US20060122309A1 - Intercalated layered silicate - Google Patents
Intercalated layered silicate Download PDFInfo
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- US20060122309A1 US20060122309A1 US11/002,615 US261504A US2006122309A1 US 20060122309 A1 US20060122309 A1 US 20060122309A1 US 261504 A US261504 A US 261504A US 2006122309 A1 US2006122309 A1 US 2006122309A1
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- NYMOYCQOHNFBML-UHFFFAOYSA-N CC.CCC.CCC(=O)OC.CCOCC(=O)OC.CCOCC(=O)OC.COC(=O)COC(C)C.COC(C)=O.COCC(=O)OC Chemical compound CC.CCC.CCC(=O)OC.CCOCC(=O)OC.CCOCC(=O)OC.COC(=O)COC(C)C.COC(C)=O.COCC(=O)OC NYMOYCQOHNFBML-UHFFFAOYSA-N 0.000 description 2
- 0 [6*]C([7*])(C)[Ar] Chemical compound [6*]C([7*])(C)[Ar] 0.000 description 2
- CKVOJRVZBMTVJM-UHFFFAOYSA-N CC.CCC.CCC(=O)OC.COC(C)=O Chemical compound CC.CCC.CCC(=O)OC.COC(C)=O CKVOJRVZBMTVJM-UHFFFAOYSA-N 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to intercalated layered silicates and to dispersed-particle compositions comprising silicate platelets exfoliated from intercalated layered silicates.
- Intercalated clays may be made using a quaternary ammonium-based intercalating agent.
- quaternary ammonium-based intercalating agents may show an unacceptably high amount of decomposition at the processing resident times and temperatures desired for processing a matrix medium incorporating the quaternary ammonium-based intercalating agent.
- One or more embodiments of the present invention may address one or more of the aforementioned problems.
- An intercalated layered silicate comprises a layered silicate and an intercalating agent sorbed between the silicate layers of the layered silicate.
- the amount of intercalating agent is effective to provide an average interlayer spacing between the silicate layers of at least about 20 ⁇ .
- the intercalating agent has a formula selected from formulas I through VII as described below.
- the intercalated layered silicate may be exfoliated by mixing it with a matrix medium and adding sufficient energy to form a dispersed-particle composition.
- a packaging film such as a food packaging film, may comprise the dispersed-particle composition.
- FIG. 1 is an X-ray diffraction pattern for montmorillonite clay intercalated with pentaerythritol monostearate, as discussed in Example 1;
- FIG. 2 is an X-ray diffraction pattern for non-intercalated montmorillonite clay
- FIG. 3 is an X-ray diffraction pattern for montmorillonite clay intercalated with dimethyl didehydrogenated tallow quaternary ammonium intercalated montmorillonite, as discussed in Comparative 1;
- FIG. 4 is an X-ray diffraction pattern for montmorillonite clay intercalated with pentaerythritol monostearate dispersed in a matrix medium of linear low density polyethylene, as discussed in Example 3;
- FIG. 5 is an X-ray diffraction pattern for montmorillonite clay intercalated with pentaerythritol monostearate dispersed in a matrix medium of isotactic polypropylene, as discussed in Example 4;
- FIG. 6 is an X-ray diffraction pattern for montmorillonite clay intercalated with pentaerythritol monostearate dispersed in a matrix medium of ethylene/vinyl acetate copolymer, as discussed in Example 5;
- FIG. 7 is an X-ray diffraction pattern for montmorillonite clay intercalated with pentaerythritol monostearate dispersed in a matrix medium of nylon-6 polymer, as discussed in Example 6;
- FIG. 8 is a thermogravimetric analysis (TGA) graph for the Example 1 PEMS intercalated montmorillonite clay.
- FIG. 9 is a thermogravimetric analysis (TGA) graph obtained for the Comparative Sample 1 Cloisite 20A intercalated clay.
- An intercalated layered silicate comprises a layered silicate comprising a plurality of silicate layers.
- An intercalating agent is sorbed between the silicate layers in an amount effective to provide an average interlayer spacing between the silicate layers of at least about 20 ⁇ .
- the intercalated layered silicate comprises a layered silicate.
- the layered silicate i.e., phyllosilicate
- exemplary layered silicates include:
- Natural clays such as smectite clays, for example, bentonite clays (e.g., montmorillonite, hectorite), mica, vermiculite, nontronite, beidellite, volkonskoite, and saponite;
- Layered polysilicates e.g., layered silicic acid
- kanemite makatite
- ilerite octosilicate
- magadiite magadiite
- kenyaite e.g., kanemite, makatite, ilerite, octosilicate, magadiite, and kenyaite
- Synthetic clays such as, synthetic silicates, synthetic mica, synthetic saponite, synthetic laponite, and synthetic hectorite.
- Layered silicates comprise a plurality of silicate layers, that is, a laminar structure having a plurality of stacked silicate sheets or layers with a variable interlayer distance between the layers.
- the layered silicate may have a 2:1 layer structure typified by an octahedral layer, comprising aluminum or magnesium, sandwiched between two tetrahedral silicate layers.
- the layers of the layered silicate may be turbostratic relative to each other, such that the layered silicate may be swellable, for example, in water.
- the average thickness of the silicate layers may be at least about any of the following: 3, 5, 8, 10, 15, 20, 30, 40, and 50 ⁇ ; and at most about any of the following: 60, 50, 45, 35, 25, 20, 15, 12, 10, 8, and 5 ⁇ .
- many layered silicates have a silicate layer thickness ranging from 8 to 11 ⁇ .
- the average interlayer spacing of the layered silicate at 60% relative humidity before intercalation with the intercalating agent may be at least about any of the following: 1, 2, 3, 4, 5, 6, 8, and 10 ⁇ ; and may be at most about any of the following: 20, 15, 10, 8, 6, 5, 3, and 2 ⁇ .
- the average interlayer spacing (i.e., the gallery spacing) of a layered silicate refers to the distance between the internal faces of the non-exfoliated, adjacent layers of representative samples of the layered silicate.
- the interlayer spacing may be calculated using standard powder wide angle X-ray diffraction techniques generally accepted in the art in combination with Bragg's law equation, as is known in the art.
- Useful layered silicates are available from various companies including Nanocor, Inc., Southern Clay Products, Kunimine Industries, Ltd., and Rheox.
- the intercalated layered silicate comprises an intercalating agent sorbed between the silicate layers of the layered silicate.
- the term “sorbed” in this context means inclusion within the layered silicate (for example, by adsorption and/or absorption) without covalent bonding.
- An intercalating agent that is sorbed between silicate layers may be held to the interlayer surface of a silicate layer by one or more of ionic complexing, electrostatic complexing, chelation, hydrogen bonding, ion-dipole interaction, dipole-dipole interaction, and van der Waals forces.
- the intercalating agent may have any one or more of the following formulas:
- R 4 may represent an acyl group, for example, an acyl group having at least any of 8, 10, 12, 14, and 16 carbon atoms; and/or at most any of 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, and 10 carbon atoms.
- the acyl group may be branched or unbranched.
- the acyl group may be saturated or unsaturated (for example, with any of one, two, three, or at least four units of unsaturation);
- R 4 may represent an alkyl group, for example, an alkyl group having at least any of 8, 10, 12, 14, and 16 carbon atoms; and/or at most any of 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, and 10 carbon atoms.
- the alkyl group may be branched or unbranched;
- R 4 may represent an alkenyl group, for example, an alkenyl group having at least any of 8, 10, 12, 14, and 16 carbon atoms; and/or at most any of 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, and 10 carbon atoms.
- the alkenyl group may be branched or unbranched;
- R 4 may represent an alkadienyl group, for example, an alkadienyl group having at least any of 8, 10, 12, 14, and 16 carbon atoms; and/or at most any of 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, and 10 carbon atoms.
- the alkadienyl group may be branched or unbranched.
- R 4 may represent a carbon chain group (branched or unbranched), for example having at least any of 8, 10, 12, 14, and 16 carbon atoms; and/or at most any of 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, and 10 carbon atoms, where the carbon chain group incorporates one or more pendant or terminal groups selected from each of a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, an aryl group (e.g., a phenyl group or a tolyl group), and an arylmethyl group having the formula “Ar” represents an aryl group.
- R 6 and R 7 may each independently represent a hydrogen, an acyl group, an alkyl group, or an alkenyl group.
- R 5 may represent any of H, —CH 3 , —CH 2 CH 3 , and any of the groups represented by R 4 .
- R 8 may represent oxylated groups selected from any one or more of the following formulas:
- “n” may be at least any of the following values: 2, 4, 5, 6, 8, 10 and/or at most any of the following values: 6, 8, 10, 12; for example, “n” may range from 4 to 12.
- “x” may be at least any of the following values: 4, 5, 6, 8, 10 and/or at most any of the following values: 6, 8, 10, 12, 13, 14; for example, “x” may range from 5 to 13.
- R 1 , R 2 and R 3 may each independently represent any of H, —CH 3 , —CH 2 CH 3 , and any of the groups represented by R 4 and R 8 , provided that any of two, at least two, or three of R 1 , R 2 , and R 3 may be H.
- a branch R 4 group may lack any branches (i.e., pendent groups) having more than two carbons (e.g., ethyl group) or more than one carbon (e.g., methyl group).
- the R 4 group may be compatible with the matrix medium of expected use.
- the R 4 group of the intercalating agent may facilitate the dispersion in the matrix medium of the silicate platelets having sorbed intercalating agent, such that a colloidal dispersion may be formed where the platelets do not settle out of the matrix medium.
- Exemplary intercalating agents having the formula I above include fatty acid esters of pentaerythritol (i.e., fatty acid esters of 2,2-bis-hydroxymethyl-1,3-propanediol), for example, pentaerythritol monostearate (“PEMS”), pentaerythritol monobehenate, pentaerythritol monooleate, pentaerythritol ricinoleate, and pentaerythritol monolaurate.
- PEMS pentaerythritol monostearate
- pentaerythritol monobehenate pentaerythritol monooleate
- pentaerythritol ricinoleate pentaerythritol monolaurate
- exemplary intercalating agents having the formula I above are pentaerythityl stearol (i.e., 2-(hydroxymethyl)-2-[(octadecyloxy)methyl]-1,3-propanediol); 2-(hydroxymethyl)-2-[(4-cyclo-hexanebutyrate)methyl]-1,3-propanediol; and 2-(hydroxymethyl)-2-[(4-phenylbutyrate)methyl]-1,3-propanediol.
