a concentrated state such as a stripped plate of a layered material and a carrier / solvent of about 10 to 90%, preferably about 20 to 80%, for example, a master gel. The master gel can later be diluted and mixed with additional carriers or solvents to reduce the viscosity of the composition to the desired level. [0098] In one embodiment, an intercalated product and / or a stripped product thereof is mixed with a carrier or solvent to produce a viscous composition of the carrier or solvent, but one or more dissolved or dispersed in the carrier or solvent. The active ingredient of the above, for example, an antiperspirant, etc., can be optionally contained. [0099] If shearing is employed for exfoliation, any method that can be used to shear the intercalant / matrix polymer nanocomposite composition can be used. The shearing action can be supplied by a variety of suitable methods known in the art, such as mechanical means, temperature shock, pressure changes or ultrasound. In a particularly useful method, the composition is sheared by a mechanical method. By using mechanical means such as a stirrer, a Banbury type mixer, a Brabender type mixer, a long-term mixer, and an extruder in such a mechanical manner, the intercalated product can be supported on the carrier. Alternatively, it is sheared in the presence or absence of a solvent. Another method uses thermal shock, in which the temperature of the composition is alternately raised or lowered to cause thermal expansion and shearing is achieved by applying internal stresses that cause shearing. Yet another method is by ultrasonic techniques in cavitation or resonant vibration, where shearing is done by abrupt changes in pressure with a pressure change method, or parts of the composition are vibrated or vibrated in different phases. Shearing is accomplished. These shearing methods merely provide representative examples of useful methods, and any method known in the art for shearing intercalated material can be adopted. [0100] As the mechanical shearing method, as described above, a method using an extruder, an injection molding machine, a Banbury type mixer, a Brabender type mixer, or the like can also be used. Shearing can also be achieved by introducing layers and intercalant monomers at one end of the extruder (single-screw or biaxial) and receiving the sheared material at the other end. Layered / intercalant monomer composition temperature, extruder length, composition residence time in extruder and extruder design (single-screw, biaxial, number of flights per unit length, channel depth, Flight clearance, mixed region, etc.) are variable factors that control the strength of the shear force applied for peeling. [0101] According to an important feature of the present invention, clays intercalated with multicharged decoupling / coupling agents are directly composited (ie, directly intercalated with cointercalant oligomers or polymers in an extruder with polycharged onium ions. It has been found that by mixing the culled clay, the clay can be co-intercalated with an oligomer or polymer (by co-intercalating the clay without significantly peeling the clay slabs). The matrix polymer filled with the cointercalation is extruded into a uniform transparent film in which the cointercalation and / or the exfoliated material is well dispersed. The cointercalation and / or strips thereof can be dispersed in the matrix polymer and take the form of multi-layered tactoids dispersed primarily in the matrix. The tactoid has a thickness and coplanarity of at least two individual plate layers and an ion-exchanged bicharged intercalant separator / coupling agent and a single layer of 1-5 monolayers of cointercalant polymer. The agglomeration comprises a small complex or agglomerate containing at least about 10 plaques, more preferably less than about 5, more preferably less than about 3, and even more preferably 2-3 plaque layers. It contains a multicharge separation / coupling agent compound and a coplanarity polymer between the surfaces of the platelets. Nanocomposite compositions containing matrix polymers can contain layered material as any intercalation, even if not completely exfoliated, and have transparency, excellent intercalate dispersibility, And maintains excellent gas permeability. [0102] A molding composition comprising a matrix polymer containing a desired loading amount of the cointercalates of the present invention and / or the individual flakes obtained by peeling the cointercalates produced according to the present invention. It is remarkably suitable in the manufacture of sheets, films and panels with diverse