USOO6232388B1 (12) United States Patent (10) Patent No.: US 6,232,388 B1 Lan et al. (45) Date of Patent: *May 15, 2001

(54) INTERCALATES FORMED BY CO- 4,053,493 10/1977 Oswald ...... 260/448 INTERCALATION OF ONIUM ION SPACING/ 4,136,103 1/1979 Oswald ...... 260/448 COUPLING AGENTS AND MONOMER, 4,851,021 7/1989 Bohrn et al...... 65/17 OLGOMER OR POLYMER MXD6 NYLON 5:2, 40 pts alm 5. INTERCALANTS AND NANOCOMPOSITES 5747,560 5/1998 RSG et al. s23/209 PREPARED WITH THE INTERCALATES 5,910,523 6/1999 Hudson ...... 523/213 5,981,029 11/1999 Harada et al...... 428/143 (75) Inventors: Tie Lan, Lake Zurich; Hannah T. 5,994,445 11/1999 Kaschel et al...... 524/444 Cruz, Elk Grove Village; Anthony S. 6,057,396 5/2000 Lan et al...... 524/445 Tomlin, Island Lake, all of IL (US) 6,071,988 6/2000 Barbee et al...... 523/210 6,084,019 7/2000 Matayabas, Jr. et al...... 524/445 (73) Assignee: AMCOL International Corporation, Arlington Heights, IL (US) FOREIGN PATENT DOCUMENTS c: - 0 0.818 508 A2 1/1998 (EP) ...... CO8L/77/OO (*) Notice: Subject to any disclaimer, the term of this 2209671 1/1998 (CA) ...... CO8L/77/06 patent is extended or adjusted under 35 WO 96/O8526 3/1996 (WO). U.S.C. 154(b) by 0 days. * cited by examiner This patent is Subject to a terminal dis claimer. Primary Examiner Edward J. Cain (74) Attorney, Agent, or Firm-Marshall, O'Toole, (21) Appl. No.: 09/272,278 Gerstein, Murray & Borun (22) Filed: Mar 19, 1999 (57) ABSTRACT O O Intercalated layered materials prepared by co-intercalation Related U.S. Application Data of an onium ion and MXD6 nylon between the planar layers (60) Pisional application No. 60/096.774, filed on Aug. 17, of a Swellable layered material, Such as a phyllosilicate, preferably a smectite clay. The spacing of adjacent layers of (51) Int. Cl." ...... C08K 3700 the layered materials is expanded at least about 3 A, pref (52) U.S. Cl...... 524/445; 524/446; 524/447 erably at least about 5 A, usually preferably to a d-spacing (58) Field of Search ...... 524/445,446, of about 15–20 A, e.g., 18A with the onium ion spacing/ 524/.447 coupling agent. The intercalation of the MXD6 nylon poly mer then increases the spacing of adjacent layers an addi (56) References Cited tional at least 3 A, e.g., to at least about 20 A, preferably about 25 A to about 30 A, generally about 28 A. U.S. PATENT DOCUMENTS 3,929,849 12/1975 Oswald ...... 260/448 52 Claims, 2 Drawing Sheets U.S. Patent May 15, 2001 Sheet 1 of 2 US 6,232,388 B1

Time 9.17 733 138 202 266 33O 394 (hrs) PURE MXD 6

Time 9.18 73.5 138 2O2 267 331 395 2.5 / no nomer Fig. 2 U.S. Patent May 15, 2001 Sheet 2 of 2 US 6,232,388 B1

O53799 O461 14 O38428 O3O742 O23O57 O15371 OO7686 OOOO Time 9.2O 73.7 138 2O3 267 331 396 (hrs) 5. O / Nonomer Fig. 3 US 6,232,388 B1 1 2 INTERCALATES FORMED BY CO individual platelets, preferably such that more than 80%; or INTERCALATION OF ONIUM ION SPACING/ more than 90% by weight of the layered material can be COUPLING AGENTS AND MONOMER, completely exfoliated into Single platelet layers. Quick, OLGOMER OR POLYMER MXD6 NYLON easy, and completely homogeneous dispersion of the onium INTERCALANTS AND NANOCOMPOSITES 5 ion/MXD6 nylon co-intercalated layered material in the PREPARED WITH THE INTERCALATES MXD6 nylon matrix polymer is achieved and the resulting nanocomposite has unexpected O-impermeability. For CROSS REFERENCE TO RELATED example, a film of the MXD6 nylon polymer with the APPLICATION layered material, particularly a Smectite clay, Such as Sodium This application is a continuation-in-part of U.S. provi bentonite, can be formed by direct compounding to provide a sheet of the MXD6 nylon without any visible intercalate sional application Ser. No. 60/096,774 filed Aug. 17, 1998. filler that has completely unexpected, extremely low gas FIELD OF THE INVENTION permeability. The present invention is directed to intercalated layered The intercalates of the present invention can be dispersed materials and, optionally, exfoliates thereof, prepared by 15 uniformly into MXD6 nylon materials to form MXD6 nylon contacting, and thereby intercalating, a layered material, polymer/clay intercalate nanocomposites by direct com e.g., a phylloSilicate, Such as a Smectite clay, with an onium pounding of the onium ion-intercalated clay with Sufficient ion spacing/coupling agent and co-intercalation of the lay MXD6 nylon for intercalation of the clay to form an MXD6 ered material with a melt of MXD6 nylon (as polymerizable nylon intercalated clay, as a concentrate, that can later be reactants, or as the nylon oligomer or polymer) to form mixed with MXD6 nylon and/or other polymeric materials nanocomposite materials with new and unexpected gas to form a nanocomposite. Alternatively, the onium ion (particularly O.) barrier properties. The MXD6 nylon can be intercalated clay can be intercalated with monomer reactants intercalated in the form of the nylon reactants (meta that are polymerizable to form MXD6 nylon (meta-xylylene xylylene diamine and adipic acid polymerizable monomers) diamine and a dicarboxylic acid, e.g., adipic acid) to form or, can be unexpectedly easily intercalated as the MXD6 25 the MXD6 nylon co-intercalate. nylon oligomer or polymer by direct compounding, e.g., by In another embodiment of the present invention, the combining the onium ion-intercalated layered material and MXD6 nylon intercalates can be dispersed in one or more the MXD6 nylon in a mixing or extruding device to produce matrix monomers followed by polymerization of the matrix the co-intercalated layered material and the nanocomposite. monomer(s), e.g., meta-xylylene diamine and adipic acid, The interlaminar spacing of adjacent layers (platelets) of with in-Situ polymerization of the monomer reactants to the layered material is expanded at least about 3 A, prefer form the polymer, in situ, between the platelets of the ably at least about 5 A, to a basal spacing of at least about layered material, and to form the matrix polymer, e.g., by 10A, preferably to at least about 15 A, and usually to about adding a curing agent, to form the nanocomposite material. 18 A by contacting the layered material with the onium ion For example, curing agents can be directly incorporated into spacing/coupling agent for Subsequent intercalation with 35 the monomeric MXD6 nylon reactants that are intercalated MXD6 nylon. The onium ion may be primary, secondary, between platelets of the onium ion-intercalated clay fol tertiary or quaternary and preferably is a long chain (C+) lowed by polymerization of the MXD6 nylon reactant onium ion spacing/coupling agent having at least one bind intercalant monomers that have been intercalated into the ing (ion-exchange) site capable of ion-exchanging or replac clay interlayer galleries. In accordance with an important 40 feature of the present invention, if an intercalant MXD6 ing Li", Na', K", Ca", Mg', or other inorganic cations that nylon polymer is intercalated into the onium ion-intercalated occur within the interlayer Spaces between adjacent layerS or clay galleries, the MXD6 nylon intercalate can be directly platelets of the layered materials. The association of the compounded with the pristine matrix polymer, preferably an layered material inorganic cations with the onium ion MXD6 nylon matrix polymer, to form a nanocomposite Spacing/coupling agent Via ion-exchange enables the con 45 version of the hydrophilic interior clay platelet Surfaces to easily, while achieving a nanocomposite material with hydrophobic platelet Surfaces. Therefore, polymerizable unheard of gas (O) impermeability. If the meta-xylylene MXD6 nylon oligomers, or polymers, or meta-xylylene and adipic acid polymerizable intercalant monomers, or a diamine and adipic acid monomers capable of reacting to polymerizable MXD6 nylon oligomer intercalant is interca form MXD6 nylon, can be easily intercalated between lated into the clay galleries, the intercalant(s) can be poly adjacent platelets of the layered material, e.g., Smectite clay 50 merized together with a desired monomer, oligomer or platelets. polymer matrix material, preferably MXD6 nylon, and the combination then can be compounded to form the nanocom In accordance with the preferred embodiment of the posites. present invention, the fully polymerized MXD6 nylon poly mer having a weight average molecular weight between 55 BACKGROUND OF THE INVENTION AND about 100 and about 5 million, preferably about 1,000 to PRIOR ART about 500,000, is intercalated between adjacent platelets of It is well known that phyllosilicates, Such as Smectite the onium ion-treated layered material, preferably Simulta clays, e.g., Sodium montmorillonite and calcium neously with dispersing the intercalate into an MXD6 nylon montmorillonite, can be treated with organic molecules, matrix polymer, i.e., by direct compounding of the onium 60 Such as organic ammonium ions, to intercalate the organic ion-treated layered material with the MXD6 nylon polymer. molecules between adjacent, planar Silicate layers, for bond The co-intercalation of the onium ions and MXD6 nylon, or ing the organic molecules with a polymer, for intercalation its monomeric reactants, or MXD6 nylon polymerizable of the polymer between the layers, thereby substantially oligomers, results in a completely homogeneous dispersion increasing the interlayer (interlaminar) spacing between the of intercalated layered material and/or exfoliated platelets. 65 adjacent Silicate layers. The thus-treated, intercalated Optionally, the nanocomposite material can be sheared to phyllosilicates, having interlayer spacings increased by at exfoliate up to 100% of the tactoids or platelet clusters into least 3 A, preferably at least 5 A, e.g., to an interlayer US 6,232,388 B1 3 4 (interlaminar) spacing of at least about 10–25 A and up to co-intercalate that has excellent intercalate dispersibility in about 100 Angstroms, then can be exfoliated, e.g., the a matrix polymer, particularly an MXD6 nylon matrix Silicate layers are separated, e.g., mechanically, by high polymer and has unexpectedly low gas (particularly O.) Shear mixing. The individual Silicate layers, when admixed permeability in an MXD6 nylon matrix polymer. The inter with a matrix polymer, before, after or during the polymer calate also can be added to any other matrix polymer to ization of the matrix polymer, e.g., a polyamide-See U.S. enhance a number of properties of the matrix polymer, Pat. Nos. 4,739,007; 4,810,734; and 5,385,776-have been including tensile Strength, heat distortion temperature, gas found to Substantially improve one or more properties of the impermeability, elongation, and the like. polymer, Such as mechanical Strength and/or high tempera The onium ion/MXD6 nylon co-intercalates and/or exfo ture characteristics. liates thereof can be admixed with a polymer or other Exemplary prior art composites, also called organic monomer compound(s) or composition to increase “nanocomposites”, are disclosed in published PCT disclo the Viscosity of the organic compound or provide a matrix sure of Allied Signal, Inc. WO 93/04118 and U.S. Pat. No. polymer/intercalate and/or matrix polymer/exfoliate compo 5,385,776, disclosing the admixture of individual platelet Sition to enhance one or more properties of the matrix particles derived from intercalated layered Silicate materials, 15 polymer, particularly an MXD6 nylon matrix polymer. with a polymer to form a polymer matrix having one or more The onium ion M6 nylon co-intercalating process of the properties of the matrix polymer improved by the addition of present invention provides an intercalate that can be added, the exfoliated intercalate. As disclosed in WO93/04118, the particularly by direct compounding (mixing the intercalate intercalate is formed (the interlayer spacing between adja directly into a matrix polymer melt) of the intercalate with cent Silicate platelets is increased) by adsorption of a Silane any matrix polymer, e.g., all market available resin Systems, coupling agent or an onium cation, Such as a quaternary particularly epoxy resins Such as: Bisphenol A-derived ammonium compound, having a reactive group which is resins, Epoxy creSol Novolac resins, Epoxy phenol Novolac compatible with the matrix polymer. Such quaternary resins, Bisphenol F resins, polynuclear phenol-glycidyl ammonium cations are well known to convert a highly ether-derived resins, cycloaliphatic epoxy resins, aromatic hydrophilic clay, Such as Sodium or calcium 25 and he tero cyclic glycidyl amine