- pentaerythityl stearol i.e., 2-(hydroxymethyl)-2-[(octadecyloxy)methyl]-1,3-propanediol
- 2-(hydroxymethyl)-2-[(4-cyclo-hexanebutyrate)methyl]-1,3-propanediol 2-(hydroxymethyl)-2-[(4-phenylbutyrate)methyl]-1,3-propanediol.
- Exemplary intercalating agents having the formula II above include 1-hydroxy-2,2-bis(hydroxymethyl)octadecane; 1-hydroxy-2,2-bis(hydroxymethyl)tetradecane; and 1-hydroxy-2,2-bis(hydroxymethyl)dodecane.
- Exemplary intercalating agents having the formula III above include 2-(hydroxymethyl)-2-[(octadecylamino)methyl]-1,3-propanediol.
- Exemplary intercalating agents having the formula IV above include 2-(hydroxymethyl)-2-[(octadecylthio)methyl]-1,3-propanediol.
- Exemplary intercalating agents having the formula V above include 2-(hydroxymethyl)-2-[(14-hydroxy-3,6,9,12-tetraoxadeacanoyl)methyl]-1,3-propandiol.
- Exemplary intercalating agents having the formula VI above include steroyl citric acid, 2-(octadecanoxy)-1,2,3-propanetricaboxylic acid, 2-(4-phenylbutanoxy)-1,2,3-propanetricaboxylic acid, and stearyl citrate.
- the intercalating agent may be a nonionic intercalating agent, that is, an intercalating agent that does not tend to form or exchange ions, for example, in intercalating a layered silicate.
- the average interlayer spacing between the silicate layers of the intercalated layered silicate may be at least about any of the following: 20, 30, 40, 50, 60, 70, 80, and 90 ⁇ ; and/or may be at most about any of the following: 100, 90, 80, 70, 60, 50, 40, 30, 25 ⁇ .
- the amount of intercalating agent sorbed between the silicate layers may be effective to provide any of the forgoing average interlayer spacing between the silicate layers.
- the measurement of the average interlayer spacing of the intercalated layered silicate may be made at a relative humidity of 60%.
- the amount of intercalating agent sorbed in the intercalated layered silicate per 100 weight parts layered silicate may be at least about and/or at most about any of the following: 5, 10, 20, 30, 50, 70, 90, 110, 150, 200, and 300 weight parts.
- the intercalated layered silicate may be essentially free of intercalating agent comprising onium functionality.
- the intercalated silicate may be essentially free of any one, or of all, or of any combination of the following compounds: ammonium compounds, quaternary ammonium compounds, tertiary ammonium compounds, secondary ammonium compounds, primary ammonium compounds, phosponium compounds, quaternary phosponium compounds, tertiary phosponium compounds, secondary phosponium compounds, primary phosponium compounds, arsonium compounds, stibonium compounds, oxonium compounds, and sulfonium compounds.
- Exemplary ammonium compounds from which the intercalated layered silicate may be essentially free include any one or any combination of the following: alkyl ammonium compounds, such as tetramethyl ammonium compounds, hexyl ammonium compounds, butyl ammonium compounds, bis(2-hydroxyethyl)dimethyl ammonium compounds, bis(2-hydroxyethyl)octadecyl methyl ammonium compounds, octadecyl trimethyl ammonium compounds, octadecyl benzyl dimethyl ammonium compounds, hexyl benzyl dimethyl ammonium compounds, benzyl trimethyl ammonium compounds, butyl benzyl dimethyl ammonium compounds, tetrabutyl ammonium compounds, dodecyl ammonium compounds, di(2-hydroxyethyl)ammonium compounds, and polyalkoxylated ammonium compounds.
- alkyl ammonium compounds such as tetramethyl ammonium
- Exemplary phosphonium compounds from which the intercalated layered silicate may be essentially free include any one or any combination of the following: alkyl phosphonium compounds, such as tetrabutyl phosphonium compounds, trioctyl octadecyl phosphonium compounds, tetraoctyl phosphonium compounds, octadecyl triphenyl phosphonium compounds.
- alkyl phosphonium compounds such as tetrabutyl phosphonium compounds, trioctyl octadecyl phosphonium compounds, tetraoctyl phosphonium compounds, octadecyl triphenyl phosphonium compounds.
- the intercalated layered silicate may be essentially free of any intercalating agent comprising a compound selected from any or all of the compounds listed in the previous three paragraphs.
- a layered silicate is mixed with the intercalating agent to effect the inclusion (i.e., sorption) of the intercalating agent in the interlayer space between the silicate layers of the layered silicate.
- the resulting intercalated layered silicate may be rendered organophilic (i.e., hydrophobic) and show an enhanced attraction to an organic matrix medium.
- the intercalating agent may first be mixed with a carrier, for example, a carrier comprising one or more solvents such as water and/or organic solvents such as ethanol to disperse or solubilize the intercalating agent in the carrier.
- a carrier for example, a carrier comprising one or more solvents such as water and/or organic solvents such as ethanol to disperse or solubilize the intercalating agent in the carrier.
- the intercalating agent/carrier blend may subsequently be mixed with the layered silicate.
- the layered silicate may be mixed with the carrier to form a slurry, to which the intercalating agent may be added.
- the intercalating agent may be mixed directly with the layered silicate without the benefit of a carrier. Intercalation may be enhanced by addition of one or more of heat, pressure, high shear mixing, ultrasonic cavitation, and microwave radiation to any of the above systems.
- the inclusion of the intercalation agent within the interlayer spaces between the silicate layers of the layered silicate increases the interlayer spacing between adjacent silicate layers. This may disrupt the tactoid structure of the layered silicate to enhance the dispersibility of the intercalated layered silicate in the matrix medium, as discussed below.
- the intercalating agent sorbed between the silicate layers may be an amount and/or type effective to increase the interlayer spacing between the silicate layers—relative to the spacing before the sorption of the intercalating agent—by at least about any of the following: 5, 6, 7, 8, 10, 12, 14, 15, 18, 20, 30, 40, 50, 60, 70, 80, and 90 ⁇ ; and/or by at most about any of the following: 100, 90, 80, 70, 60, 50, 40, 30, 25, 20, 18, 15, 12, 10, 8, and 7 ⁇ .
- the intercalated layered silicate may be further treated to aid dispersion and/or exfoliation in a matrix medium and/or improve the strength of a resulting polymer/silicate interface.
- the intercalated layered silicate may be treated with a surfactant to enhance compatibility with the matrix medium.
- the intercalated layered silicate may be further intercalated with a compatibilizer, such as a polyolefin oligomer having polar groups.
- a compatibilizer such as a polyolefin oligomer having polar groups.
- An example is maleic anhydride modified olefin oligomer or maleic anhydride modified ethylene vinyl acetate oligomer.
- An oligomer may be modified (e.g., grafted) with unsaturated carboxylic acid anhydride (i.e., anhydride-modified oligomer) to incorporate anhydride functionality, which promotes or enhances the adhesion characteristics of the oligomer.
- unsaturated carboxylic acid anhydrides include maleic anhydride, fumaric anhydride, and unsaturated fused ring carboxylic acid anhydrides.
- Anhydride-modified polymer may be made by grafting or copolymerization, as is known in the art.
- Useful anhydride-modified oligomers may contain anhydride group in an amount (based on the weight of the modified polymer) of at least about any of the following: 0.1%, 0.5%, 1%, and 2%; and/or at most about any of the following: 10%, 7.5%, 5%, and 4%.
- the intercalated layered silicate may have a peak degradation temperature of at least about any of the following: 360, 380, 390, 395, 400, 405, 410, 420, 430, and 440° C.; and/or at most about any of the following: 380, 390, 395, 400, 405, 410, 420, 430, 440, and 450° C.
- the intercalated layered silicate may have an onset temperature of degradation of at least about any of the following: 200, 210, 220, 230, 240, 250, and 280° C.; and/or at most about any of the following: 220, 230, 240, 250, 280, and 300° C.
- the peak degradation temperature and onset temperature of degradation may be determined by thermogravimetric analysis (TGA) of the sample operating at a 20° C. per minute scan rate from room temperature to 800° C. in an argon purged atmosphere, and utilizing first derivative of weight loss analysis.
- TGA thermogravimetric analysis
- a useful TGA machine for such analysis is the TGA Q50 model available from TA Instruments, Inc.
- the intercalated layered silicate may be exfoliated to form a dispersed-particle composition comprising a plurality of dispersed particles comprising exfoliated silicate platelets dispersed within a matrix medium.
- the dispersed particles may comprise silicate platelets having sorbed intercalating agent of the type previously discussed.
- the matrix medium may comprise one or more polymers, for example, one or more thermoplastic polymers, such as one or more polymers selected from polyolefin, ethylene/vinyl alcohol copolymer, ionomer, vinyl plastic, polyamide, polyester, and polystyrene.
- thermoplastic polymers such as one or more polymers selected from polyolefin, ethylene/vinyl alcohol copolymer, ionomer, vinyl plastic, polyamide, polyester, and polystyrene.
- the matrix medium may comprise one or more energy curable polymer precursors, for example, one or more energy curable precursors selected from multifunctional acrylates or methacrylates, thiol-ene systems, epoxy/amine or epoxy polyol systems, and polyurethane precursors such as isocyanates and polyols.
- energy curable polymer precursors for example, one or more energy curable precursors selected from multifunctional acrylates or methacrylates, thiol-ene systems, epoxy/amine or epoxy polyol systems, and polyurethane precursors such as isocyanates and polyols.
- the matrix medium may comprise one or more compounds useful in the formulation of paints, coatings, varnishes, greases, cosmetics, or pharmaceutical excipients (either topical or internal).
- the matrix medium may comprise one or more polyolefins.
- Exemplary polyolefins include ethylene homo- and co-polymers and propylene homo- and co-polymers.
- the term “polyolefins” includes copolymers that contain at least 50 mole % monomer units derived from olefin.
- Ethylene homopolymers include high-density polyethylene (“HDPE”) and low density polyethylene (“LDPE”).
- Ethylene copolymers include ethylene/alpha-olefin copolymers (“EAOs”), ethylene/unsaturated ester copolymers, and ethylene/(meth)acrylic acid.
- EAOs ethylene/alpha-olefin copolymers
- Copolymer as used in this application means a polymer derived from two or more types of monomers, and includes terpolymers, etc.
