EP1963439A2 - Method for preparing layered nanoparticles, and nanoparticles obtained - Google Patents
Method for preparing layered nanoparticles, and nanoparticles obtainedInfo
- Publication number
- EP1963439A2 EP1963439A2 EP06847163A EP06847163A EP1963439A2 EP 1963439 A2 EP1963439 A2 EP 1963439A2 EP 06847163 A EP06847163 A EP 06847163A EP 06847163 A EP06847163 A EP 06847163A EP 1963439 A2 EP1963439 A2 EP 1963439A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- nanoparticles
- agent
- laminated material
- mixture
- clay
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0078—Pigments consisting of flaky, non-metallic substrates, characterised by a surface-region containing free metal
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/42—Clays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the invention relates to a method for preparing nanoparticles in sheets and the resulting nanoparticles.
- Mineral particles are widely used to reinforce polymers of various kinds.
- Such particles in the form of platelets are particularly sought after because they can be oriented in a given direction in the polymer to be reinforced, and thus provide the polymer with barrier properties, especially with water and gases.
- the particular shape of the particles and their arrangement substantially parallel to each other make it more difficult the flow of water and gases in the polymer matrix, thereby delaying their diffusion.
- Particles in the form of platelets are generally obtained from laminated materials, most often natural, such as clays.
- the laminated material is subjected to one or more mechanical treatments, for example grinding, and / or chemical, for example by ion exchange, to obtain particles having the desired size and particle size.
- the particles obtained can then be modified to give them specific properties, for example to make their surface hydrophobic so as to further reduce the diffusion of water and gases in the polymers.
- EP-A-927,748 describes the preparation of hydrophobic particles of clay which comprises contacting an aqueous suspension of clay with an organic compound containing silicon such as an organosilane or an organosiloxane in the presence of an acid and a water-miscible solvent, and adding a water-immiscible solvent to effect the separation of the particles.
- an organic compound containing silicon such as an organosilane or an organosiloxane
- nanoparticles in the form of platelets are able to give a barrier effect to water and gases when they are incorporated into a polymer. Nevertheless, it has been observed that this effect is greater if the nanoparticles are in the form of individualized platelets rather than platelet aggregates.
- the object of the present invention relates to a process for preparing nanoparticles in sheets by treating a laminated material with an expansion agent capable of being interposed between the sheets to dissociate them.
- Another subject of the invention relates to a process for preparing nanoparticles in graft-modified layers.
- the process according to the invention is characterized in that it comprises the following steps consisting of: a) mixing a laminated material with an expansion agent chosen from polyols, b) reacting the foamed laminated material with a grafting agent in the presence of water and an acid, said agent having the general formula
- R represents a hydrogen atom or a hydrocarbon radical containing 1 to 40 carbon atoms, the R groups possibly being identical or different,
- X represents a silicon, zirconium or titanium atom
- Y is an alkoxy group containing 1 to 12 carbon atoms, or a halogen
- a is equal to 1, 2 or 3
- laminated material is meant a mineral material consisting of a plurality of substantially parallel sheets having a thickness of a few nanometers.
- the sheets of such a material are integrally or only partially connected to each other by interactions of the hydrogen type or ionic between the free hydroxyl groups present on the surface of the leaflets and the water and / or the cations contained in the space interlayers.
- the laminated material can be a natural material or obtained by chemical synthesis.
- laminated materials belonging to the group of clays and boehmites are laminated materials belonging to the group of clays and boehmites.
- clay is here to be considered in its general definition accepted by those skilled in the art, namely that it defines hydrated aluminosilicates of general formula AI 2 O 3 -SiO 2 -XH 2 O, where x is the degree hydration.
- phyllosilicates of the mica type such as smectites, montmorillonite, hectorite, bentonites, nontronite, beidellite, volonskoite, saponite, sauconite, magadiite, vermiculite, mica, kenyaite and synthetic hectorites.