resins, montmorillonite, into an organophilic clay capable of Sorb tetraglycidylmethylenedianiline-derived resins, nylons, Such ing organic molecules. as nylon-6 and nylon 66, and particularly MXD6 nylon. In accordance with one embodiment of the present Definitions invention, intercalates are prepared by contacting a phyllo Silicate with a monomeric onium ion spacing/coupling agent Whenever used in this Specification, the terms set forth compound. To achieve the full advantage of the present shall have the following meanings: invention, the onium ion should include at least one long “Layered Material' shall mean an inorganic material, chain radical (Ca+) that may be aliphatic, Straight or Such as a Smectite clay mineral, that is in the form of a branched chain, or aralkyl. Exemplary of Such Suitable C+ plurality of adjacent, bound layers and has a thickness, for onium ion molecules include primary, Secondary, tertiary or 35 each layer, of about 3 A to about 50 A, preferably about 10 quaternary ammonium ions, Sulfonium ions, phosphonium A. ions, Oxonium ions, or any ion of an element in Groups V or “Platelets' shall mean individual layers of the Layered VI of the periodic table of elements. Material. In accordance with an important feature of the present “Intercalate” or “Intercalated” shall mean a Layered invention, best results are achieved by mixing the layered 40 Material that includes an onium ion spacing/coupling agent material with the onium ions, e.g., C+onium ion spacing/ disposed between adjacent platelets of the layered Material coupling agent, in a concentration of at least about 2% by to increase the interlayer Spacing between the adjacent weight, preferably at least about 5% by weight onium ion platelets at least 3 A, preferably at least 5 A, to an interlayer compound, more preferably at least about 10% by weight spacing, for example, of at least about 10 A, preferably at onium ion compound, and most preferably about 30% to 45 least about 15 A, e.g., 18 A; and after MXD6 nylon about 80% by weight, based on the weight of onium ion co-intercalation, the d-spacing is increased to at least about compound and carrier (e.g., water, with or without an 20 A, preferably to 25 A to 35 A, e.g., 28 A. organic Solvent for the onium ion compound) to achieve “Intercalation' shall mean a proceSS for forming an Inter better Sorption of the onium ion spacing/coupling agent calate. compound between the platelets of the layered material. 50 “Onium Ion Spacing/Coupling Agent” or “Onium Ion Regardless of the concentration of onium ion compound in Compound' shall mean an organic compound that includes the intercalating composition, the weight ratio of MXD6 a positively charged atom Selected from the group consisting nylon intercalant:layered material should be at least 1:20, of a nitrogen atom, a phosphorous atom, a Sulfur atom or an preferably at least 1:10, more preferably at least 1:5, and oxygen atom, preferably a quaternary ammonium most preferably about 1:4 to achieve sufficient MXD6 nylon 55 compound, and when dissolved in water and/or an organic (or its monomeric reactants) intercalation between adjacent Solvent, an anion dissociates from the onium ion spacing/ inner Surfaces of adjacent platelets of the layered material. coupling agent leaving an onium cation that can ion The onium ion Spacing/coupling agent compound Sorbed eXchange with a Silicate platelet eXchangeable cation, e.g., between and bonded to (or complexed with) the silicate Na", Ca, Li", Mg', or K". platelets via ion-exchange causes Surprisingly easy interca 60 “MXD6 nylon' shall mean a nylon polymer, or meta lation of the MXD6 nylon polymer, or its monomeric Xylylene dianine and a dicarboxylic acid, Specifically adipic reactants for MXD6 nylon (meta-xylylene diamine and acid, monomer reactants or prepolymer (oligomer) that can adipic acid) polymerization in-situ. react and/or polymerize with curing agents to yield an In accordance with an important feature of the present MXD6 nylon polymer. The polymer, monomer reactants, or invention, it has been found that an onium ion-intercalated 65 prepolymer (oligomer) shall be a polymer of an amide that phyllosilicate, Such as a Smectite clay, can be intercalated is the reaction product of meta-xylylene diamine and adipic easily with MXD6 nylon to form anonium ion/MXD6 nylon acid. US 6,232,388 B1 S 6 “Co-intercalation' shall mean a proceSS for forming an weight nanomer, the oxygen permeability of the nanocom intercalate by intercalation of an onium ion Spacing/coupling posite is reduced to about 0.01 to about 0.02 cc/100 inf/day, agent and, at the same time or Separately, intercalation of or about a 95% reduction in oxygen permeability. MXD6 nylon polymer, or intercalation of polymerizable It is theorized that the Surprising reduction in Oxygen monomers capable of reacting and polymerizing to form an permeability is a result of the nanomer acting (alone, or in MXD6 nylon polymer, or intercalation of an MXD6 nylon combination with the MXD6 matrix polymer) as an oxygen oligomer. Scavenger to bind oxygen that it contacts to prevent the “Concentrate” shall mean an intercalate or exfoliate, transmission of oxygen through the matrix polymer that the formed by intercalation of MXD6 nylon into a layered nanomer is dispersed within. Silicate material, to form a concentrate comprising 10-90% The present invention is directed to the method of pre MXD6 nylon intercalant polymer and 10-90% intercalated paring intercalated layered materials prepared by layered Silicate material. co-intercalation of onium ion Spacing/coupling agents and “Intercalating Carrier' shall mean a carrier comprising MXD6 nylon into the galleries of the layered materials to water and/or an organic Solvent used with the onium ion form intercalates or intercalate concentrate compositions spacing/coupling agent and/or with the MXD6 nylon inter 15 that provide new and unexpected gas, particularly Oxygen, calant monomer/oligomer or polymer to form an Intercalat impermeability when incorporated into, as by direct com ing Composition capable of achieving Intercalation of the pounding with, matrix polymers, particularly MXD6 nylon. onium ion spacing/coupling agent and, at the same time or The present invention also is directed to the intercalates separately, intercalation of the MXD6 nylon polymer or and exfoliateS prepared from the intercalate or intercalate monomer reactants between platelets of the Layered Mate concentrate compositions. The exfoliate can be prepared by rial. adding the concentrate to polymerizable monomer/oligomer, “Intercalating Composition” or “Intercalant Composi or adding the polymer, e.g., MXD6 nylon, and then curing. tion' shall mean a composition comprising an onium ion The presence of polymerizable monomer or oligomer in the spacing/coupling agent and/or MXD6 nylon Intercalants, galleries of the layered materials makes the layered mate 25 rials compatible to the parent matrix polymer, e.g., MXD6 and a Layered Material, with or without an Intercalating nylon, when the intercalate is added to additional matrix Carrier. polymer that is the same as the monomer or oligomer “Exfoliate' or “Exfoliated” shall mean individual plate intercalated. Therefore, for example, when mixed with more lets of an Intercalated Layered Material or tactoids or MXD6 nylon, the layered materials are unexpectedly ready clusters of individual platelets, e.g., 2-10 platelets, prefer to be dispersed or exfoliated in the MXD6 nylon matrix ably 2-5 platelets, that are Smaller in total thickness than the polymer. When a polymer curing agent is added, the layered non-exfoliated Layered Material, dispersed as individual materials may be exfoliated by Virtue of the expanding, platelets or tactoids throughout a carrier material, Such as polymerizing MXD6 nylon monomer and resulting polymer water, a polymer, an alcohol or glycol, or any other organic molecules dispersed between platelet layers, depending solvent, or throughout a matrix polymer, such as MXD6 35 upon the degree of polymerization achieved. The exfoliated nylon. individual layers and tactoids of the layered materials will “Exfoliation” shall mean a process for forming an Exfo perform as a polymer reinforcement and molecule (gas) liate from an Intercalate. barrier in a matrix polymer to improve the mechanical “Matrix Polymer” shall mean a thermoplastic or thermo properties and barrier properties, e.g., gas impermeability, of Setting polymer that the Intercalate or Exfoliate is dispersed 40 the matrix polymer. The exfoliate also can be prepared by within to improve the mechanical Strength, thermal directly adding a curing agent to the monomer?-oligomer/or resistance, and/or particularly the gas (O) impermeability polymer/intercalated concentrate. The curing agent will pen of the Matrix Polymer, particularly MXD6 nylon. etrate into the gallery region of the intercalate to react with the polymerizable monomers, oligomers or polymers previ SUMMARY OF THE INVENTION 45 ously intercalated in the interlayer gallery and form uni In brief, the present invention is directed to intercalated formly dispersed platelets or a multi-layer intercalate in the layered materials prepared by co-intercalation of an onium resulting nanocomposite, having a high Solids content. ion and MXD6 nylon between the planar layers of a In another embodiment of the present invention, the Swellable layered material, Such as a phylloSilicate, prefer intercalate can be added into a polar organic compound or a ably a Smectite clay. The Spacing of adjacent layers of the 50 polar organic compound-containing composition carrier or layered materials is expanded at least about 3 A, preferably Solvent to provide unexpectedly Viscous carrier at least about 5 A, to at least about 10 A, preferably to at compositions, for delivery of the carrier or Solvent, or for least about 15 A, usually to about 15-30 A, e.g., 18 A with administration of an active compound that is dissolved or an onium ion spacing/coupling agent. The intercalation of dispersed in the carrier or Solvent. Such compositions, the MXD6 nylon polymer then increases the d-spacing of 55 especially the high Viscosity gels, are particularly useful for adjacent layers to at least about 20 A, preferably about 25 A delivery of active compounds, Such as oxidizing agents for to about 35A, generally about 28 A. hair waving lotions, and drugs for topical administration, As shown in the examples, MXD6 nylon film that does Since extremely high Viscosities are obtainable; and for not include the intercalates and/or exfoliates of the present admixtures of the intercalate, or exfoliate thereof, with polar invention has an oxygen permeability of about 0.16 to about 60 Solvents in modifying rheology, e.g., of cosmetics, oil-well 0.17 cc/100 inf/day, at atmospheric pressure, over a test drilling fluids, paints, lubricants, especially food grade period of 378 hours. By incorporating only 2.5% by weight lubricants, in the manufacture of oil and grease, and the like. of the intercalates and/or exfoliates (nanomers) of the Such intercalates and/or exfoliates also are especially useful present invention, the oxygen permeability is reduced to in admixture with matrix thermoplastic or thermosetting about 0.04 to about 0.05 cc/100 inf/day (less than /3 of the 65 polymers in the manufacture of polymeric articles, particu oxygen permeability). By doubling the amount of nanomer larly when added to and mixed with an MXD6 nylon matrix included in the MXD6 nanocomposite to about 5% by polymer. US 6,232,388 B1 7 8 The intercalate-containing and/or exfoliate-containing compositions can be in the form of a stable thixotropic gel -continued that is not Subject to phase Separation and can be used to Setup Information For FIGS. 1-3 deliver any active materials, Such as in the cosmetic, hair Data of FIGS. 1-3 were obtained on a Mocon OX-TRAN 2/20 Oxygen care and pharmaceutical industries. The layered material is 5 Transmission Analysis System in accordance with the following Setup intercalated by contact with the onium ion Spacing/coupling Information and parameters: agent and simultaneously or thereafter adding the MXD6 nylon to the onium ion-treated layered material, Such as by Material Type/Area Thick Indiv. Cycle Cond Elapsed direct compounding in an extruder, to co-intercalate the Identity F/P cm mil Zero Count Hr. Status Time onium ion and MXD6 nylon between adjacent phyllosilicate platelets and optionally separate (exfoliate) the layered FIG. 2: material into individual platelets. 