- EAOs are copolymers of ethylene and one or more alpha-olefins, the copolymer having ethylene as the majority mole-percentage content.
- the comonomer may include one or more C 3 -C 20 ⁇ -olefins, one or more C 4 -C 12 ⁇ -olefins, and one or more C 4 -C 8 ⁇ -olefins.
- Useful ⁇ -olefins include 1-butene, 1-hexene, 1-octene, and mixtures thereof.
- Exemplary EAOs include one or more of the following: 1) medium density polyethylene (“MDPE”), for example having a density of from 0.926 to 0.94 g/cm3; 2) linear medium density polyethylene (“LMDPE”), for example having a density of from 0.926 to 0.94 g/cm3; 3) linear low density polyethylene (“LLDPE”), for example having a density of from 0.915 to 0.930 g/cm3; 4) very-low or ultra-low density polyethylene (“VLDPE” and “ULDPE”), for example having density below 0.915 g/cm3, and 5) homogeneous EAOs.
- MDPE medium density polyethylene
- LLDPE linear medium density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very-low or ultra-low density polyethylene
- ULDPE ultra-low density polyethylene
- Useful EAOs include those having a density of less than about any of the following: 0.925, 0.922, 0.92, 0.917, 0.915, 0.912, 0.91, 0.907, 0.905, 0.903, 0.9, and 0.898 grams/cubic centimeter. Unless otherwise indicated, all densities herein are measured according to ASTM DI 505.
- the polyethylene polymers may be either heterogeneous or homogeneous. As is known in the art, heterogeneous polymers have a relatively wide variation in molecular weight and composition distribution. Heterogeneous polymers may be prepared with, for example, conventional Ziegler-Natta catalysts.
- homogeneous polymers are typically prepared using metallocene or other single-site catalysts. Such single-site catalysts typically have only one type of catalytic site, which is believed to be the basis for the homogeneity of the polymers resulting from the polymerization.
- Homogeneous polymers are structurally different from heterogeneous polymers in that homogeneous polymers exhibit a relatively even sequencing of comonomers within a chain, a mirroring of sequence distribution in all chains, and a similarity of length of all chains. As a result, homogeneous polymers have relatively narrow molecular weight and composition distributions.
- homogeneous polymers examples include the metallocene-catalyzed linear homogeneous ethylene/alpha-olefin copolymer resins available from the Exxon Chemical Company (Baytown, Tex.) under the EXACT trademark, linear homogeneous ethylene/alpha-olefin copolymer resins available from the Mitsui Petrochemical Corporation under the TAFMER trademark, and long-chain branched, metallocene-catalyzed homogeneous ethylene/alpha-olefin copolymer resins available from the Dow Chemical Company under the AFFINITY trademark.
- ethylene/unsaturated ester copolymer is the copolymer of ethylene and one or more unsaturated ester monomers.
- Useful unsaturated esters include: 1) vinyl esters of aliphatic carboxylic acids, where the esters have from 4 to 12 carbon atoms, and 2) alkyl esters of acrylic or methacrylic acid (collectively, “alkyl(meth)acrylate”), where the esters have from 4 to 12 carbon atoms.
- first (“vinyl ester”) group of monomers include vinyl acetate, vinyl propionate, vinyl hexanoate, and vinyl 2-ethylhexanoate.
- the vinyl ester monomer may have from 4 to 8 carbon atoms, from 4 to 6 carbon atoms, from 4 to 5 carbon atoms, and preferably 4 carbon atoms.
- alkyl(meth)acrylate Representative examples of the second (“alkyl(meth)acrylate”) group of monomers include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, hexyl acrylate, and 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate.
- the alkyl(meth)acrylate monomer may have from 4 to 8 carbon atoms, from 4 to 6 carbon atoms, and preferably from 4 to 5 carbon atoms.
- the unsaturated ester (i.e., vinyl ester or alkyl (meth)acrylate)comonomer content of the ethylene/unsaturated ester copolymer may range from about 6 to about 18 weight %, and from about 8 to about 12 weight %, based on the weight of the copolymer.
- Useful ethylene contents of the ethylene/unsaturated ester copolymer include the following amounts: at least about 82 weight %, at least about 85 weight %, at least about 88 weight %, no greater than about 94 weight %, no greater than about 93 weight %, and no greater than about 92 weight %, based on the weight of the copolymer.
- ethylene/unsaturated ester copolymers include ethylene/methyl acrylate, ethylene/methyl methacrylate, ethylene/ethyl acrylate, ethylene/ethyl methacrylate, ethylene/butyl acrylate, ethylene/2-ethylhexyl methacrylate, and ethylene/vinyl acetate.
- ethylene/(meth)acrylic acid is the copolymer of ethylene and acrylic acid, methacrylic acid, or both.
- Useful propylene copolymer includes: 1) propylene/ethylene copolymers (“EPC”), which are copolymers of propylene and ethylene having a majority weight % content of propylene, such as those having an ethylene comonomer content of less than 15%, less than 6%, and at least about 2% by weight and 2) propylene/butene copolymers having a majority weight % content of propylene.
- EPC propylene/ethylene copolymers
- Ethylene/vinyl alcohol copolymer (“EVOH”) is another useful thermoplastic.
- EVOH may have an ethylene content of about 32 mole %, or at least about any of the following values: 20 mole %, 25 mole %, and 30 mole %.
- EVOH may have an ethylene content of below about any of the following values: 50 mole %, 40 mole %, and 33 mole %.
- EVOH may be derived by saponifying or hydrolyzing ethylene/vinyl acetate copolymers, for example, to a degree of hydrolysis of at least about any of the following values: 50%, 85%, and 98%.
- thermoplastic is ionomer, which is a copolymer of ethylene and an ethylenically unsaturated monocarboxylic acid having the carboxylic acid groups partially neutralized by a metal ion, such as sodium or zinc.
- metal ion such as sodium or zinc.
- Useful ionomers include those in which sufficient metal ion is present to neutralize from about 10% to about 60% of the acid groups in the ionomer.
- the carboxylic acid is preferably “(meth)acrylic acid”—which means acrylic acid and/or methacrylic acid.
- Useful ionomers include those having at least 50 weight % and preferably at least 80 weight % ethylene units.
- Useful ionomers also include those having from 1 to 20 weight percent acid units.
- Useful ionomers are available, for example, from Dupont Corporation (Wilmington, Del.) under the SURLYN trademark.
- Useful vinyl plastics include polyvinyl chloride (“PVC”), vinylidene chloride polymer (“PVdC”), and polyvinyl alcohol (“PVOH”).
- Polyvinyl chloride (“PVC”) refers to a vinyl chloride-containing polymer or copolymer—that is, a polymer that includes at least 50 weight percent monomer units derived from vinyl chloride (CH 2 ⁇ CHCl) and also, optionally, one or more comonomer units, for example, derived from vinyl acetate.
- One or more plasticizers may be compounded with PVC to soften the resin and/or enhance flexibility and processibility. Useful plasticizers for this purpose are known in the art.
- PVdC vinylidene chloride polymer
- VdC vinylidene chloride polymer
- a vinylidene chloride-containing polymer or copolymer that is, a polymer that includes monomer units derived from vinylidene chloride (CH 2 ⁇ CCl 2 ) and also, optionally, monomer units derived from one or more of vinyl chloride, styrene, vinyl acetate, acrylonitrile, and C 1 -C 12 alkyl esters of (meth)acrylic acid (e.g., methyl acrylate, butyl acrylate, methyl methacrylate).
- PVdC vinylidene chloride polymer
- (meth)acrylic acid refers to both acrylic acid and/or methacrylic acid
- (meth)acrylate refers to both acrylate and methacrylate.
- PVdC include one or more of the following: vinylidene chloride homopolymer, vinylidene chloride/vinyl chloride copolymer (“VDC/VC”), vinylidene chloride/methyl acrylate copolymer (“VDC/MA”), vinylidene chloride/ethyl acrylate copolymer, vinylidene chloride/ethyl methacrylate copolymer, vinylidene chloride/methyl methacrylate copolymer, vinylidene chloride/butyl acrylate copolymer, vinylidene chloride/styrene copolymer, vinylidene chloride/acrylonitrile copolymer, and vinylidene chloride/vinyl acetate copolymer.
- Useful PVdC includes that having at least about 75, at most about 95, and at most about 98 weight % vinylidene chloride monomer.
- Useful PVdC (for example, as applied by latex emulsion coating) includes that having at least about any of 5%, 10%, and 15%—and/or at most about any of 25%, 22%, 20%, and 15 weight %—comonomer with the vinylidene chloride monomer.
- a layer that includes PVdC may also include a thermal stabilizer (e.g., a hydrogen chloride scavenger such as epoxidized soybean oil) and a lubricating processing aid (e.g., one or more acrylates).
- a thermal stabilizer e.g., a hydrogen chloride scavenger such as epoxidized soybean oil
- a lubricating processing aid e.g., one or more acrylates
- Useful polyamides include those of the type that may be formed by the polycondensation of one or more diamines with one or more diacids and/or of the type that may be formed by the polycondensation of one or more amino acids and/or of the type formed by the ring opening of cyclic lactams.
- Useful polyamides include aliphatic polyamides and aliphatic/aromatic polyamides.
- Representative aliphatic diamines for making polyamides include those having the formula: H 2 N(CH 2 ) n NH 2 where n has an integer value of 1 to 16.
- Representative examples include trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, hexadecamethylenediamine.
- Representative aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′ diaminodiphenyl sulphone, 4,4′-diaminodiphenylethane.
- Representative alkylated diamines include 2,2-dimethylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4 trimethylpentamethylenediamine.
- Representative cycloaliphatic diamines include diaminodicyclohexylmethane.
- Other useful diamines include heptamethylenediamine, nonamethylenediamine, and the like.
- diacids for making polyamides include dicarboxylic acids, which may be represented by the general formula: HOOC-Z-COOH where Z is representative of a divalent aliphatic or cyclic radical containing at least 2 carbon atoms.
- Representative examples include aliphatic dicarboxylic acids, such as adipic acid, sebacic acid, octadecanedioic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, and glutaric acid; and aromatic dicarboxylic acids, such as such as isophthalic acid and terephthalic acid.