- the clay is chosen from phyllosilicates of type 2: 1, advantageously smectites.
- the most preferred clay is montmorillonite.
- clays in the form of powder whose particles consist of platelets stacked on top of each other in the manner of playing cards.
- the particles may be treated to reduce their size and / or to achieve the desired particle size, for example by mechanical treatment in a mixer operating at a high speed.
- the clay may be a clay having undergone a calcination step, for example at a temperature of at least 75 ° C.
- the clay may also be a modified clay, for example by cation exchange in the presence of a solution of an ammonium, phosphonium, pyridinium or imidazolinium salt, preferably containing one or more alkyl groups, and better still monoalkyl derivatives of these salts.
- the laminated material may also be a boehmite consisting of hydroxyalumin, more particularly a synthetic boehmite obtained by hydrothermal reaction from aluminum hydroxide which is in the form of platelets. Boehmite powder is available on the market. If necessary, mechanical treatment as described above for clays can be applied to reduce the particle size and / or obtain the desired particle size.
- step a) the laminated material is mixed with a blowing agent which interposes between the layers and increases the distance therebetween, which promotes separation into individual platelets.
- the blowing agent according to the invention is chosen from polyols, preferably diols, for example ethylene glycol, 1,3-propanediol, 1,4-butanediol and polyethylene glycols.
- the polyethylene glycols have a molecular weight of at most 1200 and more preferably at most 600.
- the quantity of laminated material in the mixture can vary to a large extent from 10 to 70%, preferably 20 to 50%. .
- the mixture may be subjected to an operation which assists in the separation of platelet leaflets, for example a mechanical treatment in a device for shearing the particles at a high speed or by the action of ultrasound.
- the mixture is made by adding the laminated material in the polyol, with stirring, and maintaining said mixture at room temperature, of the order of 20 to 25 ° C., for a time sufficient for the polyol to penetrate between the layers and interact with the free hydroxyl groups of the material.
- a contact time of at least ten minutes is required, preferably at least 2 hours and more preferably at least 6 hours.
- the mixture may further contain an agent which aids in the dispersion of the laminated material, for example a polyalkoxylated compound such as an ethoxylated / propoxylated alkylphenol, an ethoxylated / propoxylated bisphenol or an ethoxylated / propoxylated fatty alcohol, the number of ethylene oxide ranging from 1 to 50, preferably 1 to 40, and the number of propylene oxide units ranging from 0 to 40, preferably 0 to 15.
- an agent which aids in the dispersion of the laminated material for example a polyalkoxylated compound such as an ethoxylated / propoxylated alkylphenol, an ethoxylated / propoxylated bisphenol or an ethoxylated / propoxylated fatty alcohol, the number of ethylene oxide ranging from 1 to 50, preferably 1 to 40, and the number of propylene oxide units ranging from 0 to 40, preferably 0 to 15.
- step b) the foamed laminated material is reacted with a grafting agent in the presence of water and an acid.
- grafting agent is meant here a compound capable of forming covalent bonds with the hydroxyl groups of the laminated material, and the grafts for modifying the surface of said material in order to endow them with specific properties, in particular to give them a hydrophobic character or hydrophilic.
- water is first added to obtain a slurry of expanded foamed material, then the grafting agent and an acid are added.
- the amount of water added varies from 5 to 90% by weight of the mixture, preferably 10 to 70%.
- the grafting agent is a compound of formula
- R XY-ia wherein R represents a hydrogen atom or a hydrocarbon radical containing 1 to 40 carbon atoms, said radical may be linear, branched or cyclic, saturated or unsaturated, may contain one or more O or N heteroatoms or be substituted with one or more amino, carboxylic acid, epoxy or amido groups, and the R groups being the same or different
- X represents Si, Zr or Ti
- Y is an alkoxy group containing 1 to 12 carbon atoms, or a halogen, preferably Cl, a is 1, 2 or 3.