properties. Such sheets, films and panels can be formed by traditional methods such as vacuuming or heat compression to form useful articles. Sheets and panels made according to the present invention are also suitable as coating agents for other materials, including, for example, wood, glass, ceramics, metals or plastics, as well as conventional conventional materials such as vinyl resin bases and the like. Adhesion promoters can be used to provide significant strength. For example, using a matrix polymer in which the cointercalation of the present invention is filled with 1 to 10% by weight, either in a single layer or in a state of being fixed between one or more other layers, a beverage container, For example, plastic beer / wine bottles can be manufactured with new and unexpected storage stability. The sheets, films and panels can also be laminated with other plastic films, sheets or panels, preferably by coextrusion to bond the sheets in a melted state. The surfaces of these sheets, films and panels, including those that have been embossed, can be improved or finished by traditional methods, such as the application of lacquering or protective films. [0103] Matrix polymer / intercalated composites are particularly useful for the production of extruded and laminated films, such as films with low oxygen permeability used for food packaging. The thickness of such a film is preferably about 10 to about 100 μm, more preferably about 20 to about 100 μm, and most preferably about 25 to about 75 μm. [0104] In the present invention, a homogeneously dispersed, cointercalated intercalated product and / or a stripped plate thereof thereof, and a matrix polymer can be formed into a film by a suitable film forming method. Typically, after oligomeric or polymer coincarnation and compounding, the composition is melted and pushed into a film-forming die. The film of the nanocomposite is subsequently subjected to a step of further directing the intercalated material and / or its stripped plate, and the intercalated material and / or its stripped plate is further co-intercalated. And / or the main plane of the stripped material may be substantially parallel to the main plane of the entire film. This is accomplished, for example, by stretching the film in the biaxial direction. For example, when the film is extruded from the die, the tension rollers that pull the film stretch the film axially or mechanically. At the same time, the film is stretched laterally by grabbing both ends of the film and pulling it apart. Alternatively, a tubular film die is used to stretch the film laterally and the film is blown as it passes through and exits the tubular film die. The film obtained based on the present invention, in particular, in addition to reducing the permeability of a gas such as oxygen gas, has an increased elastic modulus, an increased wet strength, an increased dimensional stability, and a decreased water adsorption property. It can exhibit at least one of the advantages such as. [0105] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. [0106] [Example] [Example 1] This example illustrates the formation of a (lipophilic) montmorillonite clay modified with dicharged onium ions. Onium ions are neutral amines (primary and secondary) and can be protonated by contact with hydrochloric acid. [0107] 100 grams of sodium-montmorillonite clay (PGW) commercially available from Nanocor, Inc. (Arlington Heights, Illinois) was dispersed in 3 liters of deionized water using a mechanical paddle mixer or colloidal mill. The clay dispersion was heated to 75-80 ° C. 26.4 g of Taro Diamine commercially available from Tomah Products was mixed with 70 ml of 2N HCl in 1 liter of deionized water at 75-80 ° C. The amine-hydrochloric acid solution was introduced into the clay dispersion and then mixed vigorously. The mixture was kept at 75-80 ° C for about 30 minutes and then subjected to a water removal process such as filtration. The filtered cake was redistributed in 4 liters of water at 75-80 ° C, the solids (filtered cake) were collected and placed in an oven at 75-80 ° C for drying and then reduced particle size. The filtered cake can also be lyophilized. The dried product had a d001 interval of 17 Å as measured by X-ray diffraction, and this code number was designated as TDA-2H-PGW. Taroamine can be used in substantially the same way to prepare treated montmorillonite, but the amount of taroamine used should be higher (eg 37.1 grams). The code number of the product was TA-PGW, which had a d001 interval of 22 Å. [0108] [Example 2] This example illustrates the formation of a (lipophilic) montmorillonite