- Representative aliphatic/aromatic polyamides include poly(tetramethylenediamine-co-isophthalic acid) (“nylon-4,1”), polyhexamethylene isophthalamide (“nylon-6,1”), polyhexamethylene terephthalamide (“nylon-6,T”), poly (2,2,2-trimethyl hexamethylene terephthalamide), poly(m-xylylene adipamide) (“nylon-MXD,6”), poly(p-xylylene adipamide), poly(hexamethylene terephthalamide), poly(dodecamethylene terephthalamide), and polyamide-MXD,I.
- poly(4-aminobutyric acid) (“nylon-4”), poly(6-aminohexanoic acid) (“nylon-6” or “poly(caprolactam)”), poly(7-aminoheptanoic acid) (“nylon-7”), poly(8-aminooctanoic acid) (“nylon-8”), poly(9-aminononanoic acid) (“nylon-9”), poly(10-aminodecanoic acid) (“nylon-10“), poly(11-aminoundecanoic acid) (“nylon-11”), and poly(12-aminododecanoic acid) (“nylon-12” or “poly(lauryllactam)”).
- copolyamides include copolymers based on a combination of the monomers used to make any of the foregoing polyamides, such as, nylon-4/6, nylon-6/6, nylon-6/9, nylon-6/12, caprolactam/hexamethylene adipamide copolymer (“nylon-6,6/6”), hexamethylene adipamide/caprolactam copolymer (“nylon-6/6,6”), trimethylene adipamide/hexamethylene azelaiamide copolymer (“nylon-trimethyl 6,2/6,2”), hexamethylene adipamide-hexamethylene-azelaiamide caprolactam copolymer (“nylon-6,6/6,9/6”), hexamethylene adipamide/hexamethylene-isophthalamide (“nylon-6,6/6,I”), hexamethylene adipamide/hexamethyleneterephthalamide (“nylon-6,6/6,T”), nylon-6,T/6,I, nylon-6/MXD,T
- Polyamide copolymers may include the most prevalent polymer unit in the copolymer (e.g., hexamethylene adipamide as a polymer unit in the copolymer nylon-6,6/6) in mole percentages ranging from any of the following: at least about 50%, at least about 60%, at least about 70%, at least about 80%, and at least about 90%, and the ranges between any of the forgoing values (e.g., from about 60 to about 80%); and may include the second most prevalent polymer unit in the copolymer (e.g., caprolactam as a polymer unit in the copolymer nylon-6,6/6) in mole percentages ranging from any of the following: less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, and the ranges between any of the forgoing values (e.g., from about 20 to about 40%).
- the most prevalent polymer unit in the copolymer e.g., hexamethylene adipamide as
- Useful polyamides include those that are approved by the controlling regulating agency (e.g., the U.S. Food and Drug Agency) for either direct contact with food and/or for use in a food packaging film, at the desired conditions of use.
- the controlling regulating agency e.g., the U.S. Food and Drug Agency
- Useful polyesters include those made by: 1) condensation of polyfunctional carboxylic acids with polyfunctional alcohols, 2) polycondensation of hydroxycarboxylic acid, and 3) polymerization of cyclic esters (e.g., lactone).
- Exemplary polyfunctional carboxylic acids include aromatic dicarboxylic acids and derivatives (e.g., terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate) and aliphatic dicarboxylic acids and derivatives (e.g., adipic acid, azelaic acid, sebacic acid, oxalic acid, succinic acid, glutaric acid, dodecanoic diacid, 1,4-cyclohexane dicarboxylic acid, dimethyl-1,4-cyclohexane dicarboxylate ester, dimethyl adipate).
- Useful dicarboxylic acids also include those discussed above in the polyamide section.
- polyesters may be produced using anhydrides and esters of polyfunctional carboxylic acids.
- Exemplary polyfunctional alcohols include dihydric alcohols (and bisphenols) such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3 butanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, poly(tetrahydroxy-1,1′-biphenyl, 1,4-hydroquinone, and bisphenol A.
- dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3 butanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, poly(tetrahydroxy-1,1′-biphenyl
- Exemplary hydroxycarboxylic acids and lactones include 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, pivalolactone, and caprolactone.
- polyesters include homopolymers and copolymers. These may be derived from one or more of the constituents discussed above. Exemplary polyesters include poly(ethylene terephthalate) (“PET”), poly(butylene terephthalate) (“PBT”), and poly(ethylene naphthalate) (“PEN”). If the polyester includes a mer unit derived from terephthalic acid, then such mer content (mole %) of the diacid component of the polyester may be at least about any the following: 70, 75, 80, 85, 90, and 95%.
- PET poly(ethylene terephthalate)
- PBT poly(butylene terephthalate)
- PEN poly(ethylene naphthalate)
- the polyester may be thermoplastic.
- the polyester (e.g., copolyester) of the film may be amorphous, or may be partially crystalline (semi-crystalline), such as with a crystallinity of at least about, or at most about, any of the following weight percentages: 10, 15, 20, 25, 30, 35, 40,and 50%.
- the matrix medium may comprise polystyrene.
- Exemplary polysytrene includes stryrene homo- and co-polymers.
- Polystyrene may be substantially atactic, syndiotactic or isotactic.
- the term “polysytrene” includes copolymer that contains at least 50 mole % monomer units derived from styrene.
- Styrene may be copolymerized with alkyl acrylates, maleic anhydride, isoprene, or butadiene. Styrene copolymers with isoprene and butadiene may be further hydrogenated.
- the matrix medium may comprise one or more energy curable polymer precursors.
- An energy curable polymer precursor is a compound (e.g., monomer or oligomer) that is intended for transformation to a cured polymer by the application of energy in the form of heat and/or radiation (e.g., light), and may also involve an initiator and/or catalyst.
- the resulting energy cured polymer may be a thermoset polymer or a thermoplastic polymer.
- a single energy curable polymer precursor may react to form a polymer, or two or more energy curable polymer precursors may react together to form a polymer.
- the energy curable polymer precursor may be multifunctional, that is, adapted to form crosslinked polymer when cured.
- the energy curable chemical reaction may be induced by heat, catalyst interaction, radiation (e.g., light), or mixing of the energy curable polymer precursors.
- Useful energy curable polymer precursors may include one or more of the energy curable polymer precursors that are precursors to one or more of the following polymers: polyester resins (e.g., alkyd resin), allyl resins (e.g., diallyl phthalate, diallyl isophtahalate, diallyl maleate, and diallyl chlorendate), amino resins (e.g., urea resins, melamine resins, and their copolymers with formaldehyde), epoxy resins, furan resins, phenolic resins (e.g., phenol-aralkyl resins, phenol-formaldehyde resins), polyacrylic ester resins, polyamide resins, polyurethane resins, polyacrylamide resins, polyimide resins, and acrylamide resins.
- polyester resins e.g., alkyd resin
- allyl resins e.g., diallyl phthalate, diallyl isophtahalate, dial
- Exemplary energy curable polymer precursors may include (meth)acrylates (i.e., methacrylates and/or acrylates), multifunctional (meth)acrylates, thiol-ene systems, and maleimides.
- Exemplary energy curable polymer precursors may include polyols and polyisocyanates (e.g., toluene diisocyanate and diphenyl-methanediisocyanate).
- polyisocyanates e.g., toluene diisocyanate and diphenyl-methanediisocyanate.
- the intercalated layered silicate may be mixed with the polyol precursor component rather than the more reactive component to help minimize premature reaction.
- the matrix medium may comprise one or more compounds useful in the formulation of one or more of any of the following: coatings (i.e., paints and/or varnishes), inks, greases, cosmetics, and pharmaceutical dosage forms.
- coatings i.e., paints and/or varnishes
- inks i.e., greases, cosmetics, and pharmaceutical dosage forms.
- the matrix medium may comprise one or more materials selected from coating (i.e., paint and/or varnish) solvents, coating binders, and coating resins.
- coating solvents, coating binders, and coating resins are known to those of skill in the art; see, for example, those discussed in Paints and Coatings, Ullmann's Encyclopedia of Industrial Chemistry, Volume 24, pages 591-790 (2003 Wiley-VCH), of which pages 591-790 are incorporated herein by reference. Examples include mineral spirits, toluene, and linseed oil.
- the matrix medium may comprise one or more materials selected from ink solvents and ink resins (e.g., ink binders and/or ink vehicles).
- ink solvents and ink resins e.g., ink binders and/or ink vehicles.
- Useful ink solvents and ink resins are known to those of skill in the art; see, for example, those discussed in Leach and Pierce, The Printing Ink Manual (5 th edition 1993), which is incorporated herein in its entirety.
- the matrix medium may comprise one or more materials selected from grease lubricating oils and grease gelling agents.
- Useful grease lubricating oils and grease gelling agents are known to those of skill in the art; see, for example, those discussed in Kirk-Othmer Encyclopedia of Chemical Technology, Volume 15, pages 493-98 (4 th edition 1995), of which pages 493-98 are incorporated herein by reference.
- the matrix medium may comprise one or more materials useful in the formulation of cosmetics, for example, one or more materials selected from lipids, emollients, humectants, film formers, binders, surfactants, and solvents.
- lipids, emollients, humectants, film formers, binders, surfactants, and solvents are known to those of skill in the art; see, for example, those discussed in Kirk-Othmer Encyclopedia of Chemical Technology, Volume 7, pages 572-619 (4 th edition 1993), of which pages 572-619 are incorporated herein by reference, and CTFA International Cosmetic Ingredient Handbook, 2 nd edition (CTFA Washington D.C. 1992), which is incorporated herein in its entirety by reference.
- compositions useful in the formulation of pharmaceutical dosage forms include pharmaceutical (e.g., medical) excipients (e.g., carriers).
- the matrix medium may comprise one or more pharmaceutical excipients, for example, one or more excipients adapted for an internal pharmaceutical dosage form and/or adapted for an external pharmaceutical dosage form.
- Useful pharmaceutical excipients are known to those of skill in the art; see, for example, those discussed in Pharmaceutical Dosage Forms, Ullmann's Encyclopedia of Industrial Chemistry, Volume 25, pages 515-547 (2003 Wiley-VCH), of which pages 515-547 are incorporated herein by reference.
- the matrix medium may comprise one or more of water, an oil-in-water emulsion, and a water-in-oil emulsion.
- the dispersed particles in the dispersed-particle composition may have an average size of less than about 100 nm in at least one dimension.
- the particles may have an average aspect ratio (i.e., the ratio of the average largest dimension to the average smallest dimension of the particles) of from about 10 to about 30,000.
- the aspect ratio for particles comprising silicate platelets exfoliated from an intercalated layered silicate may be taken as the length (largest dimension) to the thickness (smallest dimension) of the platelets.
