US20070032585A1 - Composite of high melting polymer and nanoclay with enhanced properties - Google Patents
Composite of high melting polymer and nanoclay with enhanced properties Download PDFInfo
- Publication number
- US20070032585A1 US20070032585A1 US11/545,452 US54545206A US2007032585A1 US 20070032585 A1 US20070032585 A1 US 20070032585A1 US 54545206 A US54545206 A US 54545206A US 2007032585 A1 US2007032585 A1 US 2007032585A1
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- United States
- Prior art keywords
- composite
- polycarbonate
- nanoclay
- modified
- compatible
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- 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.)
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- RBJVUENLWPUNQL-UHFFFAOYSA-N CCC(CC(C)C(=O)OCC[N+](C)(C)C)C1=CC=CC=C1.[I-] Chemical compound CCC(CC(C)C(=O)OCC[N+](C)(C)C)C1=CC=CC=C1.[I-] RBJVUENLWPUNQL-UHFFFAOYSA-N 0.000 description 6
- JCHDBFVOIKDFCE-UHFFFAOYSA-N CCC(CC(C)(C)C(=O)OCCN(C)C)C1=CC=CC=C1 Chemical compound CCC(CC(C)(C)C(=O)OCCN(C)C)C1=CC=CC=C1 JCHDBFVOIKDFCE-UHFFFAOYSA-N 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
Definitions
- This invention is directed at composites of high melting polymers and nanoclays.
- Nanoclays are known to be added to polymers to improve some properties of the polymers.
- the nanoclays must be modified to be hydrophobic so as to be miscible with the polymers by conversion of the nanoclays to ammonium or phosphonium form.
- ammonium form nanoclays can be prepared that will form composites with high melting polymers that have enhanced modulus and strength without loss in elongation and toughness, and can provide formed objects which are transparent and without coloration
- these advantages are provided by a composite of polymer that requires a temperature of 200° C. or more for forming, with from 0.1 to 10% by weight of a nanoclay which has been modified to contain an ammonium cation that is stable at the temperature required for forming the polymer and which provides a modified nanoclay which is compatible (miscible) with the polymer.
- a copolymer for use for modifying cationic form nanoclay so the nanoclay contains ammonium cation that is stable at a temperature of at least 200° C. and is miscible with high melting polymers in one case the copolymer has the structure: where n ranges from 10 to 200 and m ranges from 1 to 5.
- a 2,1-layered silicate that is modified to contain organic cation which is where n ranges from 10 to 200 and m ranges from 1 to 5.
- the exemplified case of the second embodiment is useful to modify cation form 2,1-layered silicate to provide the third embodiment.
- the polymer requires a temperature of 200° C. or more for forming.
- This polymer can be, for example, a polycarbonate or other polyester.
- Nanoclays are known as nanoclays because of 1 nanometer spacing between layers.
- the modified nanoclays herein are 2:1 layered silicates modified to contain an ammonium cation that is stable at the temperature required for forming the polymer and which provides a modified nanoclay which is compatible (miscible). with the polymer.
- the term “2:1 layered silicates” is a known term and describes silicates containing lattice layers containing two tetrahedral sheets that share an edge with an octahedral sheet of either aluminum or magnesium hydroxide.
- the stacking of the layers provides interlayers or galleries between the layers.
- the galleries are normally occupied by cations that balance the charge deficiency that is generated by the isomorphous substitution within the layers. Besides the charge-balancing cations, water is also present in the galleries where it tends to associate with the cations.
- the silicates may be referred to as gallery-containing to describe this characteristic of 2:1 layered silicates which allows for intercalation therein of polymers.
- the silicates may be either natural or synthetic.
- the natural silicates include, for example, smectite clay minerals (e.g., montmorillonite, saponite, beidellite, nontronite, hectorite and stevensite), vermiculite and halloysite.
