EP1200515A1 - Polyamidzusammensetzung enthaltend schichtton welcher mit einer alkoxylierten oniumverbindung modifiziert ist - Google Patents

Polyamidzusammensetzung enthaltend schichtton welcher mit einer alkoxylierten oniumverbindung modifiziert ist

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Publication number
EP1200515A1
EP1200515A1 EP00942840A EP00942840A EP1200515A1 EP 1200515 A1 EP1200515 A1 EP 1200515A1 EP 00942840 A EP00942840 A EP 00942840A EP 00942840 A EP00942840 A EP 00942840A EP 1200515 A1 EP1200515 A1 EP 1200515A1
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EP
European Patent Office
Prior art keywords
alkoxylated
ammonium cation
composition
acid
layered clay
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00942840A
Other languages
English (en)
French (fr)
Inventor
Shriram Bagrodia
John Walker Gilmer
James Christopher Matayabas, Jr.
Jeffrey Todd Owens
Linda Gale Bernard
Sam Richard Turner
Tie Lan
Vasiliki Psihogios
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South Carolina Research Foundation SCRF
Original Assignee
Eastman Chemical Co
South Carolina Research Foundation SCRF
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/452,826 external-priority patent/US6417262B1/en
Application filed by Eastman Chemical Co, South Carolina Research Foundation SCRF filed Critical Eastman Chemical Co
Priority claimed from PCT/US2000/016483 external-priority patent/WO2001004197A1/en
Publication of EP1200515A1 publication Critical patent/EP1200515A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • This invention relates generally to a polymer-clay composition having improved gas permeability comprising a clay material and at least one organic cation. More particularly, this invention relates to a polyamide composition comprising layered clay material modified with an alkoxylated onium compound. This invention further relates to articles produced from the composition, and a process for preparing the composition. Background of the Invention
  • Polymer-platelet particle composites have received much attention lately due to their potential to improve polymer properties, including gas barrier, heat deflection temperature, and modulus.
  • U.S. Pat. No. 4,739,007 discloses composite materials comprising a polyamide matrix and a well dispersed, layered silicate material that is incorporated during polymerization and imparts high mechanical strength and excellent high temperature properties.
  • U.S. Pat. No. 5,385,776 discloses composite materials comprising a Nylon-6 matrix and a minor amount of a layered silicate material that is incorporated during melt extrusion and imparts rapid nucleation of the polyamide into the gamma crystal structure thereby improving modulus and resistance to plasticization by water.
  • U.S. Pat. No. 4,810,734 discloses nylon composites comprising a layered silicate material that has been treated with certain organic ammonium compounds and incorporated by synthesis using a dispersing aid.
  • PCT application WO 93/04117 discloses composite materials comprising a polyamide matrix and a layered silicate material that has been modified with certain primary or secondary organic ammonium compounds incorporated during melt extrusion and impart improved modulus to the polymer composite.
  • PCT application WO 93/11190 discloses Nylon composites comprising a layered silicate material that may optionally contain certain organic ammonium compounds, WHICH ARE TREATED WITH certain silane compounds and incorporated by melt blending. Journal of Applied Polymer Science. Vol. 71 (1999), pg. 1139-1146, discloses the rapid crystallization of composite materials comprising a polyethylene terephthalate (“PET”) matrix and an undisclosed clay material.
  • PET polyethylene terephthalate
  • PCT application WO 98/29499 discloses high molecular weight polyester- platelet particle composites prepared by solid state polymerization of precursor composites prepared by incorporation of treated layered silicate materials by synthesis and by melt compounding. The use of alkoxylated ammonium compounds to pretreat the layered silicate is specifically disclosed.
  • PCT application WO 99/02593 discloses polyester composites comprising layered silicate materials that are treated with at least one polyalkoxylated ammonium salt comprising alkoxy ligands with greater than 5 alkyl oxide repeat units.
  • Amorphous polyamides have been prepared and proposed as polymers for food packaging, offering improved resistance to whitening or hazing upon exposure to moisture, as described in U.S. Patent Nos. 5,028,462 and 4,983,719, and offering improved physical properties, as described in U.S. Patent No. 4,018,746.
  • these patents do not disclose or suggest incorporation of a clay material into such amorphous polyamide to improve the barrier propertis of the polyamide or an article made therefrom. Further, these patents do not disclose or suggest that haze would be reduced in a composite comprising a clay material and an amorphous polyamide.
  • polymer-platelet particle composites of both polyethylene terephthalate (“PET”) and polyamides often exhibit rapid crystallization, which has been attributed to nucleation of the polymer matrix by the platelet particles.
  • Clay particles in a nylon-6 nanocomposite for example, induce crystallization, as described in U.S. Pat. No. 5,385,776.
  • This can be an advantage for applications involving opaque, crystalline molded parts, as well as for imparting improved heat resistance and modulus to the parts.
  • opaque crystalline composites are the nylon composites disclosed in U.S. Pat. Nos. 5,385,776 and 4,739,007, and the PET composites discussed in Journal of Applied Polymer Science. Vol. 71 (1999), pg. 1139- 1146.
  • rapid crystallization of polymer-clay composites is not always desirable, especially applications including, but not limited to, profile extrusion, extrusion blow molding, stretch blow molding, film extrusion, and blown film, and other applications where optical clarity of the composite is desired, and especially in two step molding applications.
  • the rapid crystallization of prior art polymer-clay composites makes it difficult, if not impossible, to obtain clear multilayer preforms and/or blow molded containers and bottles, wherein the ability to further process an initially formed article is important. Rapid crystallization greatly reduces the available processing window when prior art polymer-clay composites are employed in conjunction with PET in the molding of clear plastic bottles.
  • Multilayer materials for packaging are known for film, bottles, and other containers.
  • this invention relates to composite compositions comprising polyamide polymers or copolymers, and certain layered clay materials, having alkoxylated "onium" cations associated therewith.
  • this invention relates to processes for preparing the compositions, involving the steps of treating a layered clay material with at least one salt having certain alkoxylated "onium", to form a treated layered clay material, then mixing the treated layered clay material with a polymer composition comprising at least one polyamide polymer or copolymer.
  • Ranges may be expressed herein as from “about” or “approximately” one particular value and/or to “about” or “approximately” another particular value. When such a range is expressed, another embodiment includes from the one particular and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • “Layered clay” or “layered clay material” shall mean any organic or inorganic material or mixtures thereof, such as a smectite clay mineral, which is in the form of a plurality of adjacent, bound layers.