- the aspect ratio may be taken as the length (largest dimension) to the diameter (smallest dimension) of the particle.
- Useful aspect ratios for the dispersed particles include at least about any of the following values: 10; 20; 25; 200; 250; 1,000; 2,000; 3,000; and 5,000; and at most about any of the following values: 25,000; 20,000; 15,000; 10,000; 5,000; 3,000; 2,000; 1,000; 250; 200; 25; and 20.
- the dispersed particles may have an average size in the shortest dimension of at least about any of the following values: 0.5 nm, 0.8 nm, 1 nm, 2, nm, 3 nm, 4 nm, and 5 nm; and at most about any of the following values: 100 nm, 60 nm, 30 nm, 20 nm, 10 nm, 8 nm, 5 nm, and 3 nm, as estimated from transmission electron microscope (“TEM”) images.
- the particles may have an average dimension small enough to maintain optical transparency of the matrix medium in which the particles are dispersed.
- the amount of exfoliated particles dispersed in the dispersed-particle composition may be at least about any of the following values 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, and 10 weight %; and/or may be at most about any of the following values: 50, 40, 30, 20, 15, 10, 8, 6, 5, 4, 3, 2, and 1 weight %, based on the weight of the dispersed-particle composition.
- the amount of exfoliated particles dispersed in the dispersed-particle composition may be at least about any of the following values: 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, and 10 weight parts; and/or may be at most about any of the following values: 100, 80, 60, 50, 40, 30, 20, 15, 10, 8, 6, 5, 4, 3, 2, and 1 weight parts, based on 100 weight parts of matrix medium, for example, based on 100 weight parts of the one or more polymers discussed above.
- the dispersed-particle composition may comprise at least about any of the following: 50, 60, 70, 80, 90, 95, and 98 weight %; and at most about any of the following: 99, 98, 95, 90, 80, 70, and 60 weight %, based on the weight of the dispersed-particle composition of any of the following: 1) the matrix medium, or 2) the one or more polymers, or 3) the energy curable polymer precursors, or 4) the coating solvents, coating binders, or coating resins, or 5) the ink solvents or ink resins, or 6) the grease lubricating oils or grease gelling agents, or 7) the cosmetic lipids, cosmetic emollients, cosmetic humectants, cosmetic film formers, cosmetic binders, cosmetic surfactants, or cosmetic solvents, or 8) pharmaceutical excipients.
- the particles may comprise silicate platelets derived from the intercalated layered silicate and an intercalating agent sorbed to the silicate platelets.
- intercalating agents are discussed above.
- the dispersed-particle composition may be essentially free of intercalating agent comprising onium functionality, such as any one, or of all, or of any combination of the onium compounds discussed above.
- the amount of intercalating agent sorbed to the silicate platelets may be at least about and/or at most about any of the following: 1, 5, 10, 20, 30, 50, 70, 90, 110, 150, 200, and 300 weight parts per 100 weight parts silicate platelets.
- exfoliated particles result when individual silicate layers of a layered silicate are no longer close enough to interact significantly with the adjacent layers via ionic or van der Waals attractions or to form strongly correlated systems due to the large aspect ratios of the platelets.
- An exfoliated layered silicate has lost its registry and may be relatively uniformly and randomly dispersed in a continuous matrix medium. It is believed that the dispersion in a matrix medium occurs when the interlayer spacing of the layered silicate is at or greater than the average radius of gyration of the molecules comprising the matrix medium.
- a dispersing aid may be used to enhance exfoliation of the intercalated layered silicate into the matrix medium.
- exemplary dispersing aids may include one or more of water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, and aromatic solvents.
- the intercalated layered silicate may be exfoliated in a matrix medium to form the dispersed-particle composition.
- the intercalated layered silicate may be added to the matrix medium under conditions effective to exfoliate at least a portion of the intercalated layered silicate into particles comprising silicate platelets dispersed in the matrix medium.
- An amount of intercalated layered silicate mixed with the matrix medium may be at least about any of the following: 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, and 10 weight parts intercalated layered silicate; and/or may be at most about any of the following values: 100, 80, 60, 50, 40, 30, 20, 15, 10, 8, 6, 5, 4, 3, 2, and 1 weight parts intercalated layered silicate, based on 100 weight parts of matrix medium, for example, based on 100 weight parts of the one or more polymers discussed above.
- At least about any of the following amounts of the intercalated layered silicate added to the matrix medium may be dispersed as exfoliated particles having an average size of less than about 100 nm in at least one dimension: 50, 60, 70, 80, 90, 95, 98, and 99 weight parts exfoliated particles per 100 weight parts added intercalated layered silicate.
- the exfoliated silicate platelets may have the average thickness of the individual layers of the layered silicate, or may have as an average thickness multiples of less than about any of 10, 5, and 3 layers of the layered silicate.
- TEM images may be used to estimate the amount and size and characteristics of the exfoliated particles.
- the effective exfoliation conditions may include the addition of mixing and/or shearing energy to the mixture of the intercalated layered silicate and the matrix medium.
- the process variables for exfoliating the intercalated layered silicate in the matrix medium include time, temperature, geometry of the mixing apparatus, and the shear rate, and generally requires a balance of these variables, as is known to those of skill in the art.
- the balancing of these variables may take into account the desire to minimize the physical degradation or decomposition of the matrix medium and/or the intercalating agent, for example, by limiting the upper temperature of the processing and/or the amount of time at a selected temperature during processing.
- An increase in temperature generally provides more thermal energy to enhance exfoliation.
- a decrease in temperature may lower the viscosity of the mixture while increasing the shear rate.
- An increase in shear rate generally enhances exfoliation. Shear rates of at least about any of the following may be applied to the mixture of the intercalated layered silicate and the matrix medium: 1 sec ⁇ 1 , 10 sec ⁇ 1 , 50 sect1, 100 sec ⁇ 1 , and 300 sec ⁇ 1 .
- Illustrative methods or systems for applying shear to effect exfoliation of the intercalated layered silicate in the matrix medium include mechanical systems, thermal shock, pressure alternation, and ultrasonics.
- a flowable mixture may be sheared by mechanical methods, such as the use of stirrers, blenders, Banbury type mixers, Brabender type mixers, long continuous mixers, injection molding machines, and extruders.
- Twin screw extruders may be useful, for example, for mixing the intercalated layered silicate with a thermoplastic matrix medium.
- a thermal shock method achieves shearing by alternatively raising and lowering the temperature of the mixture to cause thermal expansions and contractions to induce internal stresses that cause shear. Sudden and alternating pressure changes may also be used to apply shear to the mixture.
- Ultrasonic methods induce shear by cavitation or resonant vibrations, which cause varying portions of the mixture to vibrate and become excited at different phases.
- the effective exfoliation conditions may comprise raising the temperature of the matrix medium, for example a matrix medium comprising one or more thermoplastic polymers, so that the matrix medium is thermally processible at a reasonable rate in the mechanical system either before, while, or after adding the intercalated layered silicate to the matrix medium.
- the mixture of the intercalated layered silicate and the matrix medium may be at a temperature, for example, of at least about and/or at most about any of the following temperatures: 100° C., 150° C., 200° C., 240° C., 280° C., 300° C., 320° C., 350° C., 380° C., and 400° C.
- the amount of residence time that the mixture of the intercalated layered silicate and the matrix medium may reside at any of these temperatures may be at least about and/or at most about any of the following times: 2, 4, 5, 8, 10, 12, 15, and 20 minutes.
- the layered silicate Before effecting exfoliation, the layered silicate may be reduced in size by methods known in the art, including, but not limited to, grinding, pulverizing, hammer milling, jet milling, and their combinations, so that the average particle diameter of the layered silicate may be, for example, less than about any of 100, 50, and 20 microns.
- the dispersed particles may be used to enhance the physical and/or performance properties of the matrix medium in which they are dispersed.
- the dispersed particles may improve one or more of the modulus, strength, permeability, rheological, and surface adhesion properties of the matrix medium incorporating the particles relative to the matrix medium without the particles.
- dispersed-particle composition Several types of products may benefit from incorporation of the dispersed-particle composition to improve, for example, performance properties.
- exemplary products that may comprise the dispersed-particle composition include:
- sheets and panels which, for example, may be further shaped by pressing, molding, and/or thermoforming to form useful objects;
- coatings i.e., paints and/or varnishes
- lubricants for example, food-grade lubricants
- cosmetics e.g., antiperspirants, deodorants, facial makeup, decorative makeup, toothpastes, shampoos, soaps, skin conditioners, skin moisturizers, and sunscreens
- cosmetics e.g., antiperspirants, deodorants, facial makeup, decorative makeup, toothpastes, shampoos, soaps, skin conditioners, skin moisturizers, and sunscreens
- topical medicinal compositions e.g., anti-fungal compositions, anti-bacterial compositions, anesthetics, anti-inflammatory compositions, pain-relief ointments, and rash/itch/irritation ointments
- internal medicinal compositions e.g., pills, tablets, capsules, powders, and solutions
- packaging materials such as packaging films (e.g., shrink films, stretch films, and food packaging films), bottles, trays, and containers.
- packaging films e.g., shrink films, stretch films, and food packaging films
- a packaging film may comprise one or more layers comprising any of the dispersed-particle compositions discussed above.
- the film may have any total thickness as long as it provides the desired properties (e.g., free shrink, shrink tension, flexibility, Young's modulus, optics, strength, barrier) for the given application of expected use.
- the film may have a thickness of less than about any of the following: 20 mils, 10 mils, 5 mils, 4 mils, 3 mils, 2 mils, 1.5 mils, 1.2 mils, and 1 mil.
- the film may also have a thickness of at least about any of the following: 0.25 mils, 0.3 mils, 0.35 mils, 0.4 mils, 0.45 mils, 0.5 mils, 0.6 mils, 0.75 mils, 0.8 mils, 0.9 mils, 1 mil, 1.2 mils, 1.4 mils, 1.5 mils, 2 mils, 3 mils, and 5 mils.
- the film may be monolayer or multilayer.
- the film may comprise at least any of the following number of layers: 1, 2, 3, 4, 5, 6, 7, 8, and 9.
- the film may comprise at most any of the following number of layers: 20, 15, 10, 9, 7, 5, 3, 2, and 1.