2.5% Film SO 2.7 Yes 13 2.OO Test 378 Addition of the onium ion/MXD6 nylon intercalate to a PGWoda polymer melt enhances one or more properties, Such as Module 1 Parameters 15 Strength or temperature resistance, and particularly gas Exam = 60 min Bp = 730 impermeability; or mixing the intercalate with a carrier or ReZr = 6/6 Oxygen = 100.0% Solvent material maintains and/or increases Viscosity and Sp = 23.0 65% Rh Tp = 23.0 Nitrogen = 64% Rh thixotropy of the carrier material. The intercalate is easily, Cell B - 2.5% PGW ?oda homogeneously and uniformly dispersed throughout the Trans. rate (cc/U/day) carrier or Solvent or matrix polymer to achieve new and unexpected Viscosities in the carrier/platelet compositions 100% O2 Level 21.0% O.7141OO U = m? O.14996.1 even after addition of an active organic compound, Such as O.O46O71 U = 100 in O.OO9675 a cosmetic component or a medicament, for administration Elapsed test = 378 hr of the active organic compound(s) from the composition; FIG. 3 and provides new and unexpected gas barrier properties to 25 matrix polymers, particularly MXD6 nylon. 5.0% Film SO 4.1 Yes 12 2.OO Test 378 PGWoda Module 2 Parameters BRIEF DESCRIPTION OF THE DRAWINGS Exam = 60 min Bp = 731 FIG. 1 is a graph showing the oxygen permeability, with ReZr = 6/6 Oxygen = 100.0% time (cc/100 in/day), of MXD6 nylon (without an interca Sp = 23.0 68%. Rh Tp = 23.0 Nitrogen = 66% Rh late or exfoliate) over 378 hours at 65% relative humidity. Cell A - 5.0% PGWoda Data are presented in Table 2. Trans. rate (cc/U/day) FIG. 2 is a graph showing the oxygen permeability, with 35 100% O2 Level 21.0% time (cc/100 in/day), of MXD6 nylon having 2.5% of the -O.O346 U = m? -O.OO73 intercalate of Example 2. Data are presented in Table 3. -OOO22 U = 100 in -OOOOS FIG. 3 is a graph showing the oxygen permeability, with Elapsed test = 378 hr time (cc/100 in/day), of MXD6 nylon having 5.0% of the intercalate of Example 2. Data are presented in Table 4. 40 To form the intercalated and exfoliated materials of the present invention, the layered material, e.g., the DETAILED DESCRIPTION OF THE phyllosilicate, should be Swelled or intercalated, in the PREFERRED EMBODIMENTS preferred embodiment, by Sorption of an onium ion spacing/ coupling agent and, Simultaneously or Subsequently inter 45 calated with MXD6 nylon. Setup Information For FIGS. 1-3 While the invention described herein is disclosed by way Data of FIGS. 1-3 were obtained on a Mocon OX-TRAN 2/20 Oxygen of the preferred embodiment via expanding the interlaminar Transmission Analysis System in accordance with the following Setup spacing between adjacent platelets of a layered Silicate Information and parameters: material, e.g., a phyllosilicate, by first intercalating onium Material Type/Area Thick Indiv. Cycle Cond Elapsed 50 ions between the Silicate platelets, prior to or Simultaneously with intercalating a MXD6 nylon intercalant, it should be Identity F/P cm mil Zero Count Hr. Status Time understood that the MXD6 nylon intercalant can be inter FIG. 1: calated between and complexed to the internal platelet faces by other well known mechanisms, Such as the dipole/dipole Pure Film SO 2.7 Yes 13 2.OO Test 378 55 (direct intercalation of the MXD6 oligomer or polymer) MXD6 method disclosed in this Assignee's U.S. Pat. Nos. 5,880, Module 1 Parameters 197 and 5,877,248, hereby incorporated by reference; and Exam = 60 min Bp = 731 by intercalating a Silane coupling agent, or by the acidifi ReZr = 6/6 Oxygen = 100.0% cation technique, by Substitution with hydrogen (ion Sp = 23.0 65% Rh Tp = 23.0 Nitrogen = 65% Rh 60 eXchanging the interlayer cations with hydrogen by use of an Cell A - Pure MXD6 acid or ion-exchange resin) as disclosed in the Deguchi U.S. Trans. reate (cc/U/day) Pat. No. 5,102,948, and in the Pinnavaia, et al. U.S. Pat. No. 5,853,886, hereby incorporated by reference. 100% O2 Level 21.0% 2.53210 U = m? O.531741 Sorption of the onium ion spacing/coupling agent should O.163361 U = 100 in O.O.34306 65 be Sufficient to achieve expansion of the interlayer spacing Elapsed test = 378 hr of adjacent platelets of the layered material (when measured dry) at least about 3 A, preferably at least about 5 A, and US 6,232,388 B1 9 10 intercalation of both the onium ion Spacing/coupling agent -phosphonium, -oxonium, or -Sulfonium derivatives of and MXD6 nylon should achieve a d-spacing of at least aliphatic, aromatic or arylaliphatic amines, phosphines, about 20 A, preferably at least about 25 A. esters, alcohols and Sulfides. Illustrative of Such materials The onium ion spacing/coupling agent is introduced into are di-onium compounds of the formula: the layered material galleries in the form of a Solid or liquid composition (neat or aqueous, with or without an organic Solvent, e.g., an aliphatic hydrocarbon, Such as heptane to, if where X" and Y, same or different, are ammonium, necessary, aid to dissolve the onium ion compound) having Sulfonium, phosphonium, or Oxonium radicals. Such as an onium ion spacing/coupling agent concentration Suffi *NH, -NH-, *N(CH), *N(CH) 2 , *N(CH), cient to provide a concentration of about 5% to about 10% (CHCH), N(CH2)(CHCH-)-, *S(CH), S(CH)--, by weight clay (90-95% water) and the onium ion com *P(CH), P(CH)-, NH, NH-, and the like; R is an pound is dissolved in the clay Slurry water, preferably at a organic spacing, backbone radical, Straight or branched, molar ratio of onium ions to exchangeable interlayer cations preferably having from 2 to 24, more preferably 3 to 10 of at least about 0.5:1, more preferably at least about 1:1. carbon atoms, in a backbone organic spacing molecule The onium ion-intercalated clay then is Separated from the 15 covalently bonded at its ends to charged N', P, S and for water easily, Since the clay is now hydrophobic, and dried in O" cations and R' can be hydrogen, or an alkyl radical of 1 an oven to less than 5% water, preferably bone dry, before to 22 carbon atoms, linear or branched, preferably having at being compounded with the MXD6 nylon for MXD6 nylon least 6 carbon atoms. Examples of R include substituted or intercalation and compounding. The onium ion spacing/ unsubstituted alkylene, cycloalkenylene, cycloalkylene, coupling agent compound can be added as a Solid with the arylene, alkylarylene, either unsubstituted or Substituted addition to the layered material onium ion compound blend with amino, alkylamino, dialkylamino, nitro, azido, alkenyl, of preferably at least about 20% water, more preferably at alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkyl, least about 30% water or more, based on the dry weight of aryloxy, arylalkylamino, alkylamino, arylamino, layered material. Preferably about 30% to about 50% water, dialkylamino, diarylamino, aryl, alkylsulfinyl, aryloxy, more preferably about 30% to about 40% water, based on the 25 alkylsulfinyl, alkylsulfonyl, arylthio, arylsulfinyl, dry weight of the layered material, is included in the onium alkoxycarbonyl, arylsulfonyl, or alkylsilane. Examples of R' ion intercalating composition, So that less water is Sorbed by include non-existent; H, alkyl having 1 to 22 carbon atoms, the intercalate, thereby necessitating less drying energy after Straight chain or branched; cycloalkenyl, cycloalkyl, aryl; onium ion intercalation. alkylaryl, either unsubstituted or substituted or substituted The onium ion Spacing/coupling agent cations interca with amino, alkylamino, dialkylamino, nitro, azido, alkenyl, lated via ion-exchange into the interlayer spaces between alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkyl, adjacent layered material platelets are primary, Secondary, aryloxy, arylalkylamino, alkylamino, arylamino, tertiary or quaternary onium ions having the following dialkylamino, diarylamino, aryl, alkylsulfinyl, aryloxy, preferred Structure: alkylsulfinyl, alkylsulfonyl, arylthio, arylsulfinyl, 35 alkoxycarbonyl, arylsulfonyl, or alkylsilane. Illustrative of useful R groups are alkylenes, Such as methylene, ethylene, octylene, nonylene, tert-butylene, neopentylene, isopropylene, Sec-butylene, dodecylene and the like; alk enylene S Such as 1-prope nylene, 1-bute nylene, 40 1-pentenylene, 1-hexenylene, 1-heptenylene, 1-octenylene wherein X=N, P, S, or O; and and the like, cycloalkenylenes Such as cyclohexenylene, wherein R, R2, R and R are H or organic moieties, Such cyclopentenylene and the like; alkanoylalkylenes Such as as linear or branched alkyl, aryl or aralkyl moieties having butanoyl octadecylene, pentanoyl nonadecylene, octanoyl 1 to about 24 carbon atoms. pentadecylene, ethanoyl undecylene, propanoyl hexade The more preferred C+ onium ions are preferably qua 45 cylene and the like, alkylaminoalkylenes, Such as methy ternary ammonium ions having Formula 1, as follows: lamino octadecylene, ethylamino pentadecylene, buty lamino nonadecylene and the like; dialkylaminoalkylene, Formula 1 Such as dimethylamino octadecylene, methylethylamino R R2 nonadecylene and the like, arylaminoalkylenes Such as N 50 phenylamino octadecylene, p-methylphenylamino nonade cylene and the like; diarylaminoalkylenes, Such as dipheny K Y 4 lamino pentadecylene, p-nitrophenyl-p'-methylphenylamino octadecylene and the like; alkylarylaminoalkylenes, Such as Wherein R is a long chain alkyl moiety ranging from C. 2-phenyl-4-methylamino pentadecylene and the like; to C, straight or branched chain, including mixtures of 55 alkylsulfinylenes, alkylsulfonylenes, alkylthio, arylthio, long chain moieties, i.e., Co, Cs, Co, C12, C14, C6, C1s, arylsulfinylenes, and arylsulfonylenes Such as butylthio Co., C22 and C2, alone or in any combination; and R2, R octadecylene, neopentylthio pentadecylene, methylsulfinyl and R are moieties, Same or different, Selected from the nonadecylene, benzylsulfinyl pentadecylene, phenylsulfinyl group consisting of H, alkyl, benzyl, Substituted benzyl, e.g., octadecylene, propylthiooctadecylene, octylthio Straight or branched chain alkyl-Substituted and halogen 60 pentadecylene, nonylsulfonyl nonadecylene, octylsulfonyl Substituted; ethoxylated or propoxylated alkyl, ethoxylated hexadecylene, methylthio nonadecylene, isopropylthio or propoxylated benzyl, e.g., 1-10 moles of ethoxylation or octadecylene, phenylsulfonyl pentadecylene, methylsulfo 1-10 moles of propoxylation. nyl nonadecylene, nonylthio pentadecylene, phenylthio Additional useful multi-charged spacing/coupling agents octadecylene, ethyltio nonadecylene, benzylthio include for example, tetra-, tri-, and di-onium Species Such 65 undecylene, phenethylthio pentadecylene, Sec-butylthio as tetra-ammonium, tri-ammonium, and di-ammonium octadecylene, naphthylthio undecylene and the like; alkoxy (primary, Secondary, tertiary, and quaternary), carbonylalkylene S Such as methoxycarbonylene, US 6,232,388 B1 11 12 ethoxycarbonylene, butoxycarbonylene and the like; montmorillonite, particularly Sodium montmorillonite, mag cycloalkylenes Such as cyclohexylene, cyclopentylene, nesium montmorillonite and/or calcium montmorillonite; cyclo-octylene, cycloheptylene and the like; alkoxyalky nontronite, beidellite; Volkonskoite; hectorite, Saponite, Sau lenes Such as methoxy-methylene, ethoxymethylene, conite, Sobockite, Stevensite; SVinfordite; Vermiculite, and butoxymethylene, propoxyethylene, pentoxybutylene and the like. Other useful layered materials include micaceous the like, aryloxyalkylenes and aryloxyarylenes Such as phenoxyphenylene, phenoxymethylene and the like, arylo minerals, Such as illite and mixed layered illite/Smectite ryalkylenes Such as phenoxydecylene, phenoxyoctylene and minerals, Such as rectorite, taroSovite, ledikite and admix the like, arylalkylenes Such as benzylene, phenthylene, tures of illites with the clay minerals named above. 