clay modified with dicharged onium ions. Onium ions are neutral amines (tertiary) and can be protonated by contact with hydrochloric acid. [0109] 100 grams of sodium-montmorillonite clay (PGW) commercially available from Nanocor, Inc. (Arlington Heights, Illinois) was dispersed in 3 liters of deionized water using a mechanical paddle mixer or colloidal mill. The clay dispersion was heated to 75-80 ° C. 33.6 g of E-DT-3 amine commercially available from Tomah Products was mixed with 70 ml of 2N HCl in 1 l of deionized water at 75-80 ° C. The amine-hydrochloric acid solution was introduced into the clay dispersion and then vigorously mixed. The mixture was kept at 75-80 ° C for about 30 minutes and then subjected to a water removal process such as filtration. The filtered cake was redistributed in 4 liters of water at 75-80 ° C, the solids (filtered cake) were collected and placed in an oven at 75-80 ° C for drying and then reduced particle size. The filtered cake can also be lyophilized. The dried product had a d001 interval of 17 Å as measured by X-ray diffraction, and this code number was designated as E-TD-3-2H-PGW. [0110] [Example 3] This example illustrates the formation of a (lipophilic) montmorillonite clay modified with dicharged onium ions. Onium ions are dicharged quaternary ammonium cations. [0111] 100 grams of sodium-montmorillonite clay (PGW) commercially available from Nanocor, Inc. (Arlington Heights, Illinois) was dispersed in 3 liters of deionized water using a mechanical paddle mixer or colloidal mill. The clay dispersion was heated to 75-80 ° C. 67.2 g of Duoquad T50 (50% solid) commercially available from Akzo Nobel was mixed with 1 l of deionized water at 75-80 ° C. The T50 solution was introduced into the clay dispersion and then vigorously mixed. The mixture was kept at 75-80 ° C for about 30 minutes and then subjected to a water removal process such as filtration. The filtered cake was redistributed in 4 liters of water at 75-80 ° C, the solids were collected and placed in an oven at 75-80 ° C for drying and then reduced particle size. The filtered cake can also be lyophilized. The dried product had a d001 interval of 19 Å as measured by X-ray diffraction, and this code number was designated as T50-PGW. [0112] [Examples 4 to 6] These examples illustrate the formation of polycharged onium ion-modified (lipophilic) montmorillonite clays. Onium ions are neutral amines (primary and secondary) and are protonated by contact with hydrochloric acid. [0113] 5 grams each of the products prepared in Examples 1-3 (TDA-2H-PGW, TA-PGW, and T50-PGW), 45 grams of the following non-polymeric organic compounds [70-90 ° C ε-caprolactam] , 70-80 ° C DGEBA DER331, and 70-80 ° C resorcinol bis- (diphenyl phosphate) (RDP, Akzo Nobel)]. The mixture was cooled to room temperature and placed on a glass slide under a microscope to measure X-ray diffraction patterns. The results are shown in Table 2. The intercalation of the clay treated with polycharged onium ions with the non-polymeric organic compound is by mixing the non-polymeric organic compound with the filtered cake, then removing the water, drying and reducing the particle size. Can also be formed. The result of d001 was almost the same as that produced in the dispersion system of Examples 1 to 3. [0114] The results shown in Table 2 suggest that the non-polymeric organic compounds were successfully intercalated into the interlayer space of the clay treated with polycharged onium ions. Clays treated with polycharged onium ions function like normal organic clays. Preferred polycharged onium ion aliphatic long chain tail (C)₆+) Achieves a significantly better degree of intercalation. [0115] [Table 2]<img file="JP4646352B2_D0014.tif" />[0116] [Comparative example 1] For comparison, 5 grams of untreated sodium-montmorillonite clay (PGW) was mixed with the non-polymeric organic compound and the mixture was examined by X-ray diffraction. The results are also shown in Table 2. No intercalation of organic molecules was observed. [0117] [Examples 7 to 9] This example illustrates the formation of polymer-clay nanocomposites by melt composites. [0118] A melt composite was used to prepare the polymer clay nanocomposite. Nylon 6 (PA6), polymethylmethacrylate (PMMA) and nylon MXD6 (MXD6), which are thermoplastic resins, were selected as materials. Biaxial extruder (Leistritz) for resin pellets and clay intercalated with polycharged onium ions The temperature was raised to a temperature exceeding the melting point of the resin (for example, in the case of PMMA, the temperature of the extruder was in the range of 210 ° C to 