WO2005003029A2 - Modified layered inorganic materials - Google Patents
Modified layered inorganic materialsInfo
- Publication number
- WO2005003029A2 WO2005003029A2 PCT/US2004/019477 US2004019477W WO2005003029A2 WO 2005003029 A2 WO2005003029 A2 WO 2005003029A2 US 2004019477 W US2004019477 W US 2004019477W WO 2005003029 A2 WO2005003029 A2 WO 2005003029A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- layered
- platy
- inorganic material
- layered inorganic
- Prior art date
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Classifications
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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
Definitions
- the polymer will not infiltrate into the space between the layers of the layered inorganic material and the layered inorganic material will not be sufficiently uniformly dispersed in the polymer.
- sodium or potassium ions normally present in natural forms of inorganic silicates or mica-type silicates and other multilayered particulate materials are exchanged with oniu ions (for example, alkylammonium ions) or the surface is functionalized with organosilanes, wherein the surface hydroxy groups are replaced with organosilanes .
- the cation exchange process with onium ions or the replacement of surface hydroxy groups with organosilane groups can render the normally hydrophilic inorganic or mica- type silicates organophilic and expand the interlayer distance of the layered material.
- Another process of rendering the mica-type silicates organophilic is to disperse or synthesize them in a glycol or other appropriate solvent.
- the organophilic mica-type silicates include those materials commonly referred to as organoclays .
- Nanocomposites are prepared by mixing the organophilic layered inorganic material (conventionally referred to as "nanofiller" ) with a monomer and/or oligomer of the polymer and then polymerizing the monomer or oligomer.
- the nanofiller may also be melt-compounded or melt- blended with the polymer. Blending the nanofillers with the monomer, oligomer or polymer may result in an increase of the average interlayer distance of the layered material by incorporation of the monomer, oligomer or polymer in the interlayer spaces. This increase in the average interlayer distance may result in an expanded ordered material, known as intercalated nanocomposite, or may result in a disordered or fully expanded material that is referred to as delaminated or exfoliated nanocomposite. Yet additional polymer composites containing these so-called nanofillers and/or their methods of preparation are described in U.S.
- U.S. Patent 5,554,670 describes cross-linked, epoxy-based nanocomposites produced from diglycidyl ether of bisphenol A (DGEBA) and certain specific curing agents.
- DGEBA diglycidyl ether of bisphenol A
- the present invention offers a great advantage in terms of processing costs and cost of materials as compared with onium ion exchange or with reaction with organosilanes . It would be desirable to provide lower cost synthetic layered materials with platy morphology rendered organophilic by low cost processes and low cost additives to make improved polymer nanocomposites by dispersion in suitable polymer matrices.
- the present invention is a modified layered inorganic platy silicate material possessing organophilic properties and comprising organic molecules having an alcohol functionality.
- the present invention is a nanocomposite comprising a polymer matrix having dispersed therein layers of the layered inorganic platy silicate material of the first aspect.
- the present invention is a method for preparing the modified layered inorganic platy silicate materials of the first aspect which comprises contacting a layered inorganic platy silicate material with a protonic acid and then contacting the acidified layered inorganic platy silicate material with an alcohol.
- the nanocomposites of this invention can exhibit an excellent balance of properties and can exhibit one or more superior properties such as improved heat or chemical resistance, ignition resistance, flame retardance, superior resistance to diffusion of polar liquids and of gases, yield strength in the presence of polar solvents such as water, methanol, or ethanol, or enhanced stiffness and dimensional stability, as compared to composites which do not contain the inorganic layered platy silicate material of the present invention.
- the nanocomposites of the present invention are useful as components in automotive and appliance parts, high barrier films for food packaging, wire and cable products with superior flame retardance, foams with superior mechanical and thermal properties, fibers for clothing and building materials.
- the layered inorganic platy silicate materials which can be employed in the practice of the present invention include any layered inorganic platy silicate materials.
- the layered inorganic platy silicate material comprises layers having two opposing faces which may be relatively flat or slightly curved. Such materials are described in detail in copending U.S. Application Serial No. 10/257487, incorporated herein in its entirety by reference.
- the layered inorganic platy silicate materials which can be employed in the practice of the present invention include, for example, the layered inorganic platy silicates such as platy magadiite, platy kenyaite, platy octasilicate, platy KHSi 2 0 5 , and platy Na 2 Si 2 0s and the like. More preferably, the layered inorganic platy silicate is a synthetic platy magadiite, the most preferred being a synthetic platy magadiite comprising more than ninety percent by weight of platy magadiite. Synthetic platy magadiites and their method of preparation are described in detail in copending U.S. Application Serial No.
- the protonic acids which can be employed in the practice of the present invention include any acid which will replace the surface sodium ions with a proton, such as, for example, hydrobromic acid, hydrochloric acid, hydrofluoric acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, phosphorus acid, p-toluenesulfonic acid, trichloroacetic acid, dichloroacetic acid, chloroacetic acid, acetic acid, benzoic acid, stearic acid, 1,4- butanedicarboxylic acid, citric acid, benzenesulfonic acid, and dinitrobenzoic acid.