8-phenyloctylene, 10-phenyldecylene and the like; alky Preferred Swellable layered materials are phyllosilicates larylenes Such as 3-decylphenylene, 4-octylphenylene, of the 2:1 type having a negative charge on the layers 4-nonylphenylene and the like; and polypropylene glycol ranging from about 0.15 to about 0.9 charges per formula and polyethylene glycol Substituents Such as ethylene, unit and a commensurate number of eXchangeable metal propylene, butylene, phenylene, benzylene, tolylene, cations in the interlayer spaces. Most preferred layered p-Styrylene, p-phenylmethylene, octylene, dodecylene, materials are Smectite clay minerals Such as 15 montmorillonite, nontronite, beidellite, Volkonskoite, octadecylene, methoxy-ethylene, moieties of the formula hectorite, Saponite, Sauconite, Sobockite, Stevensite, and -CHCOO-, -CHCOO-, -CHCOO-, SVinfordite. -C7HCOO-, -CHCOO-, -CHCOO-, AS used herein the “interlayer spacing refers to the -CHCOO-, -CHCOO-, and -C7HCOO distance between the internal faces of the adjacent layers as and -C=C(CH2)COOCHCH-, and the like. Such they are assembled in the layered material before any tetra-, tri-, and di-ammonium, -Sulfonium, -phosphonium, delamination (exfoliation) takes place. The preferred clay - Oxonium, ammonium/sulfonium, ammonium/ materials generally include interlayer cations Such as Na", phosphonium; ammonium/oxonium; phosphonium/ Ca", K", Mg', NH." and the like, including mixtures Oxonium; Sulfonium/oxonium; and Sulfonium/phosphonium thereof. medicals are well known in the art and can be derived from 25 The amount of onium ion spacing/coupling agent inter the corresponding amines, phosphines, alcohols or ethers, calated into the SWellable layered materials, in order that the and Sulfides. intercalated layered material platelet Surfaces Sufficiently The preferred multi-charged spacing/coupling agent com complex or bond via ion-exchange to the onium ion spacing/ pounds are multi-onium ion compounds that include at least coupling agent molecules Such that the layered material may two primary, Secondary, tertiary or quaternary ammonium, be sufficiently spaced for easy intercalation of MXD6 nylon phosphonium, Sulfonium, and/or Oxonium ions having For or its monomeric/oligomeric reactants, may vary Substan mula 2, as follows: tially between about 2%, preferably at least about 10%, and about 200%, based on the dry weight of the layered material. Formula 2 In the preferred embodiments of the invention, amounts of R R 35 onium ion employed, with respect to the dry weight of Z1 7' R-Yi-Z2 layered material being intercalated, will preferably range from about 8 grams of onium ion Spacing/coupling agent R2 R4 compound: 100 grams of layered material (dry basis), pref erably at least about 10 grams of onium ion spacing/ wherein R is an alkylene, aralkylene or Substituted alkylene 40 coupling agent compound:100 grams of layered material to charged atom Spacing moiety, preferably ranging from C to about 80-90 grams onium ion spacing/coupling agent com C, more preferably about C to C for relatively high pound: 100 grams of layered material. More preferred charge density (150 milliequivalents/100grams C.E.C. to 70 amounts are from about 20 grams of onium ion spacing/ millieduivalents/100 grams C.E.C.) layered materials; and coupling agent compound:100 grams of layered material to preferably from C to C for medium to low charge density 45 about 60 grams of onium ion spacing/coupling agent com (70 millie quivalents/100 grams C.E.C. to 30 pound: 100 grams of layered material (dry basis). milliequivalents/100 grams C.E.C.) layered materials. R can The onium ions and MXD6 nylon intercalants may be be straight or branched chain, including mixtures of Such introduced into (sorbed within) the interlayer spaces of the moieties, i.e., C4, Cs, Co, C7, Cs, Co, Co, C11, C12, C13, C14, layered material in a number of ways. In a preferred method C1s, C16, C7, C1s, Co, Co., C21, C22, C2a and C24, alone or 50 of intercalating the onium ions between adjacent platelets of in any combination; and R, R2, R and R are moieties, the layered material, the layered material is slurried in water, Same or different, Selected from the group consisting of e.g., at 5-20% by weight layered material and 80-95% by hydrogen, alkyl, aralkyl, benzyl, Substituted benzyl, e.g., weight water, and the onium ion compound is dissolved in Straight or branched chain alkyl-Substituted and halogen the water in which the layered material is slurried. If Substituted; ethoxylated or propoxylated alkyl, ethoxylated 55 necessary, the onium ion compound can be dissolved first in or propoxylated benzyl, e.g., 1-10 moles of ethoxylation or an organic Solvent, e.g., propanol. The layered material then 1-10 moles of propoxylation. Z' and Z, same or different, is separated from the Slurry water and dried prior to com may be non-existent, or may be any of the moieties pounding with MXD6 nylon for intercalation of the MXD6 described for R, R, R or R. Also, one or both of Z' and nylon and to form the nanocomposite material in MXD6 Z may include one or more positively charged atoms or 60 nylon matrix polymer. In a preferred method of intercalating onium ion molecules. the MXD6 nylon, the onium ion-treated layered material is Any Swellable layered material that sufficiently sorbs the intimately mixed with the MXD6 nylon, e.g., by extrusion or onium ion spacing/coupling agent to increase the interlayer pug milling, to form an intercalating composition compris spacing between adjacent phyllosilicate platelets at least ing the onium ion-intercalated layered material and MXD6 about 3 A, preferably at least about 5 A, can be used in the 65 nylon polymer. practice of this invention. Useful Swellable layered materials To achieve Sufficient intercalation of the onium ions include phyllosilicates, Such as Smectite clay minerals, e.g., between adjacent platelets of the layered material, the lay US 6,232,388 B1 13 14 ered material onium ion intercalating composition contains weight of the mixture, and most preferably from about at least about 5% by weight, preferably at least about 10% 0.05% to about 20% or 0.05% to about 10% by weight. by weight onium ion compound, based on the dry weight of In accordance with a preferred embodiment of the present the layered material, So that the resulting onium ion invention, the onium ion-intercalated layered material can intercalated layered material has interior platelet Surfaces be intercalated with MXD6 nylon and then dispersed into that are sufficiently hydrophobic and sufficiently spaced for one or more melt-processible thermoplastic and/or thermo intercalation of the MXD6 nylon. The onium ion carrier Setting matrix oligomers or polymers, or mixtures thereof, (preferably water, with or without an organic Solvent) can be by direct compounding. Matrix polymers for use in this added by first Solubilizing or dispersing the onium ion embodiment of the process of this invention may vary compound in the carrier; or a dry onium ion compound and widely, the only requirement is that they are melt proces relatively dry phylloSilicate (preferably containing at least Sible. In this embodiment of the invention, the polymer, e.g., about 4% by weight water) can be blended and the interca MXD6 nylon, includes at least ten (10), preferably at least lating carrier added to the blend, or to the phyllosilicate prior thirty (30) recurring monomeric units. The upper limit to the to adding the dry onium ion. When intercalating the phyl number of recurring monomeric units is not critical, pro losilicate with onium ions in slurry form (e.g., 900 pounds 15 vided that the melt index of the matrix polymer under use water, 100 pounds phyllosilicate, 100 pounds onium ion conditions is Such that the matrix polymer forms a flowable compound), the amount of water can vary Substantially, e.g., mixture. Most preferably, the matrix polymer is MXD6 from about 4% by weight, preferably from a minimum of at nylon that is intercalted into the onium ion-intercalated least about 30% by weight water, with no upper limit to the layered material simultaneously with dispersing the MXD6 amount of water in the intercalating composition (the phyl nylon-intercalated clay uniformly into the MXD6 nylon losilicate intercalate is easily Separated from the intercalat matrix polymer. The MXD6 nylon matrix polymer prefer ing composition due to its hydrophobicity after onium ion ably includes from at least about 10 to about 100 recurring treatment). monomeric units. In the most preferred embodiments of this Alternatively, the onium ion intercalating carrier, e.g., invention, the number of recurring units is Such that the water, with or without an organic Solvent, can be added 25 matrix polymer has a melt index of from about 0.01 to about directly to the phyllosilicate prior to adding the onium ion 12 grams per 10 minutes at the processing temperature. compound, either dry or in Solution. Sorption of the onium MXD6 nylon, from Mitsubishi Gas Chemical Company, ion compound molecules may be performed by exposing the Inc., Tokyo, Japan is a polymer having the following For layered material to a dry or liquid onium ion compound in mula 3: the onium ion intercalating composition containing at least about 2% by weight, preferably at least about 5% by weight Formula 3 onium ion compound, more preferably at least about 10% onium ion compound, based on the dry weight of the layered H (NH-CH CH-NHCO-CH-CO-in-OH material. In accordance with another method of intercalating the 35 onium ions and MXD6 nylon between the platelets of the layered material, the layered material, preferably containing at least about 4% by weight water, more preferably about wherein 10% to about 15% by weight water, is blended with water n for the monomer=1; and/or organic Solvent Solution of an onium ion spacing/ 40 n for the oligomer=2-10; and coupling agent compound in a ratio Sufficient to provide at n for the polymer=11-20,000, least about 5% by weight, preferably at least about 10% by preferably 11-1,000, weight onium ion compound, based on the dry weight of the more preferably 11-500. layered material. The onium ion compound can be interca Other thermoplastic resins and rubbers for use as matrix lated into the layered material Simultaneously with the 45 monomers, oligomers or polymers in the practice of this intercalation of the MXD6 nylon, or the MXD6 nylon may invention may vary widely. Illustrative of useful thermo be intercalated after intercalation of the onium ion spacing/ plastic resins, which may be used alone or in admixture, are coupling agent. The dry onium ion-intercalated clay then is polyactones Such as poly(pivalolactone), poly(caprolactone) extruded with MXD6 nylon for direct compounding, with and the like; polyureanes derived from reaction of diisocy intercalation, of the MXD6 nylon into the onium ion 50 anates Such as 1,5-naphthalene diisocyanate; p-phenylene intercalated layered material. diisocyanate, m-phenylene diisocyanate, 2,4-toluene The onium ion spacing/coupling agents have an affinity diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'- for the phyllosilicate so that they are sorbed between, and dimethyl-4,4'-biphenyl diisocyanate, 4,4'- are ion-exchanged with the cations on the inner Surfaces of diphenylisopropylidene diisocyanate, 3,3'-dimethyl-4,4'- the Silicate platelets, in the interlayer Spaces. 