  • the layered clay comprises platelet particles and is typically swellable. Such clays may be naturally occurring or synthetically derived.
  • Plate particles shall mean individual or aggregate unbound layers of the layered clay material. These layers may be in the form of individual platelet particles, ordered or disordered small aggregates of platelet particles (tactoids), and small aggregates of tactoids.
  • Dispersion or “dispersed” is a general term that refers to a variety of levels or degrees of separation of the platelet particles. The higher levels of dispersion include, but are not limited to, “intercalated” and “exfoliated.”
  • Intercalated or “intercalate” shall mean a layered clay material that includes organic cations disposed between adjacent platelet particles or tactoids of the layered material to increase the interlayer spacing between the adjacent platelets and tactoids.
  • Exfoliate or “exfoliated” shall mean platelets dispersed predominantly in an individual state throughout a carrier material, such as a matrix polymer. Typically, “exfoliated” is used to denote the highest degree of separation of platelet particles, as compared to dispersed or intercalated particles.
  • Exfoliation shall mean a process for forming an exfoliate from an intercalated or otherwise less dispersed state of separation.
  • Nanocomposite(s) or “nanocomposite composition(s)” shall mean a polymer or copolymer having dispersed therein a plurality of individual platelet particles obtained from exfoliated, layered clay material.
  • a weight percent of a component is based on the total weight of the formulation or composition in which the component is included.
  • a residue of a chemical species refers to the moiety that is the resulting product of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the moiety is actually obtained from the chemical species or is still identifiable as the starting chemical species.
  • an ethylene glycol residue in a polyester refers to one or more -OCH2CH2O- repeat units in the polyester, regardless of whether ethylene glycol is used to prepare the polyester, and regardless of whether the residue contains hydroxyl groups.
  • the dicarboxylic acids of this invention include, but are not limited to dicarboxylic acids having from 3 to about 40 carbon atoms, and more preferably dicarboxylic acids selected from aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, and/or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
  • the dicarboxylic acid component comprises iminodiacetic acid, oxydiacetic acid, thiodiacetic acid, 1,4- phenylenedioxydiacetic acid, 1,3- phenylenedioxydiacetic acid, etc., or mixtures thereof.
  • Suitable diamine components may vary widely, as is known in the art.
  • the diamine component comprises an aliphatic diamine having about 2 to about 12 carbon atoms.
  • the aliphatic diamines may contain aromatic groups, as long as an alkylene group (e.g., a methylene group) is interposed between an amino group and an aromatic ring.
  • the aliphatic diamines also include cycloaliphatic diamines such as piperazine.
  • Suitable diamine components include 1 ,2-ethylenediamine, 1,3- propylenediamine, 1 ,6-hexamethylenediamine, 1,12-dodecylenediamine, 1,4- cyclohexanebismethylamine, piperazine, -xylylenediamine, w-xylylenediamine, or a mixture thereof.
  • a particularly preferred diamine component is w-xylylenediamine, which is refered to as "MX" herein.
  • Suitable polyamides include partially aromatic polyamides, aliphatic polyamides, wholly aromatic polyamides and/or mixtures thereof.
  • partially aromatic polyamide it is meant that the amide linkage of the partially aromatic polyamide contains at least one aromatic ring and a nonaromatic species.
  • More prefened partially aromatic polyamides include, but are not limited to poly( -xylylene adipamide), poly(hexamethylene isophthalamide-co-terephthalamide), poly(w-xylylene adipamide-co-isophthalamide), and/or a mixture thereof.
  • the most preferred partially aromatic polyamide is poly(w-xylylene adipamide), i.e. "MXD6" which is available from Mitsubishi Gas and Chemical Company, Chiyodaku, Tokyo, Japan.
  • Poly(m- xylylene adipamide) is a preferred polyamide due to its availability, high gas barrier properties, and processabihty in conjunction with PET.
  • MXD6-platelet particle composites exhibit significantly improved oxygen barrier and, therefore, provide multilayer bottles with improved barrier and or permit the preparation of high-barrier multilayer bottles comprising thin layers of the barrier material, thereby reducing raw material costs and improving recyclability.
  • Prefened aliphatic polyamides include, but are not limited to polycapramide (nylon 6), poly-aminoheptanoic acid (nylon 7), poly-aminonanoic acid (nylon 9), polyundecane-amide (nylon 11), polyaurylactam (nylon 12), poly(ethylene-adipamide) (nylon 2,6), poly(tetramethylene-adipamide) (nylon 4,6), poly(hexamethylene- adipamide) (nylon 6,6), poly(hexamethylene-sebacamide) (nylon 6,10), poly(hexamethylene-dodecamide) (nylon 6,12), poly (octamethylene-adip amide) (nylon 8,6), poly(decamethylene-adipamide) (nylon 10,6), poly(dodecamethylene-adipamide) (nylon 12,6) and poly(dodecamethylene-sebacamide) (nylon 12,8).
  • More preferred aliphatic polyamides include, but are not limited to poly(hexamethylene adipamide) and poly(caprolactam). The most preferced aliphatic polyamide is poly(hexamethylene adipamide).
  • the I.V. is typically measured in a mixture of 60 weight % phenol and 40 weight % 1,1,2,2- tetrachloroethane at a concentration of 0.5 g/lOOml (solvent) at 25°C.
  • the oligomeric polyamide prior to melt mixing is preferably from about 0.1 and 0.5 dL/g, and more preferably from 0.3 dL/g to 0.5 dL/g as measured in a mixture of 60 weight percent phenol and 40 weight percent 1,1,2,2-tetrachloroethane at a concentration of 0.5 g/lOOml (solvent) at 25°C.
  • the I.V is preferably from about 0.1 and 0.5 dL/g, and more preferably from 0.3 dL/g to 0.5 dL/g as measured in a mixture of 60 weight percent phenol and 40 weight percent 1,1,2,2-tetrachloroethane at a concentration of 0.5 g/lOOml (solvent) at 25°C.
  • solvent 0.5 g/lOOml
  • Low molecular weight polyamides may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromelhtic dianhydride, or other polyamide forming polyacids and polyamines known in the art, which may improve the processing characteristics of the final polymer blends.
  • trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromelhtic dianhydride, or other polyamide forming polyacids and polyamines known in the art, which may improve the processing characteristics of the final polymer blends.
  • the polymers of the present invention may also include suitable additives normally used in polymers.
  • additives may be employed in conventional amounts and may be added directly to the reaction forming the matrix polymer.
  • Illustrative of such additives known in the art are colorants, pigments, carbon black, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, reheat aids, crystallization aids, acetaldehyde reducing compounds, recycling release aids, oxygen scavengers, plasticizers, nucleators, mold release agents, compatibilizers, processing aids and the like, or their combinations.
  • Preferred "layered clay materials" or “clay materials” employed in the invention include any solid material having at least some inorganic anionic atoms, ions, or chemical groups arranged in generally planar layers in the solid state, wherein the spacing between at least some of the generally planar layers are capable of being increased, swelled, or separated by the insertion of inorganic or organic materials therebetween.
  • silicate shall mean any composition having silicon atoms bound to one or more oxygen atoms to form anionic groups, in combination with one or more additional cations, wherein the cations may be inorganic, metalic, or organic cations.
  • Suitable clays are available from various companies including Nanocor, Inc., Arlington Heights Illinois, Southern Clay Products, Gonzalez Texas, Kunimine Industries, Ltd., Chiyodaku, Tokyo, Japan, and Rheox of Hightown, New York.
  • the most preferred platelet particles are derived from sodium bentonite or sodium montmorillonite.
  • Such clays are readily available in the U.S., and are also sometimes refened to as Wyoming-type bentonite or Wyoming type montmorillonite.
  • Wyoming type montmorillonite and/or Wyoming-type bentonite are naturally occuring layered clay materials comprising large proportions of sodium bentonite or sodium montmorillonite.
  • highly preferred platelet particles for use in the present invention are residues derived from further treatment of any of sodium bentonite, sodium montmorillonite, "Wyoming type” bentonite or “Wyoming type” montmorillonite. It is to be understood that at least some of the sodium cations of a natural or synthetic sodium bentonite or sodium bentonite , a naturally occurring "Wyoming type” bentonite or “Wyoming type” montmorillonite are removed and/or exchanged when treated with salts of the alkoxylated onium cations of the invention.
  • the residues of the treated clays may be referred to, and are defined as a "Wyoming type bentonite", a “Wyoming type montmorillonite", a “sodium bentonite”, or a “sodium montmorillonite”. Residues of such clays need not contain detectible amounts of sodium after the clays have undergone treatment with the alkoxylated onium cation salts of the invention. However, some sodium cations may remain.
  • Preferred clay materials are phyllosilicates of the 2:1 type having a cation exchange capacity of 0.5 to 2.0 meq/g.
  • the most prefened clay materials are smectite clay minerals, particularly bentonite or montmorillonite, more particularly Wyoming- type sodium montmorillonite or Wyoming-type sodium bentonite having a cation exchange capacity from about 0.95 to about 1.25 meq/g.
  • the most prefened layered clay materials are derived from sodium bentonite or sodium montmorillonite.
  • TEM images of polymer-platelet composites show that platelet exist in a variety of forms, including, but not limited to, individual platelets (the exfoliated state), disordered agglomerates of platelets, well ordered or stacked aggregates of platelets (tactoids), swollen aggregates of stacked platelets (intercalated tactoids), and aggregates of tactoids.
  • Organic cations used to intercalate a clay material or a mixture of clay materials of a nanocomposite of this invention are derived from organic cation salts, preferably onium salt compounds.
  • "Onium" salts useful for the nanocomposite and process of this invention may generally be represented by the following formula (I):
  • M is either nitrogen or phosphorous;
  • X " is a halide, hydroxide, or acetate anion, preferably chloride and bromide; and R], R 2 , R 3 , and R are independently organic and/or oligomeric ligands or may be hydrogen.
  • Examples of useful organic ligands include, but are not limited to, linear or branched alkyl groups having 1 to 22 carbon atoms, aralkyl groups which are benzyl and substituted benzyl moieties including fused-ring moieties having linear chains or branches of 1 to 100 carbon atoms in the alkyl portion of the structure, aryl groups such as phenyl and substituted phenyl including fused-ring aromatic substituents, beta, gamma unsaturated groups having six or less carbon atoms, and alkyleneoxide groups having repeating units comprising 2 to 6 carbon atoms.
  • organic cations for this invention include, but are not limited to alkyl ammonium ions such as dodecyl ammonium, octadecyl trimethyl ammonium, bis(2 -hydroxyethyl) octadecyl methyl ammonium, octadecyl benzyl dimethyl ammonium, and the like or mixtures thereof.
  • alkyl ammonium ions such as dodecyl ammonium, octadecyl trimethyl ammonium, bis(2 -hydroxyethyl) octadecyl methyl ammonium, octadecyl benzyl dimethyl ammonium, and the like or mixtures thereof.
  • alkoxylated as used herein is an adjective referring to a chemical compound, ion, or residue having an alkoxyl group or residue, regardless of the method used to prepare the chemical compound, ion, or residue.
  • alkoxylate may also be a verb referring to a process of attaching an alkoxyl group to another chemical compound, ion, or group.
  • alkoxyl refers to a hydrocarbon group or residue of about 1 to 36 carbon atoms having (a) at least one terminal alkoxy group (i.e. -OR), or (b) at least one terminal hydroxyl group (i.e. -OH), bound to any one of the carbon atoms of the hydrocarbon group or residue.
  • An alkoxyl group may be branched or unbranched, saturated or unsaturated. As one of ordinary skill in the art would recognize, an alkoxyl group may or may not have additional heteroatomic substitutent atoms or groups, including oxygen, halides, nitrogen containing groups, amines, sulfur containing groups, and the like.
  • alkoxyl groups include a hydroxymethyl group, a 1- or 2-hydroxyethyl group, a 1-or 2- methoxyethyl group, a 2- ethoxybutyl group, a 4-ethoxybutyl group, a 4-hydroxybutyl group, a poly(ethylene glycol) group, a poly(butyleneglycol) group, and higher branched, straight chain, or cyclic analogs thereof.