- the synthetic silicates include for example, laponite, fluoromica, fluorohectorite, hydroxyl hectorite, boron fluophlogopite, hydroxyl boron phlogopite, and solid solutions among those and between those and structurally compatible natural silicates selected from the group consisting of talc, fluorotalc, polylithionite, fluoropolylithionite, phlogapite, and fluorophlogopite.
- charge balancing cations selected from the group consisting of sodium ions, potassium ions, lithium ions, calcium ions and magnesium ions.
- the 2,1-layered silicate preferably has a cationic chain capacity of 60-190 meq/100 grams.
- charge-balancing ammonium cation that is stable at the temperature required for forming the polymer and which provides a modified nanoclay which is compatible (miscible) with the polymer, is exchanged for those that are normally associated with the nanoclays.
- the exchange constitutes ion exchange and may be carried out as taught in Okada et al U.S. Pat. No.
- Suitable exchange may be carried out, for example, by suspending the clay in a solution of modifying agent or by passing solution of modifying agent through a column containing the nanoclay in particulate form.
- Suitable exchange in the specific case of the working example is carried out by dispensing particulate clay into a coater containing solvent for the modifying agent, adding the modifying agent to form a solution of the modifying agent in admixture with the particulate clay, with the admixture at 50° C.
- a suitable modifying quaternary ammonium salt to provide modified nanoclay herein is that of the second embodiment herein.
- a modified 2,1-layered silicate where the cation is stable at a temperature for forming the polymer and which is compatible (miscible) with the polymer is where, for example, the modification is to convert pristine cationic form silicate to quaternary ammonium form where the quaternary ammonium substituent is quaternized copolymer of styrene and 2-(dimethylamine) ethyl methacrylate.
- the modified 2,1-layered silicate is the modified 2,1-layered silicate of the third embodiment herein.
- Composite of the first embodiment is readily prepared by melting the polymer and blending the melted polymer with modified nanoclay, e.g., ground to through 250 mesh, in an extruder whereby extruded product is constituted of the composite.
- modified nanoclay e.g., ground to through 250 mesh
- the copolymer of the second embodiment has the structure where n ranges from 10 to 200 and m ranges from 1 to 5.
- the copolymer of the second embodiment can be prepared from styrene and 2-(dimethylamine) ethyl methacrylate by reacting these in the presence of a vinyl polymerization catalyst, e.g., azobisisobutyronitrile, in suitable solvent, e.g., tetrahydrofuran, e.g., at 70° C., to produce the amine corresponding th the above structure and then quaterizing with methyl iodide, e.g., in tetrahydrofuram at 60° C.
- a vinyl polymerization catalyst e.g., azobisisobutyronitrile
- suitable solvent e.g., tetrahydrofuran, e.g., at 70° C.
- 2,1-Layered silicates so modified in the working example herein are montmorrilonite and fluoromica. Modification is carried out by ion exchange with the composition of the second embodiment.
- Styrene (9.5 g) and 2-(dimethylamine) ethyl methacrylate (0.5 g) were dissolved in tetrahydrofiran together with azoisobisisobutyronitile (1 gram in 20 ml tetrahydrofuran) and the solution was heated at 70° C. overnight to cause polymerization and form where n is 50 and m is 1.
- the polymerization product was quaternized using 1 gram methyl iodide (in excess) in solution in tetrahydrofuran at 60° C. for 4 hours to produce where n is 50 and m is 1.
- Montmorrilonite (cationic form) and fluoromica (cationic form) was modified as described above.
- the montmorrilonite and fluoromica were obtained commercially.
- a modified nanoclay was obtained where the balancing organic cation was where n is 50and m is 1.
- Composites were prepared from polycarbonate of melt index of 10-12 (available from Aldrich Chemical Company) and in one case, the modified montmorrilonite and in a second the modified fluoromica. In each case the composite contained 3% by weight modified nanoclay.