- the term “layer” refers to a discrete film component which is coextensive with the film and has a substantially uniform composition. Any of the layers of the film may have a thickness of at least about any of the following: 0.05, 0.1, 0.2, 0.5, 1, 2, and 3 mil. Any of the layers of the film may have a thickness of at most about any of the following:. 20, 10, 5, 2, 1, and 0.5 mils.
- any of the layers of the film may have a thickness as a percentage of the total thickness of the film of at least about any of the following values: 1, 3, 5, 7, 10, 15, 20, 30, 40, 50, 60, 70, 80, and 90%. Any of the layers of the film may have a thickness as a percentage of the total thickness of the film of at most about any of the following values: 90, 80, 50, 40, 35, 30, 25, 20, 15, 10, and 5%.
- a layer of the film may comprise at least about and/or at most about any of the following amounts of dispersed-particle composition based on the layer weight: 0.1, 0.5, 1, 3, 5, 10, 20, 50, 60, 70, 80, 90, 95, 99, and 100 weight %.
- a layer of the film comprising any of the foregoing amounts of dispersed-particle composition may also have a thickness of at least about, and/or at most about, any of the following percentages based on the total thickness of the film: 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, and 5%.
- a layer comprising the dispersed-particle composition may be an outer layer of the film.
- An outer layer may be an “outside layer” of the film (i.e., an outer layer adapted or designed to face to the outside of a package incorporating the film) or an “inside layer” of the film (i.e., an outer layer adapted or designed to face the inside of a package incorporating the film). If the film comprises only one layer, then the one layer may be considered an “outer layer.”
- a layer comprising the dispersed-particle composition may be an inner or interior layer of the film. An inner or interior layer of the film is between two outer layers of the film.
- an internal tie layer of a film such as disclosed in U.S. patent application Ser. No. 10/452892 filed Jun. 2, 2003 by Grah et al, which is incorporated herein in its entirety by reference, may comprise the dispersed-particle composition discussed above.
- the film comprising the dispersed-particle composition may be formed into a package (e.g., bag or casing) for packaging (e.g., enclosing) an object such as a food product (e.g., coffee, nuts, snack foods, cheese, ground or processed meat products, fresh red meat products, and more specifically, meats such as poultry, pork, beef, sausage, lamb, goat, horse, and fish).
- a food product e.g., coffee, nuts, snack foods, cheese, ground or processed meat products, fresh red meat products, and more specifically, meats such as poultry, pork, beef, sausage, lamb, goat, horse, and fish.
- the package may be formed by sealing the film to itself, or by sealing the film to a support member (e.g., a tray, cup, or tub), which supports the product (e.g., a food product) that may be disposed on or in the support member.
- Seals may be made by adhesive or heat sealing, such as bar, impulse, radio frequency (“RF”) or dielectric sealing.
- Suitable package configurations include end-seal bag, side-seal bag, L-seal bag, pouch, and seamed casing (e.g., back-seamed tubes by forming an overlap or fin-type seal). Such configurations are known to those of skill in the art.
- the support member e.g., tray
- the support member may also comprise any of the dispersed-particle compositions discussed above.
- the support member may also comprise a thermoformed web comprising a thermoplastic.
- the package may also be formed by laminating or sealing the film comprising the dispersed-particle composition to another substrate.
- Suitable substrates may comprise: 1) a film comprising one or more of the following materials: polyester (e.g., PET), metalized polyester (e.g., metalized PET), PVdC-coated PET, polypropylene (e.g., biaxially oriented polypropylene or BOPP), metalized BOPP, PVdC, and coated BOPP, 2) paper, 3) paperboard, and 4) metal foil.
- a composite packaging structure may also be formed by extrusion coating of one or more polymer layers, any or all of which may comprise the dispersed-particle composition, to any of the above substrates.
- one end of the tube may be closed by tying, clipping (e.g., metal clips), or sealing.
- the tube may then be filled through the remaining open end with an uncooked food product (e.g., a sausage emulsion or another flowable meat product).
- the remaining open end may then be closed by tying, clipping, or sealing to form a package enclosing a food product.
- This filling procedure may take place, for example, by vertical form-fill-seal or horizontal form-fill-seal processes known to those of skill in the art.
- the packaged food product enclosed within the package comprising the film comprising the dispersed-particle composition may be processed (e.g., cooked, retorted, or pasteurized) for example, by immersing the packaged food in a liquid hot water bath, exposing the packaged food to steam, or exposing the packaged food to hot air, for an effective amount of time and at an effective temperature and pressure. This exposure may also shrink the package tightly about the enclosed food product by heat shrinking the film.
- the packaged food may also be exposed to an amount of radiation such as microwave radiation effective to cook the packaged food. After the food product has been processed (e.g., cooked or retorted) to a desired level, the packaged food may be sold in the packaged form, or the package may be stripped from the cooked food so the food may be processed further or consumed.
- a film comprising the dispersed-particle composition may be manufactured by thermoplastic film-forming processes known in the art.
- the film may be prepared by extrusion or coextrusion utilizing, for example, a tubular trapped bubble film process or a flat film (i.e., cast film or slit die) process.
- the film may also be prepared by extrusion coating.
- the film may be prepared by adhesively or extrusion laminating the various layers. These processes are known to those of skill in the art. A combination of these processes may also be employed.
- a film comprising the dispersed-particle composition may be non-oriented.
- a film comprising the dispersed-particle composition may be oriented in either the machine (i.e., longitudinal), the transverse direction, or in both directions (i.e., biaxially oriented), in order to reduce the permeability and/or to enhance the strength, optics, and durability of the film.
- the orientation of the film may also enhance the orientation of the silicate platelets of the dispersed-particle composition, so that generally the major plane through the platelets is substantially parallel to the major plane through the film.
- the film may be oriented in at least one direction by at least about any of the following ratios: 2.5:1, 3:1, 3.5:1, and 3.7:1; and/or by at most about 10:1.
- a film comprising the dispersed-particle composition may be non-heat shrinkable—for example, having a free shrink in any direction at 185° F. (85° C.) of less than about any of the following: 4%, 3%, 1%, and 0.5%.
- a film comprising the dispersed-particle composition may be heat shrinkable (i.e., has a shrink characteristic), which as used herein, means that the film has a free shrink at 185° F. (85° C.) in at least one direction of at least about 5% at 185° F.
- film comprising the dispersed-particle composition may have a free shrink at 185° F.
- the film may have any of the preceding free shrink values measured at a temperature selected from any of 200° F., 220° F., 240° F., 260° F., and 280° F.
- the film may have unequal free shrink in both directions, that is differing free shrink in the machine and transverse directions.
- the film may have a free shrink (185° F.) in the machine direction of at least 40% and a free shrink (185° F.) in the transverse direction of at least 25%.
- the film may not have a heat shrink characteristic in both directions.
- the film may have a free shrink at 185° F. in one direction of less than about any of the following: 5%, 4%, 3%, 2% and 1%; or the film may have 0% free shrink at 185° F. in one direction.
- the free shrink of the film is determined by measuring the percent dimensional change in a 10 cm ⁇ 10 cm film specimen when subjected to selected heat (i.e., at a specified temperature exposure) according to ASTM D 2732, which is incorporated herein in its entirety by reference. All references to free shrink in this application are measured according to this standard.
- a heat-shrinkable film shrinks upon the application of heat while the film is in an unrestrained state. If the film is restrained from shrinking to some extent—for example by a packaged product around which the film shrinks—then the tension of the heat-shrinkable film increases upon the application of heat. Accordingly, a heat-shrinkable film that has been exposed to heat so that at least a portion of the film is either reduced in size (unrestrained) or under increased tension (restrained) is considered a heat-shrunk (i.e., heat-contracted) film.
- a film comprising the dispersed-particle composition may exhibit a shrink tension at 185° F. in at least one direction of at least about, and/or at most about, any of the following: 100 psi, 150 psi, 175 psi, 200 psi, 225 psi, 250 psi, 275 psi, 300 psi, 325 psi, 350 psi, 400 psi, 450 psi, 500 psi, 550 psi, and 600 psi.
- the film may have any of the preceding shrink tensions measured at a temperature selected from any of 200° F., 220° F., 240° F., 260° F., and 280° F.
- the film may have unequal shrink tension in both directions, that is differing shrink tension in the machine and transverse directions.
- the film may not have a shrink tension in one or both directions.
- Shrink tension is measured at a specified temperature (e.g., 185° F.) in accordance with ASTM D 2838 (Procedure A), which is incorporated herein in its entirety by reference. All references to shrink tension in this application are by this standard.
- a film comprising the dispersed-particle composition may be annealed or heat-set to reduce the free shrink slightly, substantially, or completely; or the film may not be heat set or annealed once the oriented film has been quenched in order that the film will have a high level of heat shrinkability.
- a film comprising the dispersed-particle composition may have low haze characteristics.
- Haze is a measurement of the transmitted light scattered more than 2.5° from the axis of the incident light. Haze is measured against the outside layer of the film. As previously discussed, the “outside layer” is the outer layer of the film that will be adjacent the area outside of the package comprising the film. Haze is measured according to the method of ASTM D 1003, which is incorporated herein in its entirety by reference. All references to “haze” values in this application are by this standard. The haze of the film may be no more than about any of the following values: 30%, 25%, 20%, 15%, 10%, 8%, 5%, and 3%.
- a film comprising the dispersed-particle composition may have a gloss, as measured against the outside layer of at least about any of the following values: 40%, 50%, 60%, 63%, 65%, 70%, 75%, 80%, 85%, 90%, and 95%. These percentages represent the ratio of light reflected from the sample to the original amount of light striking the sample at the designated angle. All references to “gloss” values in this application are in accordance with ASTM D 2457 (60° angle), which is incorporated herein in its entirety by reference.
- a film comprising the dispersed-particle composition may be transparent (at least in the non-printed regions) so that a packaged article may be visible through the film.
- Transparent means that the film transmits incident light with negligible scattering and little absorption, enabling objects (e.g., the packaged article or print) to be seen clearly through the film under typical viewing conditions (i.e., the expected use conditions of the material).
- the transparency (i.e., clarity) of the film may be at least about any of the following values: 65%, 70%, 75%, 80%, 85%, and 90%, as measured in accordance with ASTM DI 746.
- the average interlayer spacing (i.e., the basal d-spacing) of the resulting intercalated layered silicate (i.e., PEMS intercalated clay) was determined using a BEDE D1 X-ray diffractometer.