- hydrobromic acid hydrochloric acid, hydrofluoric acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, phosphorus acid, p-toluenesulfonic acid, trichloroacetic acid, dichloroacetic acid, chloroacetic acid, acetic acid, be
- Preferred protonic acids are hydrochloric acid, nitric acid, p-toluenesulfonic acid; more preferred are hydrochloric acid and p-toluenesulfonic acid; and most preferred is hydrochloric acid.
- the protonic acid is used in an amount which is sufficient to produce enough silanol sites to react with alcohol molecules [ROH] to render the platy silicate organophilic .
- the protonic acid is used in an amount of from about 10 percent to about 100 percent, preferably from about 50 percent to about 100 percent, more preferably from about 75 percent to about 100 percent and, most preferably, from about 90 percent to about 100 percent, to convert the alkali metal silicate into the silicic acid form.
- the alcohols which can be employed in the practice of the present invention include primary, secondary or tertiary alcohols, including aliphatic and aromatic alcohols and any other compounds containing an alcohol group capable of reacting with the acid-treated layered platy silicate.
- Preferred alcohols are methanol, ethanol, n- butanol, the most preferred being ethanol.
- the amount of alcohols used depends on a variety of factors, including the specific inorganic layered material employed and the desired end-uses of the nanocomposites, in general, the alcohols can be present in an amount of from about 1 wt. percent to about 30 wt . percent, more preferably, from about 3 wt. percent to about 20 wt. percent and, most preferably, from about 3 wt. percent to about 10 wt percent, based on the weight of the modified magadiite.
- the polymers which can be employed in the practice of the present invention for preparing the nanocomposite include, for example, polypropylene, polyethylene, polyesters, polycarbonates, epoxies and polyurethanes .
- the modified inorganic layered material of the present invention can be prepared by contacting a layered inorganic material with an acid and then contacting the acid-treated layered inorganic material with an alcohol. This treatment can be carried on under reflux conditions at the boiling point of the alcohol, but it can also be advantageously conducted at room temperature by dispersing the acid-treated layered inorganic platy material in alcohol or mixture of alcohols .
- the layered inorganic material of the present invention can be dispersed the polymer matrix, in melted or liquid form.
- H+magadiites were prepared by adding a platy sodium magadiite to an acid solution as described in Table 1. The resulting acidified magadiite was filtered and washed with water to remove excess acid. The wet cake was dried in air at room temperature or at temperatures under 100 C.
- Example 2 The acidified magadiite (dry) prepared in Example 1 was added directly to a liquid alcohol and stirred at room temperature or was refluxed at the boiling temperature of the alcohol for sufficient time to render the product organophilic .
- C. Preparation of Polymer Nanocomposite The polymer used was polypropylene having a melt index of 0.7. Compounding of experimental samples was completed in a HAAKETM torque rheometer at 165°C, for 10 minutes, with a blending speed of 60 RPM. The treated H+magadiite and polymer were mixed dry before being added into the rheometer mixing head. Time of mixing was started when the polymer material was in a melt by visual observation.
- Table 1 show that the compounded test samples containing the alcohol-treated H+ magadiite exhibited increased modulus compared with the compounded test samples containing untreated H+ magadiite or with sodium magadiite. Moreover, the alcohol-treated H+-magadiite nanocomposites exhibited modulus comparable to amine treated H+-magadiites .
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A layered inorganic material possessing organophilic properties and comprising acid-treated layered platy silicate functionalized with organic molecules having alcohol functionality; a nanocomposite comprising the inorganic layered material and a method for preparing the inorganic layered material which comprises contacting a layered inorganic material with a protonic acid and then contacting the acidified layered inorganic material with an alcohol.
Description
MODIFIED LAYERED INORGANIC MATERIALS
Government Interests This application is under a Government contract with the National Institute of Standards and Technology, Advanced Technology Program Project # 97020047.
Background of the Invention The present invention relates to layered inorganic materials and nanocomposites . Layered inorganic materials such as talc, smectite clays and mica of micron size have been used in preparing nanocomposites . Nanocomposites are polymer composites in which at least one of its constituents has one or more dimensions, such as length, width or thickness, in the nanometer size range. Additives are often added to enhance one or more properties of the composition. A number of techniques have been described for dispersing the inorganic layered material into a polymer matrix to manufacture nanocomposites. However, without some additional treatment of the layered inorganic material or some additive added to the polymer, the polymer will not infiltrate into the space between the layers of the layered inorganic material and the layered inorganic material will not be sufficiently uniformly dispersed in the polymer. To facilitate a more uniform dispersion of the layered inorganic material in the polymer, as described in U.S. Patent 4,889,885, sodium or potassium ions normally present in natural forms of inorganic silicates or mica-type silicates and other multilayered particulate materials are exchanged with oniu ions (for example, alkylammonium ions) or the surface is functionalized with organosilanes, wherein the surface hydroxy groups are replaced with organosilanes .