- the composites were prepared by melting the polycarbonate and blending it with modified nanoclay (ground to through 250 mesh) in a twin screw microextruder at 270° C. and 130 rpm for 5 min. This caused the polycarbonate to intercalate between layers in the modified nanoclays.
- PC polycarbonate
- PCN-M composite of polycarbonate and 3% by weight modified montimorrilonite
- PCN-FM composite of polycarbonate and 3% modified fluoromica
Abstract
Composite of high melting polymer and nanoclay converted so the balancing cation is quaterized copolymer of styrene and 2-(dimethylamine)ethyl methacrylate provides transparent form without coloration and enhanced modulus and strength without loss of elongation and toughness.
Description
- This invention is directed at composites of high melting polymers and nanoclays.
- Nanoclays are known to be added to polymers to improve some properties of the polymers.
- For this purpose, the nanoclays must be modified to be hydrophobic so as to be miscible with the polymers by conversion of the nanoclays to ammonium or phosphonium form.
- Conventional ammonium form nanoclays when used to form composites with high melting polymers, while providing modest increase in modulus, because of low thermal stability begin to decompose at around 200° C. resulting in composites with significant coloration (so their use is limited to forming dark colored objects) and have poor elongation and toughness (impact resistance).
- Conventional phosphonium form nanoclays when used to form composites with high melting polymers, while having acceptable thermal stability, have defective modulus and elongation properties and may be immiscible with the polymers.
- It has been discovered herein that ammonium form nanoclays can be prepared that will form composites with high melting polymers that have enhanced modulus and strength without loss in elongation and toughness, and can provide formed objects which are transparent and without coloration
- In a first embodiment herein, these advantages are provided by a composite of polymer that requires a temperature of 200° C. or more for forming, with from 0.1 to 10% by weight of a nanoclay which has been modified to contain an ammonium cation that is stable at the temperature required for forming the polymer and which provides a modified nanoclay which is compatible (miscible) with the polymer.
- In a second embodiment herein, there is provided a copolymer for use for modifying cationic form nanoclay so the nanoclay contains ammonium cation that is stable at a temperature of at least 200° C. and is miscible with high melting polymers. In one case the copolymer has the structure:
where n ranges from 10 to 200 and m ranges from 1 to 5. -
- The exemplified case of the second embodiment is useful to modify cation form 2,1-layered silicate to provide the third embodiment.
- We turn now to the first embodiment of the invention herein.
- The polymer requires a temperature of 200° C. or more for forming. This polymer can be, for example, a polycarbonate or other polyester. A polycarbonate of melt index of 10-12, commercially available from Aldrich Chemical Company, is used in the working example herein.
- Nanoclays are known as nanoclays because of 1 nanometer spacing between layers. The modified nanoclays herein are 2:1 layered silicates modified to contain an ammonium cation that is stable at the temperature required for forming the polymer and which provides a modified nanoclay which is compatible (miscible). with the polymer.