- a representative sample of the PEMS intercalated clay was set upon a fritted glass slide for scanning by the diffractometer, which was operated in the powder diffraction mode using a copper X-ray source (X-ray wave-length 0.154 nm) and a sweep of 0.5 to 20 2Theta-Omega.
- the diffraction pattern for the PEMS intercalated clay is shown in FIG. 1 .
- the pattern indicated a diffraction peak or shoulder at a 2 ⁇ of from 1.22° to 1.30°, which calculates to an average interlayer spacing of the layered silicate (i.e., the primary basal d-spacing) of from 68 to 72 ⁇ .
- FIG. 2 shows the diffraction pattern for the non-intercalated montmorillonite clay.
- the pattern indicated a diffraction peak at a 2 ⁇ of 7.42°, which calculates to an average interlayer spacing (i.e., the primary basal d-spacing) for the montmorillonite clay before intercalation of 11.9 ⁇ , measured and calculated as set forth above.
- the inclusion of the PEMS intercalating agent between the silicate layers of the montmorillonite increased the average interlayer spacing of the silicate layers by from about 56.1 to about 60.1 ⁇ .
- Thermogravimetric analysis was obtained for the Example 1 PEMS intercalated montmorillonite clay and the Cloisite 20A intercalated clay describe below as Comparative Sample 1.
- the TGA equipment used was a TGA Q50 model available from TA Instruments, Inc. operating at a 20° C. per minute scan rate from room temperature to 800° C. in an argon purged atmosphere.
- FIG. 8 shows the TGA results for the primary and first derivative of weight loss for the Example 1 PEMS intercalated montmorillonite.
- FIG. 9 shows the TGA results for the primary and first derivative weight loss for the Comparative Sample 1.
- the peak degradation temperature of the Example 1 PEMS intercalated montmorillonite was 399.94° C., which is about 87° C. higher than the 312.92° C. peak degradation temperature of the Comparison Sample 1 intercalated montmorillonite. Further, the onset temperature of degradation for the Example 1 PEMS intercalated montmorillonite was approximately 50° C. higher than for the Comparison Sample 1.
- montmorillonite (Cloisite Na+, Southern Clay Products) was mixed with 100 grams of water in a Hobart mixing bowl at room temperature to form a clay/water slurry.
- PEMS pentaerythritol monostearate
- the resulting mixture was compounded using a Hobart auger extruder at room temperature for 30 minutes and with a rotor rotation speed of 200 rpm to form an intercalated layered silicate, namely, a PEMS intercalated montmorillonite clay.
- the intercalated clay was dried in an 80° C. oven overnight, ground, and sieved through a 325 mesh screen to yield a fine powder of the PEMS intercalated montmorillonite.
- a commercially available dimethyl didehydrogenated tallow quaternary ammonium intercalated montmorillonite (Cloisite 20A) was obtained from Southern Clay Products. The concentration of the intercalating agent was 95 meq/100 g clay. The average interlayer spacing of the intercalated clay was determined as described above with respect to Example 1.
- the diffraction pattern for Cloisite 20A is shown in FIG. 3 . The pattern indicated a diffraction peak at a 2 ⁇ of 3.65°, which calculated to an average interlayer spacing of the layered silicate of 24.2 ⁇ .
- the PEMS intercalated clay of Example 1 was mixed with a matrix medium of linear low density polyethylene (LLDPE) from the Dow Corporation under the Dowlex 2045 trade name.
- LLDPE linear low density polyethylene
- the ratio of the mixture was 5 weight % PEMS intercalated clay to 95 weight % LLDPE matrix medium.
- the mixture was compounded for 45 minutes at 145° C. using a Haake Rheomix 600 Bowl Mixer operating at 55 rpm mixer speed to form the Example 3 dispersed-particle composition.
- the resulting dispersed-particle composition was pressed on a Carver press between two glass plates into a transparent film having a thickness varying from 40 to 100 microns.
- Example 3 dispersed-particle composition using the method described above with respect to Example 1 and is shown in FIG. 4 .
- the PEMS intercalated clay of Example 1 was mixed with a matrix medium of isotactic polypropylene from ExxonMobil Corporation under the Escorene PP-4292 tradename. The ratio of the mixture was 5 weight % PEMS intercalated clay to 95 weight % polypropylene matrix medium. The mixture was compounded for 45 minutes at 170° C. using a Haake Rheomix 600 Bowl Mixer operating at 50 rpm mixer speed to form the Example 4 dispersed-particle composition. The resulting dispersed-particle composition was pressed on a Carver press between two glass plates into a transparent film having a thickness varying from 40 to 100 microns.
- Example 4 dispersed-particle composition using the method described above with respect to Example 1 and is shown in FIG. 5 .
- the PEMS intercalated clay of Example 1 was mixed with a matrix medium of ethylene/vinyl acetate copolymer (EVA) having 28 weight % vinyl acetate content from Exxon Chemical Corporation under the Escorene LD-761 tradename.
- EVA ethylene/vinyl acetate copolymer
- the ratio of the mixture was 5 weight % PEMS intercalated clay to 95 weight % EVA matrix medium.
- the mixture was compounded for 45 minutes at 155° C. using a Haake Rheomix 600 Bowl Mixer-operating at 60 rpm mixer speed to form the Example 5 dispersed-particle composition.
- the resulting dispersed-particle composition was pressed on a Carver press between two glass plates into a transparent film having a thickness varying from 40 to 100 microns.
- Example 5 dispersed-particle composition using the method described above with respect to Example 1 and is shown in FIG. 6 .
- the PEMS intercalated clay of Example 1 was mixed with a matrix medium of nylon-6 polymer (PA6) from BASF Corporation under the Ultramid B35 tradename.
- PA6 nylon-6 polymer
- the ratio of the mixture was 5 weight % PEMS intercalated clay to 95 weight % PA6 matrix medium.
- the mixture was compounded for 45 minutes at 210° C. using a Haake Rheomix 600 Bowl Mixer operating at 50 rpm mixer speed to form the Example 6 dispersed-particle composition.
- the resulting dispersed-particle composition was pressed on a Carver press between two glass plates into a transparent film having a thickness varying from 40 to 100 microns.
- Example 6 dispersed-particle composition using the method described above with respect to Example 1 and is shown in FIG. 7 .
- any numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
- the amount of a component or a value of a process variable e.g., temperature, pressure, time
- the amount of a component or a value of a process variable may range from any of 1 to 90, 20 to 80, or 30 to 70, or be any of at least 1, 20, or 30 and/or at most 90, 80, or 70, then it is intended that values such as 15 to 85, 22 to 68, 43 to 51, and 30 to 32, as well as at least 15, at least 22, and at most 32, are expressly enumerated in this specification.
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Priority Applications (12)
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US11/002,615 US20060122309A1 (en) | 2004-12-02 | 2004-12-02 | Intercalated layered silicate |
BRPI0515820A BRPI0515820B1 (pt) | 2004-12-02 | 2005-12-02 | silicato de camadas intercaladas, método de esfoliar um silicato em camadas, composição de partículas dispersas, alimento embalado, filme de embalagem e processo de embalagem de um alimento |
NZ590183A NZ590183A (en) | 2004-12-02 | 2005-12-02 | Intercalated layered silicate comprising pentaerythritol derivatives as an intercalating agent |
US11/667,424 US8568808B2 (en) | 2004-12-02 | 2005-12-02 | Intercalated layered silicate |
CN2005800475211A CN101120047B (zh) | 2004-12-02 | 2005-12-02 | 插层的层状硅酸盐 |
JP2007544566A JP5033639B2 (ja) | 2004-12-02 | 2005-12-02 | 挿入層状ケイ酸塩 |
CA2586792A CA2586792C (fr) | 2004-12-02 | 2005-12-02 | Silicate en couches intercale |
NZ555071A NZ555071A (en) | 2004-12-02 | 2005-12-02 | Intercalated layered silicate comprising pentaerythritol derivatives as an intercalating agent |
AU2005311657A AU2005311657B2 (en) | 2004-12-02 | 2005-12-02 | Intercalated layered silicate |
AT05848875T ATE509981T1 (de) | 2004-12-02 | 2005-12-02 | Interkaliertes geschichtetes silicat |
PCT/US2005/043741 WO2006060716A1 (fr) | 2004-12-02 | 2005-12-02 | Silicate en couches intercale |
EP05848875A EP1833902B1 (fr) | 2004-12-02 | 2005-12-02 | Silicate en couches intercale |
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AT (1) | ATE509981T1 (fr) |
AU (1) | AU2005311657B2 (fr) |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040223931A1 (en) * | 2003-05-05 | 2004-11-11 | L'oreal | Exfoliated phyllosilicate-based cosmetic compositions |
US20090216207A1 (en) * | 2006-02-10 | 2009-08-27 | Soeren Kirkegaard Nielsen | Biodegradable Barrier Film |
US20090229775A1 (en) * | 2008-03-15 | 2009-09-17 | Fushan Zhang | Clay slurries and use thereof in pulp and papermaking applications |
US20090297568A1 (en) * | 2005-08-19 | 2009-12-03 | Grah Michael D | Intercalated layered silicate |
US20100040653A1 (en) * | 2004-12-02 | 2010-02-18 | Grah Michael D | Intercalated layered silicate |
US20120318700A1 (en) * | 2007-08-24 | 2012-12-20 | Illsley Derek R | Gas barrier coating having improved bond strength |
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WO2018050770A1 (fr) * | 2016-09-15 | 2018-03-22 | Instituto Tecnológico Del Embalaje, Transporte Y Logística (Itene) | Nanocomposite polymère comprenant du polyéthylène téréphtalate renforcé avec un phyllosilicate intercalé |
US20200407226A1 (en) * | 2018-02-02 | 2020-12-31 | Queen's University At Kingston | Graphene Nanoplatelets Derived from Thermomechanical Exfoliation of Graphite |