  • alkoxylated ammonium cations and/or compounds of the invention have a cation of the structure
  • n is an integer of one or more, x is an integer from 1 to 4, R a is a C)-C 20 carbon-containing residue, R is hydrogen or a C ⁇ -C ⁇ 6 carbon -containing group or residue, and the ((R a -O) Stamm -R b ) groups may be the same or different; and R ⁇ is hydrogen or a C ⁇ -C 0 carbon-containing group or residue, and the R ⁇ groups may be the same or different.
  • Prefened alkoxylated ammonium compounds have at least one hydroxyalkyl group in that at least one R group is hydrogen. Alkoxylated ammonium compounds may be primary, secondary, tertiary, or quaternary, depending on the number of R ⁇ groups that are hydrogen. Prefened alkoxylated ammonium cations are tertiary (i.e. only one of R e may be hydrogen), or quartenary (i.e. none of the R ⁇ groups is hydrogen).
  • Electrically neutral alkoxylated amine compounds may be converted to primary, secondary, or tertiary ammonium salts by reaction with a Bronsted acid, to form an N- H bond. Electrically neutral alkoxylated amine compounds may also be converted to quaternary ammonium salts or cations by complete alkylation with an alkylating agent, wherein suitable alkylating agents that include but are not limited to alkyl halides, alkyl sulfates, and the like. Suitable electrically neutral alkoxylated amine compounds include but are not limited to, those sold under the trade name of JEFF AMINETM (from Huntsman Chemical, Twin Falls Idaho).
  • Hydroxyalkyl groups are a sub-genus of the larger genus of "alkoxyl” groups in that they must have a terminal hydroxyl group, although "alkoxy" groups optionally may also be present on a hydroxyalkyl group.
  • hydroxyalkyl groups include but are not limited to hydroxymethyl groups (i.e. a -CH 2 -OH group), 1- or 2- hydroxyethyl groups (i.e. a -CH(OH)-CH 3 group or a -CH 2 -CH -OH group, 1- or 3- hydroxypropyl groups, 4-hydroxybutyl groups, and higher branched, straight chain, or cyclic analogs thereof.
  • Useful alkoxylated ammonium compounds (salts) for use in the composites, nanocomposites and processes of this invention include mono-alkoxylated, di- alkoxylated, tri-alkoxylated, and tetra-alkoxylated ammonium compounds.
  • Hydroxyalkylated compounds are also useful in the present invention and may include mono-hydroxyalkylated, di- hydroxyalkylated, tri- hydroxyalkylated, or tetra- hydroxyalkylated ammonium cations.
  • Prefened mono-alkoxylated ammonium salts for use in the composites and processes of this invention include compounds that can be represented as follows:
  • N represents nitrogen
  • X " represents an anion, which is preferably a halide atom such as chloride or bromide
  • R 1 ⁇ R 2 , and R 3 may be the same or different and are organic or oligomeric ligands comprising 1 to 30 carbon atoms, or may be hydrogen
  • n is at least 1
  • * is hydrogen or a hydrocarbon comprising 1 to 4 carbon atoms
  • R 5 is hydrogen or a hydrocarbon comprising 1 to 7 carbon atoms.
  • prefened alkoxyl groups comprise a group or residue exemplified above and below by the formula:
  • Prefened di-alkoxylated ammonium salts for the compositions, nanocomposites, and processes of this invention can be represented as follows:
  • N represents nitrogen
  • X " represents an anion which is preferably a halide atom such as chloride or bromide
  • Ri and R 2 may be the same or different and are organic or oligomeric ligands comprising 1 to 30 carbon atoms, or may be hydrogen
  • p and n are at least 1 and can be the same or different
  • R 3 , R4, R 5 and R 6 may be same or different and are hydrogen or hydrocarbons comprising 1 to 4 carbon atoms.
  • Examples of useful di-alkoxylated ammonium cations include, but are not limited to bis(l- hydroxymethyl), octadecyl ammonium (having a hydrogen attached to nitrogen); bis(2-hydroxyethyl),octadecyl,methyl ammonium; octadecyl, isopropoxy, dimethyl ammonium; and the like or a mixture thereof.
  • R] and R 2 are organic ligands.
  • Prefened di-alkoxylated ammonium cations are tertiary (i.e. only one of Ri or R 2 are hydrogen) or are quarternary (i.e. neither Ri or R 2 are hydrogen).
  • Prefened di-alkoxylated ammonium cations within this class have at least one hydroxyalkyl residue (i.e. at least one of R 5 or R ⁇ are hydrogen). Even more prefened di-alkoxylated ammonium cations within this class are tertiary or quarterary, and have two hydroxyalkyl ligands (i.e. Ri and R 2 are not hydrogen, and R 5 and R 6 are hydrogen).
  • Useful tri-alkoxylated ammonium salts for the compositions, nanocomposites, and processes of this invention can be represented as follows:
  • N represents nitrogen
  • X " represents an anion which is preferably a halide such as chloride or bromide
  • Rj is an organic or oligomeric ligand comprising 1 to 30 carbon atoms, or may be hydrogen
  • n, p, and q are at least 1 and can be the same or different
  • R 2 , R 3 , R , R , R ⁇ and R 7 may be the same or different and are hydrocarbons comprising 1 to 4 carbon atoms or hydrogen.
  • Ri and R 2 are not oligomeric.
  • tri-alkoxylated ammonium salts are inherently at least tertiary, and will be quaternary if Rj is not hydrogen.
  • Useful tetra-alkoxylated ammonium salts for the nanocomposite and process of this invention can be represented as follows:
  • N represents nitrogen
  • X " represents an anion which is preferably a halide atom such as chloride or bromide
  • m, n, p, and q are at least 1 and can be the same or different
  • R ⁇ , R 2 , R 3 , Rt, R 5 , R ⁇ 5 , R and R may be the same or different and are hydrocarbons comprising 1 to 4 carbon atoms or hydrogen.
  • Certain prefened alkoxylated ammonium salts for the compositions, nanocomposites and processs of this invention is a di-ethoxylated ammonium salt represented as follows:
  • N represents nitrogen;
  • X " represents an anion which is preferably a halide atom such as chloride or bromide;
  • R] is an organic or oligomeric ligand comprising at least 8 carbon atoms;
  • R 2 is hydrogen or an organic and oligomeric ligand comprising at least 8 carbon atoms;
  • p and n are at least 1 and can be the same or different.
  • Ri and R 2 are not oligomeric.