55 diphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane It is preferred that the onium ion/MXD6 nylon intercalate diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, loading be less than about 10% for purposes of increasing dianisidine diisocyanate, toluidine diisocyanate, hexameth the Viscosity of an organic liquid carrier. Intercalate loadings ylene diisocyanate, 4,4'-diisocyanatodiphenylmethane and within the range of about 0.05% to about 40% by weight, the like and linear long-chain diols Such as poly preferably about 0.5% to about 20%, more preferably about 60 (tetramethylene adipate), poly(ethylene adipate), poly(1,4- 1% to about 10% significantly enhances viscosity. In butylene adipate), poly(ethylene Succinate), poly(2,3- general, the amount of intercalate and/or exfoliated particles butylene Succinate), polyether diols and the like; thereof incorporated into a liquid carrier, Such as a polar polycarbonates Such as polymethane bis(4-phenyl) Solvent, e.g., a glycol Such as glycerol, is less than about carbonate, poly 1,1-ether bis(4-phenyl) carbonate, poly 90% by weight of the mixture, and preferably from about 65 diphenylmethane bis(4-phenyl)carbonate, poly 1,1- 0.01% to about 80% by weight of the composite material cyclohexane bis(4-phenyl)carbonate and the like; polysul mixture, more preferably from about 0.05% to about 40% by fones; polyethers; polyketones; polyamides Such as poly(4- US 6,232,388 B1 15 16 aminobutyric acid), poly(hexamethylene adipamide), poly manufactured by Shell Chemical Company under the trade (6-aminohexanoic acid), poly(m-xylylene adipamide) or name KRATONCE). MXD6 nylon, poly(p-xylylene Sebacamide), poly(2,2,2- Useful thermosetting resins useful as matrix polymers trimethyl hexamethylene terephthalamide), poly include, for example, the polyamides, polyalkylamides; (metaphenylene isophthalamide) (NOMEX), poly(p- polyesters, polyurethanes, polycarbonates, polyepoxides; phenylene terephthalamide) (KEVLAR), and the like; and mixtures thereof. polyesterS Such as poly(ethylene azelate), poly(ethylene-1, Most preferred thermoplastic polymers for use as a matrix 5-naphthalate, poly(1,4-cyclohexane dimethylene polymer are thermoplastic polymerS Such as polyamides, terephthalate), poly(ethylene oxybenzoate) (A-TELL), poly particularly nylons, most particularly MXD6 nylon. Polya (para-hydroxybenzoate) (EKONOL), poly(1,4- mides which may be used as matrix polymers in the process cyclohexylidene dimethylene terephthalate) (KODEL) (cis), of the present invention are Synthetic linear polycarbon poly(1,4-cyclohexylidene dimethylene terephthalate) amides characterized by the presence of recurring carbon (KODEL) (trans), polyethylene terephthalate, polybutylene amide groups as an integral part of the polymer chain which terephthte and the like; poly(arylene oxides) Such as poly are Separated from one another by at least two carbon atoms. (2,6-dimethyl-1,4-phenylene oxide), poly(2,6-diphenyl-1,4- 15 Polyamides of this type include polymers, generally known phenylene oxide) and the like; poly(arylene Sulfides) Such as in the art as nylons, obtained from diamines and dibasic poly(phenylene Sulfide) and the like; polyetherimides, vinyl acids having the recurring unit represented by the general polymers and their copolymerS Such as polyvinyl acetate, formula: polyvinyl alcohol, polyvinyl chloride; polyvinyl butyral, polyvinylidene chloride, ethylene-Vinyl acetate copolymers, -NHCORCOHNR and the like; polyacrylics, polyacrylate and their copolymers in which R" is an alkylene group of at least 2 carbon atoms, Such as polyethyl acrylate, poly(n-butyl acrylate), preferably from about 2 to about 11; or arylene having at polymethylmethacrylate, polyethyl methacrylate, poly(n- least about 6 carbon atoms, preferably about 6 to about 17 butyl methacrylate), poly(n-propyl methacrylate), carbon atoms; and R'' is selected from Randaryl groups. polyacrylamide, polyacrylonitrile, polyacrylic acid, 25 Also, included are copolyamides and terpolyamides ethylene-acrylic acid copolymers, ethylene-Vinyl alcohol obtained by known methods, for example, by condensation copolymers acrylonitrile copolymers, methyl methacrylate of hexamethylene diamine or meta-xylylene diamine and a Styrene copolymers, ethylene-ethyl acrylate copolymers, mixture of dibasic acids consisting of terephthalic acid and methacrylated butadiene-Styrene copolymers and the like; adipic acid. Polyamides of the above description are well polyolefins Such as low density poly(ethylene), poly known in the art and include, for example, the copolyamide (propylene), chlorinated low density poly(ethylene), poly(4- of 30% hexamethylene diammonium isophthalate and 70% methyl-1-pentene), poly(ethylene), poly(styrene), and the hexamethylene diammonium adipate, poly(hexamethylene like; ionomers; poly(epichlorohydrins); poly(urethane) Such adipamide) (nylon 6,6), poly(hexamethylene sebacamide) as the polymerization product of diols Such as glycerin, (nylon 6,10), poly(hexamethylene isophthalamide), poly trimethylol-propane, 1,2,6-hexane triol, Sorbitol, 35 (hexamethylene terephthalamide), poly(heptamethylene pentaerythritol, polyether polyols, polyester polyols and the pimelamide) (nylon 7.7), poly(octamethylene Sebacamide) like with a polyisocyanate Such as 2,4-tolylene diisocyanate, (nylon 8.8), poly(nonamethylene azelamide) (nylon 9.9) 2,6-tolylene diisocyante, 4,4'-diphenylmethane poly(decamethylene azelamide) (nylon 10,9), poly diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'- (decamethylene Sebacamide) (nylon 10,10), polybis(4- dicyclohexyl-methane diisocyanate and the like; and 40 amino cyclohexyl)methane-1,10-decane-carboxamide), poly Sulfones Such as the reaction product of the Sodium Salt poly(m-xylylene adipamide), poly(p-xylylene Sebacamide), of 2,2-bis(4-hydroxyphenyl) propane and 4,4'- poly(2,2,2-trimethylhexamethylene terephthalamide), poly dichlorodiphenyl Sulfone, furan resins Such as poly(furan); (piper a Zine Seba camide), poly (p-phenylene cellulose ester plastics Such as cellulose acetate, cellulose terephthalamide), poly(metaphenylene isophthalamide) and acetate butyrate, cellulose propionate and the like; Silicones 45 the like. Such as poly(dimethyl siloxane), poly(dimethyl siloxane Other useful polyamides for use as a matrix polymer are co-phenylmethyl siloxane), and the like; protein plastics; those formed by polymerization of amino acids and deriva and blends of two or more of the foregoing. tives thereof, as, for example, lactams. Mustrative of these Vulcanizable and thermoplastic rubbers useful as matrix useful polyamides are poly(4-aminobutyric acid) (nylon 4), polymers in the practice of this embodiment of the invention 50 poly(6-aminohexanoic acid) (nylon 6), poly(7- may also vary widely. Illustrative of such rubbers are aminoheptanoic acid) (nylon 7), poly(8-aminooctanoic acid) brominated butyl rubber, chlorinate butyl rubber, polyure (nylon 8), poly(9-aminononanoic acid) (nylon 9), poly(10 thane elastomers, fluoroelastomers, polyester elastomers, aminodecanoic acid) (nylon 10), poly(11-aminoundecanoic polyvinylchloride, butadiene/acrylonitrile elastomers, sili acid) (nylon 11), poly(12-aminododecanoic acid) (nylon 12) cone elastomers, poly(butadiene), poly(isobutylene), 55 and the like. ethylene-propylene copolymers, ethylene-propylene-diene Other matrix or host polymers which may be employed in terpolymers, Sulfonated ethylene-propylene-diene admixture with the onium ion and MXD6 nylon intercalates ter polymers, poly (chlorop rene), poly (2,3- of the present invention to form nanocomposites are linear dimethylbutadiene), poly(butadiene-pentadiene), chlorosul polyesters. The type of polyester is not critical and the phonated poly(ethylenes), poly(sulfide) elastomers, block 60 particular polyesters chosen for use in any particular Situa copolymers, made up of Segments of glassy or crystalline tion will depend essentially on the physical properties and blockS Such as poly(styrene), poly(Vinyl-toluene), poly(t- features, i.e., tensile Strength, modulus and the like, desired butyl styrene), polyesters and the like and the elastomeric in the final form. Thus, a multiplicity of linear thermoplastic blockS Such as poly(butadiene), poly(isoprene), ethylene polyesters having wide variations in physical properties are propylene copolymers, ethylene-butylene copolymers, poly 65 Suitable for use in admixture with exfoliated layered mate ether and the like as for example the copolymers in poly rial platelets in manufacturing nanocomposites in accor (styrene)-poly(butadiene)-poly(styrene) block copolymer dance with this invention. US 6,232,388 B1 17 18 The particular polyester chosen for use as a matrix methacrylic acid, chlorotrifluoroethylene, Vinyl chlo polymer can be a homo-polyester or a copolyester, or ride and the like. Preferred are poly(propylene), pro mixtures thereof, as desired. Polyesters are normally pre pylene copolymers, poly(ethylene) and ethylene pared by the condensation of an organic dicarboxylic acid copolymers. More preferred are poly(ethylene) and and an organic diol, and, the reactants can be added to the 5 poly(propylene). intercalates, or exfoliated intercalates for in Situ polymer The mixture may include various optional components ization of the polyester while in contact with the layered which are additives commonly employed with polar organic material, before or after exfoliation of the intercalates. liquids. Such optional components include nucleating Polyesters which are suitable for use as matrix polymers agents, fillers, plasticizers, impact modifiers, chain in this embodiment of the invention are those which are extenders, plasticizers, colorants, mold release lubricants, derived from the condensation of aromatic, cycloaliphatic, antistatic agents, pigments, fire retardants, and the like. and aliphatic diols with aliphatic, aromatic and These optional components and appropriate amounts are cycloaliphatic dicarboxylic acids and may be cycloaliphatic, well known to those skilled in the art. aliphatic or aromatic polyesters. The amount of onium ion/MXD6 nylon intercalated lay Exemplary of useful cycloaliphatic, aliphatic and aro 15 ered material included in the liquid carrier or Solvent com matic polyesters which can be utilized as matrix polymers in positions to form the Viscous compositions Suitable to the practice of this embodiment of the invention are poly deliver the carrier or Some carrier-dissolved or carrier (ethylene terephthalate), poly(cyclohexylenedimethylene dispersed active material, Such as a pharmaceutical, may terephthalate), poly(ethylene dodecate), poly(butylene vary widely depending on the intended use and desired terephthalate), polyethylene(2,7-naphthalate), poly Viscosity of the composition. For example, relatively higher (methaphenylene isophthalate), poly(glycolic acid), poly amounts of intercalates, i.e., from about 10% to about 30% (ethylene Succinate), poly(ethylene adipate), poly(ethylene by weight of the total composition, are used in forming Seba cate), poly (de came thylene a Zelate), poly Solvent gels having extremely high Viscosities, e.g., 5,000 to (decamethylene adipate), poly(decamethylene Sebacate), 5,000,000 centipoises. Extremely high viscosities, however, poly(dimethylpropiolactone), poly(para-hydroxybenzoate) 25 also can be achieved with a relatively Small concentration of (EKONOL), poly(ethylene oxybenzoate) (A-tell), poly intercalates and/or exfoliates thereof, e.g., 0.1% to 5% by (ethylene isophthalate), poly(tetramethylene terephthalate, weight, by adjusting the pH of the composition in the range poly(hexamethylene terephthalate), poly(decamethylene of about 0-6 or about 10-14 and/or by heating the compo te rephthalate), poly(1,4-cyclohexane dimethylene Sition above room temperature, e.g., in the range of about terephthalate) (trans), poly(ethylene 1,5-naphthalate), poly 25° C. to about 200° C., preferably about 75° C. to about (ethylene 2,6-naphthalate), poly(1,4-cyclohexylidene dim 100° C. It is preferred that the intercalate or platelet loading ethylene terephthalate), (KODEL) (cis), and poly(1,4- be less than about 10% by weight of the composition. cyclohexylidene dimethylene terephthalate (KODEL) Intercalate or platelet particle loadings within the range of (trans). about 0.01% to about 40% by weight, preferably about Polyester compounds prepared from the condensation of 35 0.05% to about 20%, more preferably about 0.5% to about a diol and an aromatic dicarboxylic acid are especially 10% of the total weight of the composition significantly Suitable as matrix polymers in accordance with this embodi increases the Viscosity of the composition. In general, the ment of the present invention. Illustrative of such useful amount of intercalate and/or platelet particles incorporated aromatic carboxylic acids are terephthalic acid, isophthalic into the carrier/solvent is less than about 20% by weight of acid and a o-phthalic acid, 1,3-naphthalene-dicarboxylic 40 the total composition, and preferably from about 0.05% to acid, 1,4-naphthale nedicarboxylic acid, 2,6- about 20% by weight of the composition, more preferably naphthalenedicarboxylic acid, 2,7-naphthalene-dicarboxylic from about 0.01% to about 10% by weight of the acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylsulfone composition, and most preferably from about 0.01% to dicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3-(p- about 5%, based on the total weight of the composition. carboxyphenyl)-idane, diphenyl ether 4,4'-dicarboxylic acid, 45 In accordance with an important feature of the present bis-p(carboxy-phenyl) methane and the like. Of the afore invention, the intercalate and/or platelet/carrier composi mentioned aromatic dicarboxylic acids, those based on a tions of the present invention can be manufactured in a benzene ring (Such as terephthalic acid, isophthalic acid, concentrated form, e.g., as a concentrate, e.g., having about orthophthalic acid) are preferred for use in the practice of 10-90%, preferably about 20-80% intercalate and/or exfo this invention. Among these preferred acid precursors, 50 liated platelets of layered material and about 10-90%, terephthalic acid is particularly preferred acid precursor. preferably about 20-80% matrix polymer, particularly Still other useful thermoplastic homopolymers and MXD6 