US11084311B2 (en) * | 2008-02-29 | 2021-08-10 | Illinois Tool Works Inc. | Receiver material having a polymer with nano-composite filler material |
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US7510992B2 (en) * | 2007-06-05 | 2009-03-31 | Amcol International Corporation | Sulfur-impregnated and coupling agent-reacted organoclay mercury and/or arsenic ion removal media |
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US20120328754A1 (en) | 2011-06-21 | 2012-12-27 | Cryovac, Inc. | Impact-Modified Polypropylene Composite |
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US9982067B2 (en) * | 2015-09-24 | 2018-05-29 | Exxonmobil Chemical Patents Inc. | Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports |
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CN111394160B (zh) * | 2020-04-14 | 2022-04-05 | 无锡市宜能石化有限公司 | 一种高性能盾尾密封脂及其制备方法 |
US11932747B2 (en) | 2020-06-24 | 2024-03-19 | Evonik Operations Gmbh | Use of long-chain citric acid esters in aqueous polyurethane dispersions |
USD981844S1 (en) | 2020-11-25 | 2023-03-28 | Berry Global, Inc. | Beverage capsule cup |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4048378A (en) * | 1976-12-08 | 1977-09-13 | Browne Packaging, Inc. | Adhesive laminated packaging materials |
US5358647A (en) * | 1991-01-09 | 1994-10-25 | Colgate-Palmolive Company | Fabric softening products based on a combination of pentaerythritol compound and bentonite |
US5952095A (en) * | 1996-12-06 | 1999-09-14 | Amcol International Corporation | Intercalates and exfoliates formed with long chain (C10 +) monomeric organic intercalant compounds; and composite materials containing same |
US5969092A (en) * | 1997-04-18 | 1999-10-19 | Arizona Chemical Oy | Preparation of a tall oil rosin ester with a low odor level |
US6461423B1 (en) * | 1996-05-29 | 2002-10-08 | Amcol International Corporation | Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composite materials containing same and methods of modifying rheology therewith |
US20020169246A1 (en) * | 1997-12-22 | 2002-11-14 | Eastman Chemical Company | Process for preparing high barrier nanocomposites |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5126060A (en) * | 1991-01-09 | 1992-06-30 | Colgate-Palmolive Co. | Biodegradable fabric softening compositions based on pentaerythritol esters and free of quaternary ammonium compounds |
FR2716372B1 (fr) | 1994-02-18 | 1996-04-12 | Oreal | Compositions cosmétiques antisolaires stables, fluides et/ou fluidifiables, procédé de préparation et utilisation. |
US5760121A (en) | 1995-06-07 | 1998-06-02 | Amcol International Corporation | Intercalates and exfoliates formed with oligomers and polymers and composite materials containing same |
US5804613A (en) | 1995-12-22 | 1998-09-08 | Amcol International Corporation | Intercalates and exfoliates formed with monomeric carbonyl-functional organic compounds, including carboxylic and polycarboxylic acids; aldehydes; and ketones; composite materials containing same and methods of modifying rheology therewith |
EP0780340B1 (fr) * | 1995-12-22 | 2002-03-20 | Amcol International Corporation | Produits d'insertion et d'exfoliation formés avec des composés organiques monomères fonctionnels; matériaux composites les contenant et méthodes pour modifier la rhéologie au moyen de ces matériaux |
US5880197A (en) | 1995-12-22 | 1999-03-09 | Amcol International Corporation | Intercalates and exfoliates formed with monomeric amines and amides: composite materials containing same and methods of modifying rheology therewith |
US6287634B1 (en) | 1995-12-22 | 2001-09-11 | Amcol International Corporation | Intercalates and exfoliates formed with monomeric ethers and esters; composite materials containing same methods of modifying rheology therewith |
BR9707663A (pt) * | 1996-02-23 | 1999-04-13 | Dow Chemical Co | Compósito de polímero |
US6124365A (en) | 1996-12-06 | 2000-09-26 | Amcol Internatioanl Corporation | Intercalates and exfoliates formed with long chain (C6+) or aromatic matrix polymer-compatible monomeric, oligomeric or polymeric intercalant compounds and composite materials containing same |
US6057035A (en) | 1997-06-06 | 2000-05-02 | Triton Systems, Inc. | High-temperature polymer/inorganic nanocomposites |
US6310339B1 (en) * | 1999-10-28 | 2001-10-30 | Hrl Laboratories, Llc | Optically controlled MEM switches |
US6864308B2 (en) * | 2002-06-13 | 2005-03-08 | Basell Poliolefine Italia S.P.A. | Method for making polyolefin nanocomposites |
CN1233742C (zh) | 2002-09-28 | 2005-12-28 | 广东炜林纳功能材料有限公司 | 稀土改性的聚酰胺/蒙脱土复合材料及其制备方法 |
CN1229429C (zh) | 2002-09-28 | 2005-11-30 | 广东炜林纳功能材料有限公司 | 稀土改性的聚烯烃/蒙脱土复合材料及其制备方法 |
KR100581358B1 (ko) | 2002-12-18 | 2006-05-17 | 나노컴 주식회사 | 무적지속성이 우수한 필름용 수지 조성물 및 이를 이용한농업용 필름 |
US20060122309A1 (en) | 2004-12-02 | 2006-06-08 | Grah Michael D | Intercalated layered silicate |
-
2004
- 2004-12-02 US US11/002,615 patent/US20060122309A1/en not_active Abandoned
-
2005
- 2005-12-02 CN CN2005800475211A patent/CN101120047B/zh not_active Expired - Fee Related
- 2005-12-02 NZ NZ590183A patent/NZ590183A/en not_active IP Right Cessation
- 2005-12-02 EP EP05848875A patent/EP1833902B1/fr not_active Not-in-force
- 2005-12-02 NZ NZ555071A patent/NZ555071A/en not_active IP Right Cessation
- 2005-12-02 WO PCT/US2005/043741 patent/WO2006060716A1/fr active Application Filing
- 2005-12-02 AU AU2005311657A patent/AU2005311657B2/en not_active Ceased
- 2005-12-02 AT AT05848875T patent/ATE509981T1/de not_active IP Right Cessation
- 2005-12-02 JP JP2007544566A patent/JP5033639B2/ja not_active Expired - Fee Related
- 2005-12-02 CA CA2586792A patent/CA2586792C/fr not_active Expired - Fee Related
- 2005-12-02 BR BRPI0515820A patent/BRPI0515820B1/pt not_active IP Right Cessation
- 2005-12-02 US US11/667,424 patent/US8568808B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4048378A (en) * | 1976-12-08 | 1977-09-13 | Browne Packaging, Inc. | Adhesive laminated packaging materials |
US5358647A (en) * | 1991-01-09 | 1994-10-25 | Colgate-Palmolive Company | Fabric softening products based on a combination of pentaerythritol compound and bentonite |
US6461423B1 (en) * | 1996-05-29 | 2002-10-08 | Amcol International Corporation | Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composite materials containing same and methods of modifying rheology therewith |
US5952095A (en) * | 1996-12-06 | 1999-09-14 | Amcol International Corporation | Intercalates and exfoliates formed with long chain (C10 +) monomeric organic intercalant compounds; and composite materials containing same |
US5969092A (en) * | 1997-04-18 | 1999-10-19 | Arizona Chemical Oy | Preparation of a tall oil rosin ester with a low odor level |
US20020169246A1 (en) * | 1997-12-22 | 2002-11-14 | Eastman Chemical Company | Process for preparing high barrier nanocomposites |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
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US20040223931A1 (en) * | 2003-05-05 | 2004-11-11 | L'oreal | Exfoliated phyllosilicate-based cosmetic compositions |
US8568808B2 (en) | 2004-12-02 | 2013-10-29 | Cryovac, Inc. | Intercalated layered silicate |
US20100040653A1 (en) * | 2004-12-02 | 2010-02-18 | Grah Michael D | Intercalated layered silicate |
US20090297568A1 (en) * | 2005-08-19 | 2009-12-03 | Grah Michael D | Intercalated layered silicate |
US20090216207A1 (en) * | 2006-02-10 | 2009-08-27 | Soeren Kirkegaard Nielsen | Biodegradable Barrier Film |
US20120318700A1 (en) * | 2007-08-24 | 2012-12-20 | Illsley Derek R | Gas barrier coating having improved bond strength |
CN103483946A (zh) * | 2007-08-24 | 2014-01-01 | 太阳化学有限公司 | 具备改进的粘合强度的阻气涂料 |
DE102007048995B4 (de) * | 2007-10-11 | 2016-05-12 | Lanxess Deutschland Gmbh | Verfahren zur Vereinzelung von Silikat-Plättchen aus Schichtsilikaten |
US11084311B2 (en) * | 2008-02-29 | 2021-08-10 | Illinois Tool Works Inc. | Receiver material having a polymer with nano-composite filler material |
US20090229775A1 (en) * | 2008-03-15 | 2009-09-17 | Fushan Zhang | Clay slurries and use thereof in pulp and papermaking applications |
US8691052B2 (en) * | 2008-03-15 | 2014-04-08 | Hercules Incorporated | Clay slurries and use thereof in pulp and papermaking applications |
WO2018050770A1 (fr) * | 2016-09-15 | 2018-03-22 | Instituto Tecnológico Del Embalaje, Transporte Y Logística (Itene) | Nanocomposite polymère comprenant du polyéthylène téréphtalate renforcé avec un phyllosilicate intercalé |
US11111379B2 (en) | 2016-09-15 | 2021-09-07 | Instituto Tecnológico Del Embalaje Transporte Y Logística (itene) | Polymer nanocomposite comprising poly(ethylene terephthalate) reinforced with an intercalated phyllosilicate |
US20200407226A1 (en) * | 2018-02-02 | 2020-12-31 | Queen's University At Kingston | Graphene Nanoplatelets Derived from Thermomechanical Exfoliation of Graphite |
US11760639B2 (en) * | 2018-02-02 | 2023-09-19 | Queen's University At Kingston | Graphene nanoplatelets derived from thermomechanical exfoliation of graphite |
Also Published As
Publication number | Publication date |
---|---|
AU2005311657A1 (en) | 2006-06-08 |
NZ555071A (en) | 2011-01-28 |
ATE509981T1 (de) | 2011-06-15 |
JP5033639B2 (ja) | 2012-09-26 |
JP2008521752A (ja) | 2008-06-26 |
EP1833902B1 (fr) | 2011-05-18 |
CA2586792A1 (fr) | 2006-06-08 |
BRPI0515820B1 (pt) | 2016-09-20 |
AU2005311657B2 (en) | 2011-09-08 |
NZ590183A (en) | 2011-06-30 |
BRPI0515820A (pt) | 2008-08-05 |
WO2006060716A1 (fr) | 2006-06-08 |
CA2586792C (fr) | 2010-02-09 |
US8568808B2 (en) | 2013-10-29 |
CN101120047B (zh) | 2012-10-24 |
US20100040653A1 (en) | 2010-02-18 |
EP1833902A1 (fr) | 2007-09-19 |
CN101120047A (zh) | 2008-02-06 |
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