  • only one of R] and R 2 is hydrogen (i.e. the cation is tertiary), or neither Ri or R 2 is hydrogen (i.e. the cation is quaternary).
  • N represents nitrogen
  • Ri is an organic ligand comprising from 1 to 30 carbon atoms
  • R 2 is hydrogen or an organic ligand from 1 to 4 carbon atoms
  • p and n are at least 1 and can be the same or different.
  • R 2 is an organic ligand (i.e. the cation is quaternary).
  • suitable di-ethoxylated ammonium salts include those available under the trade name ETHOQUAD or ETHOMEEN from Akzo Chemie America,Chicago Illinois, namely, ETHOQUAD 18/25, which is octadecyl methyl bis(polyoxyethylene[15]) ammonium chloride and ETHOMEEN 18/25, which is octadecyl bis(polyoxyethylene[15])amine, wherein the numbers in brackets refer to the total number of ethylene oxide units.
  • the most prefened alkoxylated ammonium cations are octadecyl methyl bis(2-hydroxyethyl) ammonium and methyl bis(2- hydroxyethyl) tallow ammonium.
  • tallow is a mixture of materials derived from the treatment of animal fats, principally comprising a 50% majority mixture of chemical compounds having saturated and unsaturated C ⁇ 8 alkyl groups also comprising smaller amounts of other alkyl groups, including C] 6 alkyl groups. Tallow may be treated to remove any unsaturated groups, to generate hydrogenated tallow. It is to be understood that a reference to “tallow” includes “hydrogenated tallow” unless otherwise specifically indicated herein.
  • p and n are integers and the sum of p + n is greater than two.
  • Ri or R 2 or both are independently from each other a C2-C30 organic ligand.
  • Ri or R 2 do not comprise a tallow residue or an octadecyl residue.
  • Mixtures of the above-described alkoxylated onium compounds may be used to treat, modify, and/or intercalate the layered clay materials of the invention.
  • the alkoxylated onium compounds may be further mixed with non- alkoxylated onium compounds, and the mixtures used to treat layered clay materials.
  • Useful non- alkoxylated onium salts that may be employed in the mixtures, or employed for additional treatments of the layered clay materials can be represented as follows:
  • M represents nitrogen or phosphorous
  • X " represents an anion, preferably a halide atom such as chloride or bromide
  • Ri, R 2 , R and R 4 are independently selected from organic and oligomeric ligands having 1 to 30 carbon atoms, or may be hydrogen.
  • One embodiment of this invention is the treatment, modification or intercalation of at least one layered clay material with an at least one ammonium compound by the process of dispersing the layered clay material(s) in hot water, most preferably from 50 to 80 °C, adding (neat or dissolved in water or alcohol) an organic onium salt, ammonium salt, or an organic amine and a Bronsted acid (thereby forming the organic onium salt in situ) or their combinations and mixtures with agitation. The mixture is blended for a period of time sufficient for the organic onium cations to exchange most of the metal cations present in the galleries between the layers of the layered clay material.
  • organic ammonium salt it is desirable to use a sufficient amount of the organic ammonium salt to permit exchange of most of the metal cations in the galleries of the layered particle for organic cations; therefore, at least about 0.5 equivalent of organic cation salt is used and up to about 3 equivalents of organic cation salt can be used. It is prefened that about 0.5 to 2 equivalents of organic cation salt be used, more preferable about 1.0 to 1.5 equivalents. It is often desirable, but not required, to remove most of the metal cation salt and most of the excess organic cation salt by washing and by other techniques known in the art.
  • useful clay treatments are known in the art, and these treatments may also be used before, during, or after treatment with the alkoxylated onium compound without deviating from the scope of this invention.
  • useful treatments include, but are not limited to treatments with silane compounds, expanding agents, oligomeric polymers, dispersing aids, and other organic cation salts.
  • dispersing aids are known, covering a wide range of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents, and the like or combinations thereof.
  • any basis dispersing aids and/or pretreatment compounds that are used may account for significant amount of the total composition, in some cases up to about 30 weight percent. While it is prefened to use as little dispersing aids and/or pretreatment compounds as possible, the amounts of dispersing aids and/or pretreatment compounds may be as much as about 9 times the amount of the platelet particles.
  • the layered clay materials may be termed a "treated layered clay material" or an "organoclay.”
  • the organically treated or modified layered silicate material is isolated by methods known in the art including, but not limited to filtration, centrifugation, spray drying, and/or their combinations.
  • the particle size of the organoclay is then reduced in size by methods known in the art, including, but not limited to, grinding, pulverizing, hammer milling, jet milling, and their combinations. It is prefened that the average particle size be reduced to less than 100 microns in diameter, more preferably less than 50 microns in diameter, and most preferably less than 20 microns in diameter.
  • nanocomposites of the present invention represent highly dispersed and/or exfolliated forms of the platelet particles within the composite compositions of the invention.
  • the composite compositions, which are part of the intended scope of the invention need not always be in the highly dispersed or exfoliated form, crude mixtures of the component parts of the compositions of the invention may be prepared, then subsequently converted to desirable nanocomposite form during final processing steps such as compounding, extrusion, molding, etc. , as is described below.
  • Many processes for forming the composites and/or nanocomposites of the invention involve melting of the polyamide and mixing the molten polyamide with the layered clay materials.
  • the polyamide, the layered clay material, and the composites and/or nanocomposites produced by mixing are preferably melt processible, meaning that they are substantially thermally stable at or somewhat above the temperatures of the molten polyamides for the time of the required processing, so that there is not an unacceptable amount of chemical degradation or discoloration during melt processing.
  • Melt processible materials must also have acceptable viscosity and other important physical properties at the temperature of the melts to allow melt processing.
  • Prefened melt processible nanocomposites have rates of crystallization slow enough to permit production of optically clear preforms suitable for use in two-step blow molding processes.
  • prefened composition and/or nanocomposites of the invention may be identified by a test protocol to identify the compositions having a smaller value of T cc - T ch , as compared with the value of T cc - T ch obtained from a conesponding composition prepared by substituting an non-alkoxylated ammonium cation, such as octadecyltrimethylammonium cation, for the alkoxylated ammonium cation.
  • an non-alkoxylated ammonium cation such as octadecyltrimethylammonium cation
  • the melt mixing step is achieved by dry mixing polymer, preferably polyamide, with treated layered particles, then passing the mixture through a compounding extruder under conditions sufficient to melt the polymer.