- the grafting agent is an organosilane, advantageously an organosilane containing two or three alkoxy groups.
- gamma-aminopropyltrimethoxysilane gamma-aminopropyltriethoxysilane
- N-phenyl-gamma-aminopropyltrimethoxysilane N-styrylaminoethyl-gamma-aminopropyltrimethoxysilane
- gamma-glycidoxypropyltrimethoxysilane gamma-methacryloxypropyltrimethoxysilane, acryloxypropytrimethoxysilane gamma, vinyltrimethoxysilane, vinyltriethoxysilane, terbutylcarbamoylpropyltrimethoxysilane and gamma (polyalkyleneoxide) propyltrimethoxysilanes.
- gamma-aminopropyltriethoxysilane N-phenyl-gamma-aminopropyltrimethoxysilane, N-styrylaminoethyl-gamma-amminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane are selected.
- the grafting agent is added in an amount of 15 to 75% by weight of the starting laminate material, preferably 30 to 70%.
- the acid is added as a catalyst for the reaction between the grafting agent and the hydroxyl groups of the laminated material.
- any type of acid, mineral or organic can be used.
- acetic acid is used.
- the acid can be generated in situ by hydrolysis of the chlorosilane or by reaction of the chlorosilane with the hydroxyl groups present on the surface of the laminated material.
- the amount of acid must make it possible to have a pH of the suspension of laminated material of between 1 and 6, preferably between 3 and 5 and better still of the order of 4. It is possible to carry out the reaction of step b) at room temperature, of the order of 20 to 25 0 C, however the reaction time can be substantially reduced if the temperature is higher. As a rule, the constituents of stage b) are mixed at room temperature, then they are heated to a temperature which does not exceed 90 ° C. In the suspension, it is possible to introduce a assisting agent to the dispersion of the laminated material as described in step a) and / or a base for adjusting the pH, for example ammonia.
- step c) the nanoparticles in sheets are recovered by any known means, for example by filtration or centrifugation, phase separation with addition of a solvent immiscible with water or evaporation of the water, if appropriate of the alcohol or alcohols resulting from the hydrolysis of the alkoxy groups of the grafting agent in step b).
- the nanoparticles in sheets thus obtained are modified on the surface by the residues of the grafting agent. They have a loss on ignition greater than 6%, preferably greater than 12% and more preferably greater than 16%.
- These particles may undergo additional treatment which contributes to the separation of the layers and thus makes it possible to increase the final proportion of thin nanoparticles.
- nanoparticles in suspension in a medium suitable for a treatment allowing a high shear, for example by means of an Ultraturrax ® device, or by ultrasound.
- This treatment is preferably carried out by adding to the suspension a nanoparticle dispersing assisting agent, as defined above, and / or an agent for viscosity control, for example polyvinyl acetate, polyvinyl pyrrolidone, hydroxymethyl cellulose or polyethylene glycol.
- Another possible treatment consists of mixing the nanoparticles with a thermoplastic or thermosetting polymer resin, for example epoxy resin, in an extruder, and to put the extrudates in emulsion in water.
- a thermoplastic or thermosetting polymer resin for example epoxy resin
- the nanoparticles in sheets can be used in particular for reinforcing polymeric materials.
- the clay is a natural montmorillonite treated by cation exchange with a quaternary ammonium salt.
- the mixture is heated at 50 ° C. with sufficient stirring to obtain a good dispersion of the clay. Then 50 g of N-styrylaminoéthyl-gamma-amminopropyl- trimethoxysilane (Silquest ® A1128; GE Silicones). The pH of the suspension is equal to 5.
- the suspension is refluxed for 4 hours, then cooled to room temperature and filtered.
- the clay recovered is washed with water, dried at 105 ° C. for 1 hour, ground and dried again under the same conditions.
- the clay contains more than 20% by weight of nanoparticles and has a loss on ignition equal to 17.4%.