- The term “2:1 layered silicates” is a known term and describes silicates containing lattice layers containing two tetrahedral sheets that share an edge with an octahedral sheet of either aluminum or magnesium hydroxide. The stacking of the layers provides interlayers or galleries between the layers. The galleries are normally occupied by cations that balance the charge deficiency that is generated by the isomorphous substitution within the layers. Besides the charge-balancing cations, water is also present in the galleries where it tends to associate with the cations. The silicates may be referred to as gallery-containing to describe this characteristic of 2:1 layered silicates which allows for intercalation therein of polymers. The silicates may be either natural or synthetic. The natural silicates include, for example, smectite clay minerals (e.g., montmorillonite, saponite, beidellite, nontronite, hectorite and stevensite), vermiculite and halloysite. The synthetic silicates include for example, laponite, fluoromica, fluorohectorite, hydroxyl hectorite, boron fluophlogopite, hydroxyl boron phlogopite, and solid solutions among those and between those and structurally compatible natural silicates selected from the group consisting of talc, fluorotalc, polylithionite, fluoropolylithionite, phlogapite, and fluorophlogopite. These normally are associated with, i.e., in the pristine state contain, charge balancing cations selected from the group consisting of sodium ions, potassium ions, lithium ions, calcium ions and magnesium ions. The 2,1-layered silicate preferably has a cationic chain capacity of 60-190 meq/100 grams. To provide the modified nanoclays herein, charge-balancing ammonium cation that is stable at the temperature required for forming the polymer and which provides a modified nanoclay which is compatible (miscible) with the polymer, is exchanged for those that are normally associated with the nanoclays. The exchange constitutes ion exchange and may be carried out as taught in Okada et al U.S. Pat. No. 4,739,007, Okada et al U.S. Pat. No. 4,849,411 or Kawasumi et al U.S. Pat. No. 4,810,734. Suitable exchange may be carried out, for example, by suspending the clay in a solution of modifying agent or by passing solution of modifying agent through a column containing the nanoclay in particulate form. Suitable exchange in the specific case of the working example is carried out by dispensing particulate clay into a coater containing solvent for the modifying agent, adding the modifying agent to form a solution of the modifying agent in admixture with the particulate clay, with the admixture at 50° C. mixing to form a suspension of the clay in the solution, then recovering the modified clay and washing and drying. A suitable modifying quaternary ammonium salt to provide modified nanoclay herein is that of the second embodiment herein. A modified 2,1-layered silicate where the cation is stable at a temperature for forming the polymer and which is compatible (miscible) with the polymer is where, for example, the modification is to convert pristine cationic form silicate to quaternary ammonium form where the quaternary ammonium substituent is quaternized copolymer of styrene and 2-(dimethylamine) ethyl methacrylate. Preferably, the modified 2,1-layered silicate is the modified 2,1-layered silicate of the third embodiment herein.
- Composite of the first embodiment is readily prepared by melting the polymer and blending the melted polymer with modified nanoclay, e.g., ground to through 250 mesh, in an extruder whereby extruded product is constituted of the composite.
- We turn now to the second embodiment herein that is directed to a copolymer for use for modifying cationic form nanoclay so that the nanoclay contains an ammonium cation that is stable at a temperature of at least 200° C. and is miscible with the polymer that requires a temperature of 200° C. or more for forming.
-
- The copolymer of the second embodiment can be prepared from styrene and 2-(dimethylamine) ethyl methacrylate by reacting these in the presence of a vinyl polymerization catalyst, e.g., azobisisobutyronitrile, in suitable solvent, e.g., tetrahydrofuran, e.g., at 70° C., to produce the amine corresponding th the above structure and then quaterizing with methyl iodide, e.g., in tetrahydrofuram at 60° C.
- We turn now to the third embodiment which is directed to a 2,1-layered silicate modified to contain the organic cation
where n ranges from 10 to 200 and m ranges from 1 to 5. 2,1-Layered silicates so modified in the working example herein are montmorrilonite and fluoromica. Modification is carried out by ion exchange with the composition of the second embodiment. - The invention is illustrated by the following working example:
- Styrene (9.5 g) and 2-(dimethylamine) ethyl methacrylate (0.5 g) were dissolved in tetrahydrofiran together with azoisobisisobutyronitile (1 gram in 20 ml tetrahydrofuran) and the solution was heated at 70° C. overnight to cause polymerization and form
where n is 50 and m is 1. The polymerization product was quaternized using 1 gram methyl iodide (in excess) in solution in tetrahydrofuran at 60° C. for 4 hours to produce
where n is 50 and m is 1. -
- Composites were prepared from polycarbonate of melt index of 10-12 (available from Aldrich Chemical Company) and in one case, the modified montmorrilonite and in a second the modified fluoromica. In each case the composite contained 3% by weight modified nanoclay. The composites were prepared by melting the polycarbonate and blending it with modified nanoclay (ground to through 250 mesh) in a twin screw microextruder at 270° C. and 130 rpm for 5 min. This caused the polycarbonate to intercalate between layers in the modified nanoclays.