  • the melt mixing step is conducted either by a batch mixing process or by a melt compounding extrusion process during which treated or untreated layered particles are introduced into a polyamide.
  • the treated or untreated layered particles Prior to melt mixing, the treated or untreated layered particles may exist in various forms including pellets, flakes, chips and powder. It is prefened that the treated or untreated layered particles be reduced in size by methods known in the art, such as hammer milling and jet milling.
  • the polyamide Prior to melt mixing, the polyamide may exist in wide variety of forms including pellets, ground chips, powder and molten.
  • the melt-mixing step is conducted by feeding the polymer and treated or untreated layered particles separately into a compounding extruder.
  • treated layered clay particles When treated layered clay particles are used in this process, it is usually prefened that the polymer be added first, to minimize degradation of treated layered clay particles.
  • Use of extrusion compounding to mix the clay and the polymer is prefened because of the ease of preparation and the potential to attain high clay loadings.
  • a dispersing aid or expanding agent may be present during or prior to the formation of the composite by melt mixing for the purposes of aiding exfoliation of the treated swellable layered clay materials and/or particles into the polymer, to form nanocomposites.
  • Many such dispersing aids are known, covering a wide range of materials including water, oligomeric polymers, water dispersible polymers, and organic compounds. Examples of suitable organic compounds include alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents, and the like or combinations thereof. Examples of suitable water dispersible compounds include sulfonated polymers such as sulfonated polyesters and sulfonated polystyrene.
  • the formation of a concentrate of the treated clay and an oligomeric polyamide, that may be the same or different from the matrix polymer, and that is then used to prepare the final nanocomposite is especially useful.
  • compositions and/or nanocomposites of this invention may be treated before, during, or after their preparation for the purpose of increasing the molecular weight of the polyamides.
  • Increasing the molecular weight of the polymer- platelet particle composite may be achieved by several different methods including, but not limited to reactive chain extension, solid state polymerization, crosslinking, and melt compounding with a high molecular weight, melt-processible polymer.
  • other fillers, additives, and reagents normally used in polymers may be incorporated into the nanocomposite.
  • Useful additives and reagents include adhesive modifiers, oxygen scavenging catalysts, oxygen scavengers, toners, dyes, coloring agents, UV absorbers, mold release agents, recycling release aids, acetaldehyde reducing compounds, impact modifiers, antioxidants, stabilizers, flame retardants, reheat aids, crystallization aids, and their combinations.
  • Useful fillers include glass fibers, glass beads, talc, carbon black, carbon fiber, titanium dioxide, and the like, or their combinations.
  • the amount of platelet particles in the composite or nanocomposite compositions are determined by measuring the amount of ash of the polymer-platelet particle compositions when treated in accordance with ASTM D5630-94.
  • the gas barrier improvement generally increases with increasing concentration of platelet particles in the composite. While amounts of platelet particles as low as 0.01 percent provide improved barrier (especially when well dispersed and ordered), compositions having at least about 0.5 weight percent of the platelet particles are prefened because they display desirable improvements in gas permeability.
  • the improved gas barrier properties are related to beneficial interactions between the prefened layered clay materials of the invention and the alkoxylated onium cations of the invention.
  • Improvements in gas banier properties may be measured by a variety of methods. For example, improvements in gas barrier properties may be measured by comparison with the gas barrier properties obtained from a conesponding composition prepared by substituting octadecyltrimethylammonium cations for the alkoxylated ammonium cations of the invention.
  • the degree of improved gas barrier properties observed in the composites of the invention depends upon the embodiment ratio of the resulting particle platelets and aggregates, the degree to which they are dispersed or uniformly distributed, and the degree to which they are ordered perpendicular to the flux of the permeant.
  • the clay representative of the bulk of the composite be exfoliated, and preferably be highly exfoliated, in the matrix polymer such that the majority, preferably at least about 75 percent and perhaps as much as at least about 90 percent or more of the clay be dispersed in the form of individual platelet particles and aggregates having a thickness in the shortest dimension of less than about 20 nm and preferably less than about 10 nm, as estimated from TEM images.
  • Polymer-clay nanocomposites containing more individual platelets and fewer aggregates, ordered or disordered, are most prefened.
  • the compositions or polymer nanocomposite material preferably comprises poly(m-xylene adipamide) (MXD6) and Wyoming-type montmorillonite and/or bentonite (clay) with a cation-exchange capacity of approximately 100 milhequivalents per hundred grams of clay.
  • the clay is preferably treated with an alkoxylated ammonium compound, which is a tethered surfactant that promotes dispersion of the clay into the polyamide.
  • the one or more polyamide polymers or copolymers comprises the polymerization reaction product of at least one diamine component, and at least one dicarboxylic acid component or dicarboxylic acid ester component; wherein the at least one dicarboxylic acid component or dicarboxylic acid ester component comprises a residue of phthalic acid, isophthalic acid, terephthalic acid, 1,4- cyclohexanedicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, sebacic acid, a succinic acid, adipic acid, glutaric acid, azelaic acid, 1,3 -phenyl enedioxydiacetic acid, iminodiacetic acid, oxydiacetic acid, thiodiacetic acid, 1 ,4-phenylenedioxydiacetic acid, phenylindane dicar
  • Example 6 illustrates the preparation of a polyamide comprising 90 mol % 1,3- phenylenedioxydiacetic acid (PDA) and 20 mol % terephthalic acid (TPA) with m- xylylenediamine (MX).
  • PDA 1,3- phenylenedioxydiacetic acid
  • TPA terephthalic acid
  • MX m- xylylenediamine
  • This example illustrates the preparation of an amorphous polyamide comprising 90 mole % of 1,3-phenylenedioxydiacetic acid (PDA) and 10 mole % of naphthalenedicarboxylic acid (NDA) with w-xylylenediamine (MX).
  • PDA 1,3-phenylenedioxydiacetic acid
  • NDA naphthalenedicarboxylic acid
  • MX w-xylylenediamine
  • Example 8 illustrates the preparation of an amorphous polyamide comprising 82 mol % adipic acid (A) and 18 mol % isophthalic acid (IP A) with m-xylylenediamine (MX).
  • Example 9 illustrates the preparation of a polyamide comprising 82 mol % adipic acid (A) and 18 mol % terephthalic acid (TPA) with r ⁇ -xylylenediamine (MX).