- EXAMPLE 2 The conditions of modified Example 1 are used in that the clay is an unmodified natural montmorillonite (Dellite ® HPS, Laviosa Chimica Mineraria) and the expansion agent is ethylene glycol.
- the clay recovered by filtration is washed with 500 ml of an aqueous solution of sodium hydrogencarbonate at 6 g / l and rinsed with 1 I of distilled water.
- the clay obtained contains more than 20% by weight of nanoparticles and has a loss on ignition equal to 14.9%.
- Example 1 device In the Example 1 device was charged 165 g of N-gamma-styrylaminoéthyl- amminopropyl-trimethoxysilane (Silquest ® A1128; GE Silicones), 50 of distilled water, 50 g of acetic acid and 100 g of propan 2-ol. The mixture is heated at 60 ° C. for 30 minutes to effect the hydrolysis of the silane.
- Silquest ® A1128 N-gamma-styrylaminoéthyl- amminopropyl-trimethoxysilane
- the recovered clay is treated under the conditions of Example 1. It has a loss on ignition equal to 26.7%.
- EXAMPLE 4 Into a vessel was charged 16.5 g of clay modified with a quaternary ammonium (Nanofil ® 5; Sud-Chemie AG), 10 g of 2-amino-2-ethyl-1, 3- propanediol, 20 g of polyvinyl alcohol (hydrolysis rate: 88%, molecular weight: 22000) and 300 g of distilled water. The mixture is kept under strong agitation for at least 30 minutes to obtain a dispersion. The dispersion is treated by Ultraturrax ® for 5 minutes at 6000 rpm and allowed to stand for 30 minutes and treated again by Ultraturrax for 1 minute at 9000 rpm.
- a quaternary ammonium Nafil ® 5; Sud-Chemie AG
- 2-amino-2-ethyl-1, 3- propanediol 20 g of polyvinyl alcohol (hydrolysis rate: 88%, molecular weight: 22000)
- the mixture is kept under strong agitation for at least
- the dispersion is introduced and 200 g of water, and then 50 g of acetic acid (90% in water). The mixture was heated at 5O 0 C under sufficient stirring to obtain a good dispersion, then added slowly 50 g of gamma-aminopropyltriethoxysilane (Silquest ® A-1100, GE
- the pH of the suspension is 5.2.
- Example 1 The suspension is refluxed for 4 hours then cooled to room temperature and filtered.
- the recovered clay is treated under the conditions of Example 1. It has a loss on ignition equal to 24.4%.
- Example 1 device 50 g of clay modified with a quaternary ammonium (Nanofil ® 5; SUD-CHEMIE AG), 200 g of polyethylene glycol (average molecular weight: 300) and 10 g of polyvinyl alcohol (hydrolysis rate: 88%, molecular weight: 22000).
- a quaternary ammonium Naofil ® 5; SUD-CHEMIE AG
- 200 g of polyethylene glycol average molecular weight: 300
- 10 g of polyvinyl alcohol hydrolysis rate: 88%, molecular weight: 22000.
- the resulting dispersion was slowly added 30 g of gamma-methacryloxypropyltrimethoxysilane (Silquest ® A-174; GE Silicones), 15 g of N- (polyéthylèneoxyéthylène) -N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane silane (Silquest ® A- 1126; GE Silicones) and 10 g of sylated polyazamide (Silquest ® A-1387, GE Silicones).
- the pH of the suspension is 4.6.
- the suspension is refluxed for 5 hours, cooled to room temperature and filtered.