- The absence of a decomposition peak in x-ray diffraction for the modified nanoclay upon blending with polycarbonate showed the modified nanoclays possess much higher thermal stability compared to conventional nanoclays. Even after injection molding the composites did not show a decomposition peak. Transmission electron microscopy images showed well dispersed hybrids were obtained (thereby demonstrating compatibility and good miscibility). Injection molded forms of the composites were transparent and without coloration.
- Mechanical properties obtained on polycarbonate (PC), composite of polycarbonate and 3% by weight modified montimorrilonite (PCN-M) and composite of polycarbonate and 3% modified fluoromica (PCN-FM) were measured, and results are shown in the table below.
TABLE Yield Tensile Modulus Elongation Strength Strength Toughness Sample (GPa) (%) (MpP) (MPa) (Mpa) PC 1.3 150 62 73 80 PCN-M 1.5 140 67 74 81 PCN-FM 1.6 170 70 82 104
Modulus, elongation, strength and toughness were all measured by tensile testing. - The results show the composites have enhanced modulus and strength without loss of elongation and toughness.
- Variations
- Variations of the above will be evident to those skilled in the art. Therefore, the scope of the invention is defined by the claims.
Claims (9)
1-7. (canceled)
8. Composite of(a) polycarbonate with (b) from 1% to 10% by weight of the composite of polycarbonate-compatible 2,1 layered silicate, the composite having enhanced modulus and strength without loss in elongation and toughness compared to the polycarbonate.
9. The composite of claim 8 which is transparent and without coloration on injection molding.
10. The composite of claim 9 where the silicate has been converted to quaternary ammonium form, to effect polycarbonate-compatibility thereof.
11. The composition of claim 10 where the polycarbonate-compatible 2,1 layered silicate is a polycarbonate-compatible cationic form fluoromica and the composite has enhanced elongation and toughness compared to the polycarbonate.
12. The composite of claim 8 where the polycarbonate is intercalated between layers of the silicate.
13. The composite of claim 12 which is transparent and without coloration or injection molding.
14. The composite of claim 13 where the silicate has been converted to quaternary ammonium form, to effect polycarbonate-compatibility thereof.
15. The composite of claim 14 where the polycarbonate-compatible 2,1 layered silicate is a polycarbonate-compatible cationic form fluorimica and the composite has enhanced elongation and toughness compared to the polycarbonate.
Priority Applications (1)
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US11/545,452 US20070032585A1 (en) | 2003-12-19 | 2006-10-11 | Composite of high melting polymer and nanoclay with enhanced properties |
Applications Claiming Priority (2)
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US10/739,534 US7148282B2 (en) | 2003-12-19 | 2003-12-19 | Composite of high melting polymer and nanoclay with enhanced properties |
US11/545,452 US20070032585A1 (en) | 2003-12-19 | 2006-10-11 | Composite of high melting polymer and nanoclay with enhanced properties |
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US10/739,534 Continuation US7148282B2 (en) | 2003-12-19 | 2003-12-19 | Composite of high melting polymer and nanoclay with enhanced properties |
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US20070032585A1 true US20070032585A1 (en) | 2007-02-08 |