  • the bath temperature was 164°C, 30 ml of water had been trapped in a condensation receiver and the reaction mixture was a white solid.
  • the stirrer was stopped. After 10 minutes, the bath temperature was 275°C, melting had begun and the stiner was started at 25 RPM. After 16 minutes, some melting had begun and the stiner set point was increased to 100 RPM. After 7 minutes, the stirring was increased to 200 RPM. After 26 minutes, the entire solid had melted and 65 ml of water was trapped in a condensation receiver. Vacuum was applied beginning at 300 mm of mercury with gradual reduction to a set point of 0.3 mm over a period of 5 minutes.
  • the bath temperature was 164°C , 30 ml of water had been trapped in a condensation receiver and the reaction mixture was a white solid.
  • the stirrer was stopped. After 10 minutes, the bath temperature was 275°C, melting had begun and the stiner was started at 25 RPM. After 16 minutes, some melting had begun and the stiner set point was increased to 100 RPM. After 7 minutes, the stirring was increased to 200 RPM. After 26 minutes the entire solid had melted and 65 ml of water was trapped in a condensation receiver. Vacuum was applied beginning at 300 mm of mercury with gradual reduction to a set point of 0.3 mm over a period of 5 minutes. As the viscosity of the melt increased, stirring was gradually reduced over a period of 13 minutes to 25 RPM.
  • This example illustrates the preparation of an amorphous polyamide comprising 81 mole % of adipic acid (A) and 19 mole % of phenylindandicarboxylic acid (PIDA) with w-xylylenediamine (MX).
  • the temperature set point was increased to 150°C and 10 ml of water had been trapped in a condensation receiver.
  • the bath temperature was increased to 160°C and 12 ml had been trapped in a condensation receiver.
  • the bath temperature was 275°C and 15 ml had been trapped in a condensation receiver.
  • the bath temperature was 198°C and 21 ml had been trapped in a condensation receiver. Some slight foaming was still present.
  • the bath temperature was 244°C and 35 ml had been trapped in a condensation receiver.
  • the reaction mix was a white thick paste and the stirring was reduced to 25 RPM. After 16 minutes, the bath temperature was 275 °C and the reaction mix was Vi melted.
  • Example 12 illustrates the preparation of one embodiment of a polyamide-clay nanocomposite of this invention.
  • An amorphous copolyamide prepared as described in Example 9 1,000 grams of A-20-IPA(MX) with an I.V. of about 0.91 dL/g), and an octadecylammonium ion- intercalated clay (29.0 grams of CWC-ODA) of Nanocor, Inc., were dry blended and then dried in a vacuum oven with a slight nitrogen sweep at about 75°C for about 16 hours.
  • the mixture was placed into an AccuRate feeder then extruded at a feed rate of about 3.8 kg/hr on a Leistritz Micro 18 corotating twin screw extruder equipped with a general compounding screw at about 300 RPM with the banel and die temperatures set at 250°C and vacuum ventilation.
  • the extrudate was quenched into water then chopped as it exited the die, to give 807 grams of the copolyamide nanocomposite with I.V. of about 0.90 dL/g and having an ash value of about 1.9 weight percent.
  • Analysis by DSC showed a minor melting endotherm of 0.4 cal g at about 200°C on the first scan and no melting endotherm was observed on the second scan after cooling at a rate of about 200°C/min.
  • Example 13 illustrates the coextrusion of one embodiment of a polyamide-clay nanocomposite of this invention and poly(ethylene terephthalate) (PET).
  • the copolyamide nanocomposite from Example 8(about 700 grams) was dried in a vacuum oven with a slight nitrogen sweep at about 75 °C for about 16 hours.
  • PET 9921 of Eastman Chemical Company, was dried separately in a hopper drier at about 120°C. Then the copolyamide nanocomposite and the PET 9921 were co-extruded to form a tri-layer film with the copolyamide nanocomposite comprising the center layer with thickness of about 7.0 mils and with the PET 9921 comprising the two outside layers with a total film thickness of about 21 mils.
  • 2-inch square pieces of the tri-layer film were biaxially oriented at a stretch ratio of 4x4 using a T. M. Long instrument.
  • the oriented film showed excellent color and clarity, with haze of about 0.6%, L* of about 94.6, a* of about -0.9, and b* of about 0.1.
  • Analysis of the oriented film by optical microscopy revealed very few large particles and almost no voids.
  • Oxygen permeability of the film was determined using a Mocon Oxatran 2/20 to be 0.48 cc- mil/100in 2 -day-atm, which is significantly better than the control sample in Comparative Example 6, and is better than the polyamide nanocomposite in Comparative Example 7.
  • Example 13 The process of Example 13 as repeated except that clay- free MXD6 6007, available from Mitsubishi Gas and Chemical Company, was used instead of the copolyamide nanocomposite to give a tri-layer film with total thickness of about 20.5 mils and a center clay- free barrier layer thickness of about 6.0 mils, as extruded.
  • the oriented film showed good color but elevated haze, with haze of about 2.45%, L* of about 94.7, a* of about -0.09, and b* of about -0.1.
  • Oxygen permeability of the film was determined using a Mocon Oxatran 2/20 to be 0.83 cc-mil/100in 2 -day- atm, significantly (0.35 cc-mil/100in 2 -day-atm) higher than the film having the nanocomposite center layer of Example 5. Comparative Example 7
  • Example 12 The process of Example 12 as repeated except that MXD6 6007, of Mitsubishi Gas and Chemical Company, was used instead of the copolyamide prepared as described in Example 8
  • Example 6 The process of Example 6 as repeated except that (1) the MXD6 nanocomposite was used instead of the copolyamide nanocomposite and (2) PET 20261, of Eastman Chemical Company, was used instead of PET 9921.
  • the tri-layer film had a total thickness of about 21 mils and a center MXD6 nanocomposite layer thickness of about 1.4 mils.
  • the oriented film showed elevated haze, with haze of about 2.5%.
  • Oxygen permeability of the film was determined using a Mocon Oxatran 2/20 to be 2.81 cc-mil/100in 2 -day-atm.
  • a low molecular weight amine terminated copolyamide is prepared as described in Example 8 except that an excess of the m-xylylenediamine is used, to provide a material with I.V. of about 0.3 dL/g. This material is then used in place of the high I.V. copolyamide in the process of Example 12.