nylon. The concentrate can be dispersed in the copolymer matrix polymers for forming nanocomposites matrix polymer and optionally exfoliated, before or after with the onium ion MXD6 nylon intercalated layered mate addition to a polymer melt to a desired intercalate and/or rials of the present invention are polymers formed by 55 platelet loading. polymerization of alpha-beta-unsaturated monomers or the In one embodiment, the onium ion/MXD6 nylon formula: intercalates, and/or exfoliates thereof, are mixed with a carrier or Solvent to produce Viscous compositions of the carrier or Solvent optionally including one or more active wherein: 60 compounds, Such as an antiperSpirant compound, dissolved R" and R'' are the same or different and are cyano, or dispersed in the carrier or Solvent. phenyl, carboxy, alkylester, halo, alkyl, alkyl Substi When shear is employed for exfoliation, any method tuted with one or more chloro or fluoro, or hydrogen. which can be used to apply a shear to the intercalate/matrix Illustrative of such preferred homopolymers and polymer nanocomposite composition can be used. The copolymers are homopolymers and copolymers of 65 Shearing action can be provided by any appropriate method, ethylene, propylene, Vinyl alcohol, acrylonitrile, as for example by mechanical means, by thermal Shock, by Vinylidene chloride, esters of acrylic acid, esters of preSSure alteration, or by ultraSonics, all known in the art. In US 6,232,388 B1 19 20 particularly useful procedures, the composition is sheared by sheets being bonded in the molten state. The surfaces of the mechanical methods in which the intercalate, with or with sheets, films and panels, including those in the embossed out the carrier or Solvent, is sheared by use of mechanical form, can be improved or finished by conventional methods, means, Such as Stirrers, Banbury(E) type mixers, Brabender(R) for example by lacquering or by the application of protective type mixers, long continuous mixers, and extruders. Another films. procedure employs thermal Shock in which shearing is MXD6 nylon matrix polymer/intercalate composite mate achieved by alternatively raising or lowering the tempera rials are especially useful for fabrication of extruded films ture of the composition causing thermal expansions and and film laminates, as for example, films for use in food resulting in internal Stresses which cause the Shear. In Still packaging that have permeabilities less than 0.1 cc, per 100 other procedures, Shear is achieved by Sudden preSSure in test area, per day, per mil thickness, and as low as 0.001 changes in pressure alteration methods; by ultrasonic tech cc per 100 in, per day, per mil thickness. Such films can be niques in which cavitation or resonant Vibrations which fabricated using conventional film extrusion techniques. The cause portions of the composition to vibrate or to be excited films are preferably from about 10 to about 100 microns, at different phases and thus Subjected to Shear. These meth more preferably from about 20 to about 100 microns and ods of Shearing are merely representative of useful methods, 15 most preferably from about 25 to about 75 microns in and any method known in the art for Shearing intercalates thickness. may be used. The homogeneously distributed intercalate, and/or exfo Mechanical Shearing methods may be employed Such as liated platelets thereof, which has been onium ion and by extrusion, injection molding machines, Banbury(E) type MXD6 nylon intercalated in accordance with the present mixers, Brabender(R) type mixers and the like. Shearing also invention, and an MXD6 nylon matrix polymer that form the can be achieved by introducing the layered material and preferred embodiment of the nanocomposite compositions intercalant monomer at one end of an extruder (single or of the present invention are formed into a film by Suitable double Screw) and receiving the Sheared material at the other film-forming methods. Typically, the composition is melted end of the extruder. The temperature of the layered material/ and forced through a film forming die after MXD6 nylon intercalant monomer composition, the length of the extruder, 25 intercalation and compounding. The film of the nanocom residence time of the composition in the extruder and the posite may go through Sequential Steps to cause the inter design of the extruder (single Screw, twin screw, number of calate and/or exfoliated platelets thereof to be further ori flights per unit length, channel depth, flight clearance, mix ented So the major planes through the intercalates and/or ing Zone, etc.) are Several variables which control the platelets thereof are Substantially parallel to the major plane amount of Shear to be applied for exfoliation. through the film. One method to accomplish this is to In accordance with an important feature of the present biaxially stretch the film. For example, the film is stretched invention, it has been found that the onium ion-intercalated in the axial or machine direction by tension rollers pulling clay can be intercalated with the MXD6 nylon polymer by the film as it is extruded from the die. The film is simulta direct compounding, i.e., by mixing the onium ion neously stretched in the transverse direction by clamping the intercalated layered material, e.g., Smectite clay, directly 35 edges of the film and drawing them apart. Alternatively, the with the MXD6 nylon in an extruder to make the onium film is Stretched in the transverse direction by using a tubular ion/MXD6 nylon intercalated clay without significant exfo film die and blowing the film up as it passes from the tubular liation of the clay platelets. The intercalate-filled MXD6 film die. The films may exhibit one or more of the following nylon matrix polymer extrudes into a homogeneous trans benefits in addition to decreased permeability to gases, parent film with excellent dispersion of the intercalate, and 40 particularly O: increased modulus, increased wet strength; exceptional gas (O) impermeability. The intercalate dis increased dimensional Stability; and decreased moisture persed within the MXD6 nylon is a combination of exfoli adsorption. ated platelets and multi-layer tactoids dispersed in the The following examples are presented to more particu MXD6 nylon matrix polymer. The tactoids have the thick larly illustrate the invention and are not to be construed as neSS of at least two individual platelet layers plus one to five 45 limiting the Scope of the invention. monolayer thicknesses of intercalated MXD6 nylon polymer, and include Small multiples or aggregates of EXAMPLE 1. platelets, in a coplanar aggregate, having the onium ions A sodium bentonite clay (PGW) was slurried in water to bonded or complexed or ion-exchanged to the platelet provide about 10% by weight clay/90% by weight water, and Surface(s). 50 two different onium ion spacing/coupling agents were inter Molding compositions comprising an MXD6 nylon calated into different PGW clay samples by adding the matrix polymer containing a desied loading of the onium onium ion-containing agent to the slurry water in an amount ion/MXD6 nylon intercalates of the present invention, and/ of 100% by weight, based on the weight of the clay. Onium or individual platelets obtained from exfoliation of the ion intercalation was evidenced by the platelet spacing intercalates manufactured according to the present 55 increasing to about 18 A. One onium compound (octadecyl invention, are outstandingly Suitable for the production of amine or ODA) was obtained by dissolving octadecyl sheets, films and panels having valuable properties. Such ammonium chloride in the slurry water. The Second onium sheets, films and panels may be shaped by conventional ion compound (Stepan) was obtained from Stepan processes Such as Vacuum processing or by hot pressing to Chemical, and was n-alkyl dimethylbenzyl amine obtained form useful objects. The sheets and panels according to the 60 by dissolving n-alkyl dimethylbenzyl ammonium chloride invention are also Suitable as coating materials for other (BTC 50 USP) in the clay slurry water, wherein the alkyl materials comprising, for example, Wood, glass, ceramic, was a Cs+ mixed Cs, C2, C1, Co alkyl. The Onium metal or other plastics, and outstanding Strengths can be ion-intercalated clay was dried in an oven overnight to 1% achieved using conventional adhesion promoters, for by weight moisture or less) and then directly compounded example, those based on Vinyl resins. The sheets, films and 65 with MXD6 nylon in amounts of 2.5% by weight onium panels can be laminated to other plastic films, sheets or ion-MXD6 nylon co-intercalated clay and 5.0% by weight panels and this is preferably effected by co-extrusion, the onium ion-MXD6 nylon co-intercalated clay in 97.5% by US 6,232,388 B1 21 22 weight and 95% by weight MXD6 nylon, respectively, in an EXAMPLE 2 extruder. In the extruder, the MXD6 nylon was intercalated into the onium ion-intercalated clay, as evidenced by an A sodium bentonite clay (PGW) was slurried in 1900 increase in d-spacing from about 18 A to about 28 A. For grams of water to provide about 5% by weight clay/95% by comparison purposes, the same octadecyl amine weight water, and an octadecylamine (ODA) onium ion spacing/coupling agent was intercalated into PGW clay intercalated clay was compounded and co-intercalated with Samples by adding the onium ion to the Slurry water in an 3.5% by weight nylon 6. The co-intercalated clay (onium amount of 100% by weight, based on the weight of the clay. ions and MXD6 nylon or onium ions and nylon 6) was then Onium ion intercalation was evidenced by the interlaminar tested for oxygen permeability, with the results shown in platelet spacing increasing from about 9 A to about 12 A. Table 1. The onium compound (octadecyl- amine or ODA) was obtained by dissolving octadecyl ammonium chloride in the TABLE 1. slurry water. The ODA-intercalated clay was dried in an NYLON 6 AND NYLON-MXD6 TEST oven overnight to 1% by weight moisture or less) and then CONDITIONS AND RESULTS SUMMARY directly compounded with MXD6 nylon in amounts of 2.5% 15 by weight onium ion-intercalated clay and 5.0% by weight Conditions For Oxygen Permeability Testing onium ion-intercalated clay in 97.5% by weight and 95% by Instrumentation: Modern Controls, Inc. weight MXD6 nylon, respectively, in an extruder. In the Ox-Tran 2/20 ML and SL modules Film Preparation: Three days conditioning at extruder, the MXD6 nylon was intercalated into the onium standard lab atmosphere after ion-intercalated clay, as evidenced by an increase in platelet extrusion spacing from about 12 A to about 26 A or more. For Film Thickness: 2-5 mills comparison purposes, a film of MXD6 nylon, without the Film Test Area: 100 sq. in. octadecylamine-intercalated clay, was also cast into a film. Test Humidity: 65% Test Temperature: 23° C. The three films were formed and tested for oxygen perme Condition Hours: 2 25 ability. The first film (FIG. 1) was prepared from MXD6 Zero Time: 40 hours nylon alone in a thickness of 2.7 mils. The second film (FIG. Test Time: 120 hours Test Gas: 100% Oxygen (flow = 20 ml/min) 2) included 2.5% by weight of the ODA/MXD6-intercalate Carrier Gas: 90% Nitrogen/10% Hydrogen and was formed to a thickness of 2.7 mils. The third film (flow = 10 ml/min) (FIG. 3) included 5.0% by weight of the ODA/MXD6 Results Summary (Value at 120 Hours) co-intercalate and was formed to a thickness of 4.1 mils. The Nylon-MXD6 non-oriented: 0.443 cc/100 in-day-mil data of Tables 6-8 and FIGS. 1-3 are total Opermeability 2.5% PGWODA-MXD6 0.012 cc/100 in -day-mil in cc/100 in/day and should be multiplied by thickness (in (direct compounding): mils) to obtain O. permeability per mill thickness. The 5.0% PGWODA-MXD6 <0.001 cc/100 in-day-mil MXD6 films containing the co-intercalated clay (ODA (direct compounding): onium ions and MXD6 nylon) and the pure MXD6 nylon 2.5% PGWBTC-5O-MXD6 0.033 cc/100 in -day-mil 35 (direct compounding): film were then tested for oxygen permeability, with the 5.0% PGWBTC-5O-MXD6 0.066 cc/100 in-day-mil results shown in the following Tables 2-4, corresponding to (direct compounding): 2.90 cc/100 in-day-mil FIGS. 1-3, respectively. Nylon 6 non-oriented: 2.5% PGW/ODA-Nylon 6 1.13 cc/100 in-day-mil AS shown in FIGS. 2 and 3, gas barrier properties are (direct compounding): 40 unexpectedly Superior for the MXD6 intercalate in an MXD6 nylon matrix polymer in comparison to the MXD6 film without the MXD6 intercalate.