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US10/739,534 Expired - Fee Related US7148282B2 (en) | 2003-12-19 | 2003-12-19 | Composite of high melting polymer and nanoclay with enhanced properties |
US11/545,452 Abandoned US20070032585A1 (en) | 2003-12-19 | 2006-10-11 | Composite of high melting polymer and nanoclay with enhanced properties |
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US10/739,534 Expired - Fee Related US7148282B2 (en) | 2003-12-19 | 2003-12-19 | Composite of high melting polymer and nanoclay with enhanced properties |
Country Status (5)
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US (2) | US7148282B2 (en) |
EP (1) | EP1694763B1 (en) |
AT (1) | ATE441691T1 (en) |
DE (1) | DE602004022979D1 (en) |
WO (1) | WO2005065086A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070191510A1 (en) * | 2006-02-15 | 2007-08-16 | Chaiko David J | Polymer composites, polymer nanocomposites and methods |
US20090213346A1 (en) * | 2008-02-22 | 2009-08-27 | Zimmerman Paul A | Immersion lithography using hafnium-based nanoparticles |
US20110039105A1 (en) * | 2009-08-13 | 2011-02-17 | Zimmerman Paul A | Non-aggregating nanoparticles and the use thereof |
US9409823B2 (en) | 2013-02-15 | 2016-08-09 | Deborah D. L. Chung | Microstructured high-temperature hybrid material, its composite material and method of making |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7148282B2 (en) * | 2003-12-19 | 2006-12-12 | Cornell Research Foundations, Inc. | Composite of high melting polymer and nanoclay with enhanced properties |
CA2552896A1 (en) * | 2004-01-16 | 2005-08-04 | Jean-Pierre Ibar | Process for dispersing a thermally sensitive additive into a melt |
DE102005060463A1 (en) * | 2005-12-17 | 2007-06-28 | Bayer Materialscience Ag | Polycarbonate molding compositions |
US8313051B2 (en) | 2008-03-05 | 2012-11-20 | Sealed Air Corporation (Us) | Process and apparatus for mixing a polymer composition and composite polymers resulting therefrom |
CA2782155A1 (en) * | 2009-12-02 | 2011-06-09 | Basf Se | Stabilizer composition for filled polymers and nanocomposites |
US10780402B2 (en) | 2012-04-22 | 2020-09-22 | King Abdullah University Of Science And Technology | Methods of membrane modification |
TW202208469A (en) | 2020-03-16 | 2022-03-01 | 臺灣塑膠工業股份有限公司 | Functionalized exfoliated nanoclay and non-polar polymer nanocomposite compositions |
Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3799799A (en) * | 1971-04-01 | 1974-03-26 | Fiberglas Canada Ltd | Coating of mica reinforcement for composite materials |
US3870559A (en) * | 1970-02-25 | 1975-03-11 | Ici Ltd | Paper treatment |
US4355167A (en) * | 1981-05-01 | 1982-10-19 | Xerox Corporation | Telomeric quaternary salt compositions |
US4582866A (en) * | 1984-04-30 | 1986-04-15 | E. I. Du Pont De Nemours And Company | Flame retardant thermoplastic multi-block copolyester elastomers |
US5219611A (en) * | 1991-09-30 | 1993-06-15 | Cornell Research Foundation, Inc. | Preparing densified low porosity titania sol gel forms |
US5260094A (en) * | 1991-09-30 | 1993-11-09 | Cornell Research Foundation, Inc. | Preparing densified low porosity titania sol-gel forms |
US5530052A (en) * | 1995-04-03 | 1996-06-25 | General Electric Company | Layered minerals and compositions comprising the same |
US5554670A (en) * | 1994-09-12 | 1996-09-10 | Cornell Research Foundation, Inc. | Method of preparing layered silicate-epoxy nanocomposites |
US5955535A (en) * | 1993-11-29 | 1999-09-21 | Cornell Research Foundation, Inc. | Method for preparing silicate-polymer composite |