- the recovered clay is treated under the conditions of Example 1. It has a loss on ignition equal to 35.9%.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Colloid Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0554076A FR2895412B1 (en) | 2005-12-23 | 2005-12-23 | PROCESS FOR THE PREPARATION OF NANOPARTICLES IN SHEETS AND NANOPARTICLES OBTAINED |
PCT/FR2006/051373 WO2007074280A2 (en) | 2005-12-23 | 2006-12-18 | Method for preparing layered nanoparticles, and nanoparticles obtained |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1963439A2 true EP1963439A2 (en) | 2008-09-03 |
Family
ID=36651357
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06847163A Ceased EP1963439A2 (en) | 2005-12-23 | 2006-12-18 | Method for preparing layered nanoparticles, and nanoparticles obtained |
Country Status (9)
Country | Link |
---|---|
US (1) | US20090305042A1 (en) |
EP (1) | EP1963439A2 (en) |
JP (1) | JP5706067B2 (en) |
CN (1) | CN101379146B (en) |
BR (1) | BRPI0620402A2 (en) |
CA (1) | CA2634227C (en) |
FR (1) | FR2895412B1 (en) |
RU (1) | RU2429261C2 (en) |
WO (1) | WO2007074280A2 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2895397B1 (en) * | 2005-12-23 | 2008-03-28 | Saint Gobain Vetrotex | GLASS YARN AND STRUCTURES OF GLASS YARNS HAVING A COATING COMPRISING NANOPARTICLES |
FR2895398B1 (en) * | 2005-12-23 | 2008-03-28 | Saint Gobain Vetrotex | GLASS YARN COATED WITH AN ENSIMAGE COMPRISING NANOPARTICLES. |
US20090246529A1 (en) * | 2008-03-28 | 2009-10-01 | Conopco, Inc., D/B/A Unilever | Particle with Bipolar Topospecific Characteristics and Process for Preparation Thereof |
CN102320618B (en) * | 2011-06-28 | 2013-06-26 | 淮阴工学院 | Clay micro/nanorization method based on high aspect ratio structure of high pressure expansion protective material |
CZ303513B6 (en) * | 2011-08-30 | 2012-10-31 | Vysoká Škola Bánská -Technická Univerzita Ostrava | Process for preparing fibrous and lamellar microstructures and nanostructures by controlled vacuum freeze-drying of nanoparticle liquid dispersion |
JP6969115B2 (en) * | 2017-03-14 | 2021-11-24 | 東亞合成株式会社 | Method for Producing Cyrilized Layered Inorganic Compound |
CN109851278B (en) * | 2019-03-27 | 2021-07-13 | 常熟京常智能科技有限公司 | Traffic detection equipment wall fixing expanding agent and preparation method thereof |
CN110526253B (en) * | 2019-09-12 | 2022-07-22 | 浙江工业大学之江学院 | Preparation method of hydrophilic organic magnesium saponite |
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US4367163A (en) * | 1981-04-15 | 1983-01-04 | Research Corporation | Silica-clay complexes |
US4510257A (en) * | 1983-12-08 | 1985-04-09 | Shell Oil Company | Silica-clay complexes |
US4830673A (en) * | 1986-10-03 | 1989-05-16 | E.C.C. America Inc. | Method for reducing the abrasion of calcined clay |
US4957889A (en) * | 1987-03-05 | 1990-09-18 | Uop | Stable intercalated clays and preparation method |
US5008227A (en) * | 1989-05-16 | 1991-04-16 | Engelhard Corporation | Process for making acid activated bleaching earth using high susceptibility source clay and novel bleaching earth product |
ES2115669T3 (en) * | 1991-01-11 | 1998-07-01 | Mobil Oil Corp | MATERIALS OF LAMINATED OXIDES AND BLOWN FORMS AND THEIR STACKED FORMS. |
US5700560A (en) * | 1992-07-29 | 1997-12-23 | Sumitomo Chemical Company, Limited | Gas barrier resin composition and its film and process for producing the same |