TABLE 2 Mocon OX-TRAN 2/20 oxygen transmission Values are expressed in cc/100 in day." Time Time Time Time Time (hours) Value (hours) Value (hours) Value (hours) Value (hours) Value Walt 43:OOO22884 86:OO .O24.942 124:O1 .15961.9 167:O1 .162284 Zero 45:OO.O24084 88:OO .O2S123 126:O1 .15936.1. 169.01 .1621.87 126226 47:OO .024516 90:OO .O25174 128:O1 .157961 172:01 .162323 .044 284 49:OO.O25084 90:00 W Gas 30:O1 .157516 174:O1 .162703 O19723 51:OOO25735 90:00 Cond 33:O1 .158523 176:01 .1621.68 O13452 53:OO.O24774 92:00 Test 35:O1 .15891O 178:01 .163735 O1283.9 56:OO ..O22110 94:01.152097 137:O1 .159768 18OO1 .164323 O14 58:OO.O23781 96:01.156O13 139:01 .161097 182:01 .164529 O17877 60:OO ..O24174 98:01.156903 141:O1 .161806 1.85:O1 .16471O O2O161 62:OO .024639 100:01.156994. 143:O1 .160606 187:01 .164OO6 O2O877 64:OOO24.981 1O2:01.157394 146:01 .160916 189:O1 165213 413 66:OO .O25116 104:01.157729 148:01 .160465 191:01 .163897 6OO 69:OO ..O23335 107:01.156123 150:01 .16O465 193:01 .164665 142 71:OO .024903 109:01.156484 152:01 .161097 195O1 .164032 O2O890 73:OOO25587 111:01.157265 154:O1 .161497 198:O1 165026 O23297 75:OO .026161 113:01.157677 156:01 .162155 2OOO1 .164097 O23942 77:OOO25355 115:01.158987 159:O1 .161845 2O2:01 .165594 O24439 79:OO.O246OO 117:01.16O4(OO 161:O1 161690 204:O1 166826 O24826 82:OO.O22935 120:01.159245 163:01 .162826 206:01 .167703 O24613 84:OO.O2471O 122:01.159329 165:O1 .162665 208:01 .167806

US 6,232,388 B1 25 26

TABLE 4 Mocon OX-TRAN 2/20 oxygen transmission Values are expressed in cc/100 in day." Time Time Time Time Time (hours) Value (hours) Value (hours) Value (hours) Value (hours) Value O:OO Wait 43:OO ..O18484 86:OO ..O2O632 124:O -O.OO25 167:01 -O.OO3O 1:58 Zero 45:OO ..O1815S 88:OO ..O2O581. 126:O -O.OO37 169:01 -O.OO27 4:00 .115284 47:OO ..O1871O 90:OO ..O2O439 128:O -OOO44 172:01 -OOO27 6:OO .041161. 49:OO ..O19490 90:OO W Gas 3O:O -OOO49 174:O1 -OOO19 8:OO ..O19129 51:OO ..O2O284 90:OO Cond 33:O -OOO33 176:01 -OOO3O 10:00 O13484 53:OO ..O186OO 91:59 Test 35:O -OOO3O 178:01 -OOO16 12:OO ..O13026 56:OO ..O18213 94:01 -0.0015 37:O -OOO24 180:01 -OOO17 14:OO ..O13819 58:OO ..O186OO 96.O1 -O.OO29 39:O -OOO2O 182:01 -OOO19 17:OO O15265 60:OO .O19303 98:01 -O.OO3 41:O -0.0012 185:01 -0.0020 19:OO O15994 62:OO .O19729 100:01 -O.OO38 43:O -OOO18, 187:01 -OOO26 21:OO O15987 64:OO .O1991O 102:01 -O.OO38 46:O -0.0025 189:01 -0.0018 23:OO ..O16174 66:OO .O2O090 104:01 -O.OO44 48:O -OOO23 191:01 -OOO31 25:OO ..O16135 69:OO .O2O290 107:01 -O.OO35 50:O -OOO23 193:01 -OOO23 27:OO O15568 70:OO O19955 109:01 -O.OO33 52:O -O.OO27 195:01 -O.OO22 3O:OO ..O16619 73:OO ..O212O6 111:01 -O.OO33 54:O -OOO24 198:01 -OOO18 32:OO O17729 75:OO ..O21645 113:OO-O.OO3 56:O -OOO22 200:01 -0.0024 34:OO ..O17884 77:OO O19690 115:OO-O.OO32 59:O -OOO24 202:01 -OOO12 36:OO ..O18252 79:OO O19277 117:01 -O.OO23 61:0 -OOO26 204:01 -OOO12 38:OO ..O18465 82:OO ..O2O019 12O:O1 -O.OO3O 63:O -OOO14 206:01 -O.OO11 40:OO ..O18058 84:OO ..O2O6(OO 122:01 -O.OO2 65:O -OOO22 208:01 -OOO12 211:01 -O.OO2O 245:01 -0.0020 280:01 -O.OO15 312:32 -OOO48 346.32 -OOO12 213:01 -0.0015 247:01 -O.OO24 282:01 -O.OO16 314:32 -0.0046 348:32 -0.0005 215:01 -0.0024 250:01 -O.OO17 284:01 -O.OO2O 316:32 -O.OO58 351:32 -O.OO23 217:01 -0.0017 252:01 -0.0014 286:01 -O.OO18 318:32 -O.OO46 353:32 -O.OO27 219:01 -OOO16 254:01 -0.0012 289:01 -0.0022 32O:32 -O.OO4O 355:32 -OOOO6 221:01 -OOO23 256:01 -0.0014 291:01 -O.OO23 322:32 -O.OO38 357:32 -O.OO17 224:01 -0.0019 258:01 -0.0016 293:01 -O.OO14 325:32 -0.0016 359:32 -0.0026 226:01 -OOO16 260:01 -O.OO17 295:01 -O.OO12 327:32 -OOO19 361:32 -OOO31 228:01 -O.OO15 263:01 -O.OO22 297:01 -O.OOO3 329:32 -0.0015 364:32 -0.0023 230:01 -OOO16 265:01 -O.OO2O 299:01 -O.OOO3 331:32 -OOO17 366:32 -OOOO6 232:01 -OOO16 267:01 -O.OO23 3O2:01 -O.OO18 333:32 -OOOO4 368:32 -OOOO9 234:01 -O.O110 269:01 -O.OO29 3O4:01 -O.OO23 335:32 -O.OO34 370:32 -O.OO11 237:01 -0.0024 271:01 -O.OO36 306:01 -OOOO6 338:32 -O.OO24 372:32 -O.OO15 239:01 -0.0022 273:01 -O.OO2O 3O8:01 -O.OO13 340:32 -OOO28 374:32 -OOO2O 241:01 -0.0020 276:01 -O.OO18 310:01 -O.OO10 342:32 -O.OO21 377:32 -O.OO22 243:01 -0.0015 278:01 -O.OO14 3.11:12 -O.OO28 344:32 -0.0014 * All values are compensated to a barometric pressure of 760 mmHg.