US6034183A (en) * | 1997-06-09 | 2000-03-07 | Arakawa Chemical Industries, Ltd. | Polymer having quaternary ammonium groups and process for the production thereof |
US6197849B1 (en) * | 1998-02-20 | 2001-03-06 | Vantico Inc. | Organophilic phyllosilicates |
US20010056136A1 (en) * | 1999-12-10 | 2001-12-27 | Kabushiki Kenkyusho | Polymer composite |
US6384121B1 (en) * | 1998-12-07 | 2002-05-07 | Eastman Chemical Company | Polymeter/clay nanocomposite comprising a functionalized polymer or oligomer and a process for preparing same |
US20020120049A1 (en) * | 1999-09-03 | 2002-08-29 | Dsm N.V. | Extruded nanocomposite moulded part comprising at least a polycondensate and a nano-filler and a process for its production |
US20030065087A1 (en) * | 2001-05-16 | 2003-04-03 | Kao Corporation | Silicone-modified water-absorbing polymer particles and method for producing the same |
US20030171485A1 (en) * | 2000-06-09 | 2003-09-11 | Catridge David John | Thickeners |
US20030176537A1 (en) * | 2002-03-18 | 2003-09-18 | The University Of Chicago | Composite materials with improved phyllosilicate dispersion |
US20050065263A1 (en) * | 2003-09-22 | 2005-03-24 | Chung James Y.J. | Polycarbonate composition |
US7148282B2 (en) * | 2003-12-19 | 2006-12-12 | Cornell Research Foundations, Inc. | Composite of high melting polymer and nanoclay with enhanced properties |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4739007A (en) | 1985-09-30 | 1988-04-19 | Kabushiki Kaisha Toyota Chou Kenkyusho | Composite material and process for manufacturing same |
US4894411A (en) | 1987-03-18 | 1990-01-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite material and process for producing the same |
JPH0778089B2 (en) | 1987-03-26 | 1995-08-23 | 株式会社豊田中央研究所 | Method of manufacturing composite material |
JPH07228762A (en) * | 1994-02-21 | 1995-08-29 | Co-Op Chem Co Ltd | Aromatic polycarbonate resin composition |
US5594062A (en) * | 1994-03-16 | 1997-01-14 | Kawasaki Steel Corporation | Polycarbonate/polyolefin based resin compositions and their production processes and uses |
JPH09143359A (en) | 1995-11-27 | 1997-06-03 | Kanegafuchi Chem Ind Co Ltd | Polycarbonate resin composition |
JPH09255939A (en) * | 1996-03-26 | 1997-09-30 | Arakawa Chem Ind Co Ltd | Heat-resistant antistatic agent and its production |
JP2000327805A (en) | 1999-05-18 | 2000-11-28 | Kanegafuchi Chem Ind Co Ltd | Resin film |
-
2003
- 2003-12-19 US US10/739,534 patent/US7148282B2/en not_active Expired - Fee Related
-
2004
- 2004-12-08 AT AT04811085T patent/ATE441691T1/en not_active IP Right Cessation
- 2004-12-08 WO PCT/US2004/038234 patent/WO2005065086A2/en not_active Application Discontinuation
- 2004-12-08 EP EP20040811085 patent/EP1694763B1/en not_active Not-in-force
- 2004-12-08 DE DE200460022979 patent/DE602004022979D1/en active Active
-
2006
- 2006-10-11 US US11/545,452 patent/US20070032585A1/en not_active Abandoned
Patent Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3870559A (en) * | 1970-02-25 | 1975-03-11 | Ici Ltd | Paper treatment |
US3799799A (en) * | 1971-04-01 | 1974-03-26 | Fiberglas Canada Ltd | Coating of mica reinforcement for composite materials |
US4355167A (en) * | 1981-05-01 | 1982-10-19 | Xerox Corporation | Telomeric quaternary salt compositions |
US4582866A (en) * | 1984-04-30 | 1986-04-15 | E. I. Du Pont De Nemours And Company | Flame retardant thermoplastic multi-block copolyester elastomers |