  • 100 grams of the extrudate pellets are dry-mixed with 300 grams of MXD6 6007 polyamide pellets, of Mitsubishi Gas and Chemical Company.
  • the mixture is then extruded on the Leistritz extruder under the same conditions as used with the clay polymer mixture but at a feed rate of 2.0 to 2.5 kg/hour.
  • the resulting copolyamide nanocomposite is found to provide tri-layer film with excellent appearance and oxygen barrier.
  • Example 8 The process of Example 8 was repeated except that an onium ion intercalated clay (29.0 grams of CWC-ODA) of Nanocor, Inc., was also charged to the flask prior to the addition of the m-xylylenediamine. The resulting copolyamide nanocomposite is found to provide tri-layer film with excellent appearance and oxygen barrier.
  • an onium ion intercalated clay 29.0 grams of CWC-ODA of Nanocor, Inc.
  • Example 16 illustrates one embodiment of a nanocomposite of the present invention.
  • MXD6 6007 poly(w-xylylene adipamide) with an I.V. of about 1.1 dL/g, was purchased from Mitsubishi Chemical Co.
  • the organo-montmorillonite clay (PGC- Q182) was provided by Nanocor Inc. of Arlington Heights, IL.
  • the clay has a quartz content of 0.33 wt% determined from X-ray diffraction method.
  • this organoclay has a Na + content of 0.12 wt%, as determined by X-ray diffraction.
  • the organo-montmorillonite clay was prepared by onium ion exchanging Na- montmorillonite with bis(2 -hydroxyethyl) octadecyl methyl ammonium chloride. The finished product was washed with alcohol/water mixture to remove excess surfactant then dried and milled. The tether on the clay is bis(2-hydroxyethyl) octadecyl methyl ammonium.
  • a low molecular weight poly(w-xylylene adipamide) polyamide was prepared as described in US Patent 5,340,884. This material was analyzed by titration of the amine and carboxylate end groups to possess a number average molecular weight of about 3,000, and was determined to have an I.V. of about 0.41 dL/g. 1421.8 grams of this oligomeric poly(m-xylylene adipamide) was dry mixed with 378.2 grams of organomontmorillonite clay from Nanocor, Inc. Prior to dry mixing, the individual components were dried at 80C under vacuum for 24 hours. The mixture was then extruded on the Leistritz Micro 18 co-rotating twin screw extruder equipped with a general compounding screw. The AccuRate pellet feeder was set at a rate of approximately 2 kg/hr with a nitrogen atmosphere over both the feeder and the hopper. The banel and die temperatures were set at 240C and the screw RPM at approximately 200.
  • the resulting nanocomposite material, of this example 16 was used as the middle layer of co-injected trilayer preforms.
  • the ash content of the resulting nanocomposite was 2.53%.
  • the inner and outer layers of the trilayer preform were made from Eastman's amber colored PET 20261, having about 0.80 dL/g I.V.
  • the nominal thickness of the middle layer was about 8% of the total thickness.
  • the preforms were stretch blow molded on Sidel SBO 2/3 machine into 16oz. beer bottle. The bottle sidewall was cut and the middle layer containing the nanocomposite material was peeled from the three-layer configuration, and analyzed for haze, oxygen permeability and optical microscopy.
  • the haze of the middle layer was 8 %.
  • the haze was determined by ASTM test method D-1003.
  • the oxygen permeability of the sidewall barrier materials in these bottles was approximately 0.1 cc mil/100 in 2 -24hr.-atm.
  • a low molecular weight oligomeric poly(w-xylylene adipamide) was prepared as described in US Patent 5,340,884. This material was analyzed by titration of the amine and carboxylate end groups to possess a number average molecular weight of about 3,000, and was determined to have an I.V. of about 0.41 dL/g. 306.4 grams of this oligomeric poly(m-xylylene adipamide) was dry mixed with 55 grams of SCPX- 1578 organomontmorillonite clay purchased from Southern Clay Products (Gonzalez, Texas) and then dried at 110°C overnight in a vacuum oven.
  • the mixture was then extruded on the Leistritz Micro 18 corotating twin screw extruder equipped with a general compounding screw.
  • the AccuRate pellet feeder was set at a rate of approximately 2 kg/hr with a nitrogen atmosphere over both the feeder and the hopper.
  • the banel and die temperatures were set at 280°C and the screw RPM at approximately 275.
  • 100 grams of the extrudate pellets are dry- mixed with 300 grams of MXD6 6001 polyamide pellets purchased from Mitsubishi Chemical.
  • the MXD6 polyamide possessed an I.V. of about 1.1 dL/g.
  • the mixture was then extruded on the Leistritz extruder under the same conditions used with the clay polymer mixture but at a feed rate of 2.0 to 2.5 kg/hour.
  • the material obtained was then characterized by optical microscopy (OM), transmission electron microscopy (TEM) and by wide angle X-ray diffraction (WAXD) to determine the degree of dispersion of the organoclay into the polymer matrix and to assess the morphology of the composite material.
  • OM optical microscopy
  • TEM transmission electron microscopy
  • WAXD wide angle X-ray diffraction
  • the WAXD analysis was carried out on a ground sample of the material using an X-ray diffractometer equipped with a Cu K ⁇ X-ray source.
  • the diffraction profile from the organoclay exhibits a diffraction maximum conesponding to a basal spacing value of 1.8 nm.
  • no diffraction maximum is exhibited in the WAXD profile.
  • optical microscopy it is determined that the composite material exhibits a high degree of clarity, indicating that most of the organoclay is well distributed into the matrix of the polymer.
  • the transmission electron micrographs verified that, in most cases, each of the clay layers is exfoliated, i.e. individually dispersed in the polymer matrix.
  • a film was formed from the nanocomposite material by compression molding on a hydraulic press at 280°C followed by immediate quenching in ice water to minimize crystallization on cooling.
  • the oxygen barrier of the film was then determined on a Mocon 2/20 oxygen permeability tester to be 0.03 cc mil 100 in 2 - 24hr.-atm.

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EP00942840A 1999-07-12 2000-06-14 Polyamidzusammensetzung enthaltend schichtton welcher mit einer alkoxylierten oniumverbindung modifiziert ist Withdrawn EP1200515A1 (de)

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