US5558777A (en) * | 1995-04-13 | 1996-09-24 | Rheox, Inc. | Oil spill flocculating agent and method of remediating oil spills |
US5721306A (en) * | 1995-06-07 | 1998-02-24 | Amcol International Corporation | Viscous carrier compositions, including gels, formed with an organic liquid carrier and a layered material:polymer complex |
US5830528A (en) * | 1996-05-29 | 1998-11-03 | Amcol International Corporation | Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composites materials containing same and methods of modifying rheology therewith |
US6239195B1 (en) * | 1996-05-13 | 2001-05-29 | Kaneka Corporation | Thermoplastic resin composition containing silan-treated foliated phyllosilicate and method for producing the same |
JP3686260B2 (en) * | 1997-07-01 | 2005-08-24 | 株式会社カネカ | Layered inorganic substance-containing resin film |
WO1999023162A1 (en) * | 1997-10-30 | 1999-05-14 | Kaneka Corporation | Polyester resin compositions and processes for the preparation thereof |
GB9726636D0 (en) * | 1997-12-17 | 1998-02-18 | Dow Corning | Method for preparing hydrophobic clay |
US6271297B1 (en) * | 1999-05-13 | 2001-08-07 | Case Western Reserve University | General approach to nanocomposite preparation |
JP4469063B2 (en) * | 2000-06-08 | 2010-05-26 | 東レ・ダウコーニング株式会社 | Surface treatment agent for alumina powder |
US7173080B2 (en) * | 2001-09-06 | 2007-02-06 | Unitika Ltd. | Biodegradable resin composition for molding and object molded or formed from the same |
US20030050380A1 (en) * | 2001-09-07 | 2003-03-13 | Lon Risley | Calcined flint clay filler and solid surface made therewith |
US6762233B2 (en) * | 2001-10-09 | 2004-07-13 | The University Of Chicago | Liquid crystalline composites containing phyllosilicates |
US20040241482A1 (en) * | 2003-06-02 | 2004-12-02 | Grah Michael D. | PVdC film with nanocomposite tie layer |
RU2353633C2 (en) * | 2003-10-10 | 2009-04-27 | Дау Глобал Текнолоджиз Инк. | Composite containing segregated clay in soot and its obtaining |
US7201949B2 (en) * | 2003-10-21 | 2007-04-10 | Eastman Kodak Company | Optical film for display devices |
-
2005
- 2005-12-23 FR FR0554076A patent/FR2895412B1/en not_active Expired - Fee Related
-
2006
- 2006-12-18 BR BRPI0620402-3A patent/BRPI0620402A2/en not_active Application Discontinuation
- 2006-12-18 RU RU2008130376/05A patent/RU2429261C2/en not_active IP Right Cessation
- 2006-12-18 US US12/158,598 patent/US20090305042A1/en not_active Abandoned
- 2006-12-18 WO PCT/FR2006/051373 patent/WO2007074280A2/en active Application Filing
- 2006-12-18 CA CA2634227A patent/CA2634227C/en not_active Expired - Fee Related
- 2006-12-18 JP JP2008546550A patent/JP5706067B2/en not_active Expired - Fee Related
- 2006-12-18 EP EP06847163A patent/EP1963439A2/en not_active Ceased
- 2006-12-18 CN CN2006800486460A patent/CN101379146B/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO2007074280A2 * |
Also Published As
Publication number | Publication date |
---|---|
US20090305042A1 (en) | 2009-12-10 |
JP5706067B2 (en) | 2015-04-22 |
BRPI0620402A2 (en) | 2011-11-16 |
WO2007074280A2 (en) | 2007-07-05 |
RU2008130376A (en) | 2010-01-27 |
CA2634227A1 (en) | 2007-07-05 |
FR2895412A1 (en) | 2007-06-29 |
CN101379146A (en) | 2009-03-04 |
JP2009520671A (en) | 2009-05-28 |
RU2429261C2 (en) | 2011-09-20 |
WO2007074280A3 (en) | 2007-08-16 |
CA2634227C (en) | 2014-07-15 |
CN101379146B (en) | 2012-09-05 |
FR2895412B1 (en) | 2008-05-23 |
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