US5219611A (en) * | 1991-09-30 | 1993-06-15 | Cornell Research Foundation, Inc. | Preparing densified low porosity titania sol gel forms |
US5260094A (en) * | 1991-09-30 | 1993-11-09 | Cornell Research Foundation, Inc. | Preparing densified low porosity titania sol-gel forms |
US6225374B1 (en) * | 1993-11-29 | 2001-05-01 | Cornell Research Foundation, Inc. | Method for preparing silicate-polymer composite |
US5955535A (en) * | 1993-11-29 | 1999-09-21 | Cornell Research Foundation, Inc. | Method for preparing silicate-polymer composite |
US5554670A (en) * | 1994-09-12 | 1996-09-10 | Cornell Research Foundation, Inc. | Method of preparing layered silicate-epoxy nanocomposites |
US5530052A (en) * | 1995-04-03 | 1996-06-25 | General Electric Company | Layered minerals and compositions comprising the same |
US6034183A (en) * | 1997-06-09 | 2000-03-07 | Arakawa Chemical Industries, Ltd. | Polymer having quaternary ammonium groups and process for the production thereof |
US6197849B1 (en) * | 1998-02-20 | 2001-03-06 | Vantico Inc. | Organophilic phyllosilicates |
US6384121B1 (en) * | 1998-12-07 | 2002-05-07 | Eastman Chemical Company | Polymeter/clay nanocomposite comprising a functionalized polymer or oligomer and a process for preparing same |
US20020120049A1 (en) * | 1999-09-03 | 2002-08-29 | Dsm N.V. | Extruded nanocomposite moulded part comprising at least a polycondensate and a nano-filler and a process for its production |
US20010056136A1 (en) * | 1999-12-10 | 2001-12-27 | Kabushiki Kenkyusho | Polymer composite |
US20030171485A1 (en) * | 2000-06-09 | 2003-09-11 | Catridge David John | Thickeners |
US20030065087A1 (en) * | 2001-05-16 | 2003-04-03 | Kao Corporation | Silicone-modified water-absorbing polymer particles and method for producing the same |
US20030176537A1 (en) * | 2002-03-18 | 2003-09-18 | The University Of Chicago | Composite materials with improved phyllosilicate dispersion |
US20050065263A1 (en) * | 2003-09-22 | 2005-03-24 | Chung James Y.J. | Polycarbonate composition |
US7148282B2 (en) * | 2003-12-19 | 2006-12-12 | Cornell Research Foundations, Inc. | Composite of high melting polymer and nanoclay with enhanced properties |
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US20070191510A1 (en) * | 2006-02-15 | 2007-08-16 | Chaiko David J | Polymer composites, polymer nanocomposites and methods |
US7919185B2 (en) | 2006-02-15 | 2011-04-05 | Chaiko David J | Polymer composites, polymer nanocomposites and methods |
US20090213346A1 (en) * | 2008-02-22 | 2009-08-27 | Zimmerman Paul A | Immersion lithography using hafnium-based nanoparticles |
US8134684B2 (en) | 2008-02-22 | 2012-03-13 | Sematech, Inc. | Immersion lithography using hafnium-based nanoparticles |
US20110039105A1 (en) * | 2009-08-13 | 2011-02-17 | Zimmerman Paul A | Non-aggregating nanoparticles and the use thereof |
US8124230B2 (en) | 2009-08-13 | 2012-02-28 | Intel Corporation | Non-aggregating nanoparticles and the use thereof |
US9409823B2 (en) | 2013-02-15 | 2016-08-09 | Deborah D. L. Chung | Microstructured high-temperature hybrid material, its composite material and method of making |
Also Published As
Publication number | Publication date |
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DE602004022979D1 (en) | 2009-10-15 |
EP1694763A2 (en) | 2006-08-30 |
WO2005065086A2 (en) | 2005-07-21 |
EP1694763B1 (en) | 2009-09-02 |
ATE441691T1 (en) | 2009-09-15 |
WO2005065086A3 (en) | 2006-04-13 |
US7148282B2 (en) | 2006-12-12 |
EP1694763A4 (en) | 2007-05-23 |
US20050137287A1 (en) | 2005-06-23 |
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