What is claimed is: 40 7. A nanocomposite composition comprising a matrix 1. A nanocomposite composition comprising about 0.05 polymer in an amount of about 40% to about 99.95% by weight percent to about 40 weight percent of a layered weight, and about 0.05% to about 60% by weight of an Silicate material intercalated with an onium ion spacing intercalated phyllosilicate material formed by contacting a agent and about 60 weight percent to about 99.95 weight phyllosilicate with intercalant onium ions to form an inter percent of a matrix polymer comprising the reaction product 45 calating composition, having a molar ratio of onium ions of meta-xylylene diamine and a dicarboxylic acid, wherein :phyllosilicate interlayer exchangeable cations of at least the intercalated layered Silicate material is dispersed uni about 0.25:1 to achieve sorption of the onium ions between formly throughout the matrix polymer. adjacent Spaced layers of the phylloSilicate to expand the 2. A nanocomposite composition in accordance with spacing between a predominance of the adjacent phyllosili claim 1, wherein the matrix polymer is co-intercalated into 50 cate platelets at least about 3 A, when measured after the layered Silicate material. Sorption of the onium ions, and a Second intercalant disposed 3. A nanocomposite composition in accordance with between adjacent spaced layers of the phyllosilicate claim 2, wherein the matrix polymer is co-intercalated into material, Said Second intercalant comprising a nylon poly the layered Silicate material while dispersing the layered mer formed by polymerizing a reaction product of meta material throughout the matrix polymer. 55 Xylylene diamine and a dicarboxylic acid. 8. A composition in accordance with claim 7, wherein the 4. A nanocomposite composition in accordance with intercalated phylloSilicate is exfoliated into a predominance claim 2, wherein the matrix polymer is co-intercalated into of individual platelets. the layered Silicate material prior to dispersing the layered 9. A composition in accordance with claim 7, wherein the Silicate material throughout the matrix polymer. dicarboxylic acid is adipic acid. 5. A nanocomposite composition in accordance with 60 10. A composition in accordance with claim 9, wherein claim 1, wherein the matrix polymer is a polymer or the Second intercalant is intercalated into the phylloSilicate oligomer of the reaction product of meta-xylylene diamine from an intercalating composition containing Said Second and adipic acid. intercalant in a concentration of at least about 5% by weight, 6. A nanocomposite composition in accordance with based on the dry weight of the phyllosilicate in the interca claim 1, wherein the onium ions include at least one moiety 65 lating composition. covalently bonded to a positively charged nitrogen atom that 11. A composition in accordance with claim 9, wherein has a length of at least Six carbon atoms. the concentration of the Second intercalant in Said interca US 6,232,388 B1 27 28 lating composition is at least about 20% by weight, based on formed by intercalating an onium ion between layers of a the dry weight of the phylloSilicate in the intercalating layered Silicate material, wherein Said matrix polymer is a composition. polymer or oligomer formed from the reaction product of a 12. A composition in accordance with claim 11, wherein meta-xylylene diamine and a dicarboxylic acid, Such that a the concentration of the Second intercalant in Said interca portion of the matrix polymer is co-intercalated between the lating composition is at least about 30% by weight, based on Silicate layers of the layered material. the dry weight of the phylloSilicate in the intercalating 26. A method in accordance with claim 25, wherein the composition. matrix polymer is an oxygen Scavenger. 13. A composition in accordance with claim 12, wherein 27. A method in accordance with claim 25, wherein the the concentration of the Second intercalant in Said interca matrix polymer is co-intercalated into the layered Silicate lating composition in the range of about 50% to about 80% material while dispersing the layered material throughout by weight, based on the dry weight of the phyllosilicate in the matrix polymer. the intercalating compound. 28. A method in accordance with claim 25, wherein the 14. A composition in accordance with claim 12, wherein matrix polymer is co-intercalated into the layered Silicate the concentration of the Second intercalant in Said interca 15 material prior to dispersing the layered Silicate material lating composition in the range of about 50% to about 200% throughout the matrix polymer. by weight, based on the dry weight of the phyllosilicate in 29. A method in accordance with claim 25, wherein the the intercalating composition. matrix polymer is a polymer or oligomer of the reaction 15. A composition in accordance with claim 7, wherein product of meta-xylylene diamine and adipic acid. the molar ratio of intercalantonium ions.phyllosilicate inter 30. A method in accordance with claim 25, wherein the layer eXchangeable cations is at least 0.5:1. onium ions include at least one moiety covalently bonded to 16. A composition in accordance with claim 7, wherein a positively nitrogen atom that has a length of at least Six the molar ratio of intercalantonium ions.phyllosilicate inter carbon atoms. layer eXchangeable cations is at least 1:1. 31. A method of manufacturing a composite material 17. A composition in accordance with claim 7, wherein 25 containing about 10% to about 99.95% by weight of a matrix the onium ions are multi-onium ion compounds that include polymer comprising a polymer or oligomer of a reaction at least two primary, Secondary, tertiary or quaternary product of meta-xylylene diamine and a dicarboxylic acid, ammonium, phosphonium, Sulfonium, or Oxonium ions. and about 0.05% to about 60% by weight of an intercalated 18. A composition in accordance with claim 7, wherein phyllosilicate material, Said intercalated phylloSilicate hav the matrix polymer is MXD6 nylon. ing an intercalant onium ion spacing agent intercalated 19. A nanocomposite concentrate composition comprising between and bonded, by ion-exchange, to an inner Surface of about 10% by weight to about 90% by weight of a layered the phylloSilicate platelets, comprising: material intercalated with a polymer or oligomer of the contacting the phylloSilicate with Said intercalant onium reaction product of meta-xylylene diamine and a dicarboxy ion spacing agent, to achieve intercalation of Said lic acid and about 10 weight percent to about 90 weight 35 intercalant onium ion spacing agent between Said adja percent of a matrix polymer comprising the reaction product cent phylloSilicate platelets in an amount Sufficient to of meta-xylylene diamine and a dicarboxylic acid, wherein Space Said adjacent phyllosilicate platelets a distance of the intercalated layered Silicate material is dispersed uni at least about 3 A; and formly throughout the matrix polymer. dispersing the intercalate throughout Said matrix polymer 20. A nanocomposite composition in accordance with 40 to achieve intercalation of a portion of the matrix claim 19, wherein the matrix polymer is intercalated into the polymer between the phyllosilicate platelets. layered Silicate material. 32. The method of claim 31, wherein said phyllosilicate is 21. A nanocomposite composition in accordance with contacted with Said intercalantonium ion Spacing agent, Said claim 20, wherein the matrix polymer is intercalated into the phyllosilicate, and a nylon oligomer or polymer intercalant layered Silicate material while dispersing the layered mate 45 formed from the reaction product of meta-xylylene diamine rial throughout the matrix polymer. and a dicarboxylic acid, wherein the concentration of the 22. A nanocomposite composition in accordance with onium ion Spacing agent is in a molar ratio of onium claim 20, wherein the matrix polymer is intercalated into the ions: phylloSilicate interlayer eXchangeable cations of at layered Silicate material prior to dispersing the layered least 0.25:1. Silicate material throughout the matrix polymer. 50 33. The method of claim 32, wherein said phyllosilicate is 23. A nanocomposite composition in accordance with contacted with Said intercalantonium ion Spacing agent, Said claim 19, wherein both the matrix polymer and the polymer phyllosilicate, and a nylon oligomer or polymer intercalant intercalated into the layered material are a polymer or formed from the reaction product of meta-xylylene diamine oligomer of the reaction product of meta-xylylene diamine and a dicarboxylic acid, wherein the concentration of the and adipic acid. 55 onium ion Spacing agent is in a molar ratio of onium 24. A nanocomposite composition in accordance with ions: phylloSilicate interlayer eXchangeable cations of at claim 19, wherein prior to intercalating the layered material least 0.5:1. with the polymer of meta-xylylene diamine and a dicarboxy 34. The method of claim 33, wherein said phyllosilicate is lic acid, the layered material is first intercalated with onium contacted with Said intercalantonium ion Spacing agent, Said ions that include at least one moiety covalently bonded to a 60 phyllosilicate, and a nylon oligomer or polymer intercalant positively charged nitrogen atom that has a length of at least formed from the reaction product of meta-xylylene diamine Six carbon atoms. and a dicarboxylic acid, wherein the concentration of the 25. A method of decreasing oxygen permeability of a film onium ion Spacing agent is in a molar ratio of onium or sheet of a matrix polymer comprising dispersing through ions: phylloSilicate interlayer eXchangeable cations of at out said matrix polymer, in an amount of about 0.05% by 65 least 1:1. weight to about 30% by weight, based on the total weight of 35. A method of manufacturing a composite material the film or sheet material and the intercalate, an intercalate containing about 40% to about 99.95% by weight of a matrix US 6,232,388 B1 29 30 thermoplastic or thermosetting polymer, and about 0.05% to and dicarboxylic acid reaction product while in contact about 60% by weight of an intercalated phyllosilicate with the intercalated phylloSilicate and to co-intercalate material, Said intercalated phyllosilicate having an intercal the resulting oligomer or polymer between adjacent ant onium ion Spacing/coupling agent intercalated between platelets of the phyllosilicate material, wherein the adjacent phyllosilicate platelets comprising: intercalate reactants are combined in amounts Such that contacting the phylloSilicate with an intercalating com the resulting composite material contains 40% to position including an intercalant onium ion spacing/ 99.95% oligomer or polymer and 0.05% to 60% inter coupling agent in a molar ratio of onium ions.phyllo calated phyllosilicate. Silicate interlayer cations of at least 0.25:1, and a nylon 44. In a method of preventing the passage of oxygen to a oligomer or polymer intercalant formed from the reac material to be protected from oxygen contact comprising tion product of meta-xylylene diamine and a dicarboxy disposing a film or sheet of material between an oxygen lic acid, to achieve intercalation of Said intercalant Source and the material to be protected, the improvement onium ion spacing/coupling agent and Said nylon inter comprising the film or sheet material, Said film or sheet calant between Said adjacent phyllosilicate platelets in material comprising a MXD6 nylon matrix polymer con an amount Sufficient to Space Said adjacent phyllosili taining an intercalated phylloSilicate containing a MXD6 cate platelets at least an additional 3 A; 15 intercalant intercalated between adjacent phyllosilicate combining the intercalated phyllosilicate with Said ther platelets in an amount Sufficient to reduce the amount of moplastic or thermosetting matrix polymer, and heating oxygen contacting the material to be protected. the matrix polymer sufficiently to provide for flow of 45. In the method of claim 44, wherein the amount of Said matrix polymer; and intercalate combined with the MXD6 nylon matrix polymer is in the range of about 2% to about 10% by weight dispersing Said intercalated phylloSilicate throughout Said intercalate, based on the total weight of the film or sheet matrix polymer. material. 36. A method in accordance with claim 35, wherein the 46. In the method of claim 44, wherein the amount of intercalating composition includes about 10% to about intercalate is in the range of about 3% to about 6% by 200% by weight of said nylon intercalant, based on the dry 25 weight. weight of phylloSilicate contacted by Said intercalating com 47. In the method of claim 44, wherein the MXD6 position. intercalant is an oligomer formed from the reaction product 37. A method in accordance with claim 35, wherein the of meta-xylylene diamine and adipic acid. amount of onium ion spacing/coupling agent intercalated 48. In the method of claim 47, wherein the amount of into the phyllosilicate material is in a molar ratio of at least intercalate is at least about 4% by weight of the film or sheet 0.5:1, onium ions:exchangeable cations in the interlayer material. Spaces of the phyllosilicate material. 49. In the method of claim 48, wherein the amount of 38. A method in accordance with claim 37, wherein the intercalate is at least about 5% by weight of the film or sheet amount of intercalant onium ion spacing/coupling agent material. intercalated into the phylloSilicate material is in a molar ratio 50. An intercalate formed by contacting a layered Silicate of at least 1:1, onium ions:exchangeable cations in the 35 material with an onium ion spacing/coupling agent interlayer Spaces of the phylloSilicate material. intercalant, Said intercalate having a molar ratio of intercal 39. A method in accordance with claim 38, wherein the ant onium ion spacing/coupling agent cation to interlayer molar ratio of intercalated onium ion spacing/coupling agent cations of at least about 0.25:1, to achieve Sorption and to interlayer phylloSilicate cations is from about 1:1 to about ion-exchange of the onium ion spacing/coupling agent with 1:5. 40 interlayer eXchangeable cations of Said layered Silicate mate 40. A method in accordance with claim 35, wherein the rial to expand the spacing between a predominance of the weight ratio of the nylon intercalant to phylloSilicate adjacent platelets of Said layered material at least about 3 A, material, dry basis, is from about 20 grams of nylon inter when measured after ion-exchange with the onium ion calant per 100 grams of phyllosilicate material to about 200 Spacing/coupling agent, and a nylon oligomer or polymer grams of nylon intercalant per 100 grams of phylloSilicate 45 Second intercalant comprising the reaction product of meta material. Xylylene diainine and a dicarboxylic acid disposed between 41. A method in accordance with claim 35, wherein the nylon oligomer or polymer is intercalated into the phyllo adjacent layers of Said layered Silicate material, to expand Silicate by melting the nylon oligomer or polymer and the spacing between a predominance of the adjacent plate dispersing the phyllosilicate throughout the nylon melt. lets an additional at least 3 A. 50 51. An intercalate in accordance with claim 50, wherein 42. A method in accordance with claim 41, wherein the the layered Silicate material is contacted with Said onium ion mixing is accomplished in an extruder. Spacing/coupling agent in an intercalant composition com 43. A method of manufacturing a composite material prising Said layered Silicate material, Said onium ion containing about 40% to about 99.95% by weight of an spacing/coupling agent and a carrier for Said onium ion oligomer or polymer formed from the reaction product of spacing/coupling agent and wherein the concentration of the meta-xylylene diamine and a dicarboxylic acid, and about 55 onium ion Spacing/coupling agent in Said intercalating com 0.05% to about 60% by weight of an intercalated phyllo position is at least about 2% by weight, based on the dry Silicate material comprising intercalating the phylloSilicate weight of the layered Silicate material. material with an onium ion spacing agent by contacting the 52. A method of intercalating a phyllosilicate with both an phyllosilicate with onium ions in a molar ratio of onium onium ion and an MXD6 nylon polymer comprising Slur ions: phylloSilicate interlayer eXchangeable cations of at 60 rying the phyllosilicate in water to form a clay/water slurry; least 0.25:1; adding the onium ion to the phyllosilicate/water Slurry; forming a mixture of the intercalated phylloSilicate mate Separating the onium ion-treated clay from the water, drying rial with meta-xylylene diamine and a dicarboxylic the phylloSilicate; and then mixing the onium ion-treated acid; and phyllosilicate with MXD6 nylon to intercalate the MXD6 Subjecting the mixture to conditions Sufficient to react and 65 nylon between adjacent platelets of the phylloSilicate. polymerize the meta-xylylene diamine with the dicar boxylic acid, to polymerize the meta-xylylene diamine k k k k k UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION

PATENT NO. : 6.232,388 B1 Page 1 of 1 DATED : May 15, 2001 INVENTOR(S) : Tie Lan et al.

It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

Column 30 Line 46, please change "dianine" to -- diamine --.

Signed and Sealed this Third Day of December, 2002

JAMES E ROGAN Director of the United States Patent and Trademark Office