230 ° C) and supplied to Micro27). The ratio of clay to resin intercalated with polycharged onium ions was controlled at 5:95 by weight. The compounded compound string from the extruder was cooled in a cold water bath prior to pelletization. The PA6, and MXD6 nanocomposites were formed on a 2 mm thick film, and OTR (oxygen permeability) results were measured at 65% RH at 23 ° C using Mocon OX-Tran 2/20. did. PMMA-clay nanocomposites were molded into ASTM standard test specimens for HDT (heat deflection temperature). Table 3 shows the results of dispersing clay intercalated with polycharged onium ions in the above resin. X-ray diffraction patterns were obtained from PA6-clay, MXD6-clay film nanocomposites and PMMA-clay nanocomposite bars. The results of X-ray diffraction are shown in Table 4. [0119] [Table 3]<img file="JP4646352B2_D0015.tif" />[0120] The molten resin polymer is intercalated into clay intercalated with other charged onium ions to form a resin-clay complex in an extrusion process. The results of X-ray diffraction show that the intercalation of the resin prevents the original clay layer from being laminated. The OTR results for PA6 and MXD6 nanocomposites were reduced by 30% or more, respectively, compared to the unfilled resin. The HDT of the PMMA nanocomposite was higher than that of pure PMMA resin by almost 10 ° C or more. [0121] [Table 4]<img file="JP4646352B2_D0016.tif" />[0122] [Comparative example 2] For comparison, 5 wt% untreated sodium montmorillonite clay (PGW) was added to nylon 6 (PA6), poly (methylmethacrylate) (PMMA) and nylon MXD6 using the same conditions as for polycharged onium ion treated clay. Combined with (MXD6). The resin filled with untreated PGW was inferior in dispersibility (Table 3). The film formed had visible voids, and the molded sample bar contained rough surfaces and clay agglomerates. The results of X-ray diffraction (Table 4) suggest that the polymer resin is not intercalated in the interlayer space of the clay. In addition, in the heating extrusion process, the clay caves were destroyed by the dehydration (drying) of the clay. [0123] [Example 10] This example illustrates the formation of nylon 6-TDA-2H-PGW nanocomposites by a caprolactam polymerization system. [0124] 70 grams of TDA-2H-PGW and 2,000 grams of caprolactam were mixed overnight at 80 ° C. before being placed in the reactor. A constant speed pedal mixer was placed in the reactor and nitrogen was purged. The reaction time was 12 hours at 260 ° C. The reaction product was crushed into small pieces by cooling with liquid nitrogen and washed with boiling water to remove residual caprolactam. A 2 mm thick film was formed and OTR was measured with Mocon OX-Tran 2/20. Nanocomposites containing TA-PGW were also prepared in the same manner. Table 5 shows the OTR results of the unfilled resin and the nanocomposite. [0125] [Table 5]<img file="JP4646352B2_D0017.tif" />[0126] Nanocomplexes prepared from polycharged onium ion-treated clays have significantly reduced oxygen permeability compared to conventional (single-charged onium ion) treated clays. Also, other mechanical properties, heat and solvent resistance are improved over those of nanocomposites prepared from conventional single-charged onium ion-treated clays. [0127] [Effect of the invention] INDUSTRIAL APPLICABILITY The present invention provides a matrix polymer with an intercalation product capable of providing favorable properties such as reduced oxygen permeability, and a nanocomposite composition containing the intercalation product. [Simple explanation of drawings] [Fig. 1] Fig. 1 (a) to 1 (d) show two adjacent interchangeable Nas on the plate surface.⁺Cations and Na⁺It is a side schematic view which shows the part of the layered small plate which shows the negative charge center just above the small plate just below a cation, shows how the negative charge is diffused radially outward from the negative charge center, and also has a negative charge. Two positively charged (N) ion-exchanged at different positions with respect to the center⁺) Positively charged onium ions at two locations are also shown, along with separations with different chain lengths that bond between atoms. FIG. 2 is a schematic view of a layered plate intercalated with monocharged (taroamine) (a) and dicharged (tarodiamine) (b) onium ions according to an embodiment of the present invention. 3 (a) and 3 (b) are intercalated with the monocharged and dicharged onium ions shown in FIGS. 2 (a) and 2 (b), and the coinca with a polymeric cointercalant. It is a schematic diagram which shows the ration, the adjacent layered small plate.