The cation exchange process with onium ions or the replacement of surface hydroxy groups with organosilane groups can render the normally hydrophilic inorganic or mica- type silicates organophilic and expand the interlayer distance of the layered material. Another process of rendering the mica-type silicates organophilic is to disperse or synthesize them in a glycol or other appropriate solvent. The organophilic mica-type silicates include those materials commonly referred to as organoclays . Nanocomposites are prepared by mixing the organophilic layered inorganic material (conventionally referred to as "nanofiller" ) with a monomer and/or oligomer of the polymer and then polymerizing the monomer or oligomer. The nanofiller may also be melt-compounded or melt- blended with the polymer. Blending the nanofillers with the monomer, oligomer or polymer may result in an increase of the average interlayer distance of the layered material by incorporation of the monomer, oligomer or polymer in the interlayer spaces. This increase in the average interlayer distance may result in an expanded ordered material, known as intercalated nanocomposite, or may result in a disordered or fully expanded material that is referred to as delaminated or exfoliated nanocomposite. Yet additional polymer composites containing these so-called nanofillers and/or their methods of preparation are described in U.S. Patents 4,739,007; 4,618,528; 4,528,235; 4,874,728; 4,889,885; 4,810,734; and 5, 385, 776 ; WO 95/14733; WO 93/04117; Chem. Mater. Vol. 6, pages 468-474 and 1719- 1725; and Vol. 7, pages 2144-2150; and Chem. Mater., Vol. 8, pages 1584-1587 (1996) . U.S. Patent 5,554,670 describes cross-linked, epoxy-based nanocomposites produced from diglycidyl ether of bisphenol A (DGEBA) and certain specific curing agents. This
patent teaches that bifunctional primary or secondary amines do not produce delaminated nanocomposite structures and instead result in opaque composites. Chem. Mater., Vol. 8, pages 1584-1587 (1996) describes the importance of complete ion-exchange in the formation of organoclays to provide nanocomposites with maximized performance. Pinnavaia et al . (United States Patent 5,993,769) disclose less than fully exchanged cation exchanging layered material. The composites and techniques described above are costly, since they require the use of amines and quaternary salts having long carbon chains, in excess of 8 to 18 atoms or more, which requires a high weight percent of these compounds and a concomitant high cost to make the organoclays . The present invention offers a great advantage in terms of processing costs and cost of materials as compared with onium ion exchange or with reaction with organosilanes . It would be desirable to provide lower cost synthetic layered materials with platy morphology rendered organophilic by low cost processes and low cost additives to make improved polymer nanocomposites by dispersion in suitable polymer matrices.
Summary of the Invention Accordingly, in a first aspect, the present invention is a modified layered inorganic platy silicate material possessing organophilic properties and comprising organic molecules having an alcohol functionality. In a second aspect, the present invention is a nanocomposite comprising a polymer matrix having dispersed therein layers of the layered inorganic platy silicate material of the first aspect.
In a third aspect, the present invention is a method for preparing the modified layered inorganic platy silicate materials of the first aspect which comprises contacting a layered inorganic platy silicate material with a protonic acid and then contacting the acidified layered inorganic platy silicate material with an alcohol. Other aspects of the present invention will become apparent from the following detailed description and claims. Surprisingly, it has been discovered that treatment of the acidified layered inorganic platy silicate materials with simple alcohols such as ethanol or n-butanol, which are less costly than amines and quaternary salts, yields a treated layered inorganic platy silicate material that improves substantially the mechanical performance of nanocomposites with polypropylene. The nanocomposites of this invention can exhibit an excellent balance of properties and can exhibit one or more superior properties such as improved heat or chemical resistance, ignition resistance, flame retardance, superior resistance to diffusion of polar liquids and of gases, yield strength in the presence of polar solvents such as water, methanol, or ethanol, or enhanced stiffness and dimensional stability, as compared to composites which do not contain the inorganic layered platy silicate material of the present invention. The nanocomposites of the present invention are useful as components in automotive and appliance parts, high barrier films for food packaging, wire and cable products with superior flame retardance, foams with superior mechanical and thermal properties, fibers for clothing and building materials.
Detailed Description of the Invention The layered inorganic platy silicate materials which can be employed in the practice of the present invention include any layered inorganic platy silicate materials. Typically, the layered inorganic platy silicate material comprises layers having two opposing faces which may be relatively flat or slightly curved. Such materials are described in detail in copending U.S. Application Serial No. 10/257487, incorporated herein in its entirety by reference. Preferably, the layered inorganic platy silicate materials which can be employed in the practice of the present invention include, for example, the layered inorganic platy silicates such as platy magadiite, platy kenyaite, platy octasilicate, platy KHSi205, and platy Na2Si20s and the like. More preferably, the layered inorganic platy silicate is a synthetic platy magadiite, the most preferred being a synthetic platy magadiite comprising more than ninety percent by weight of platy magadiite. Synthetic platy magadiites and their method of preparation are described in detail in copending U.S. Application Serial No. 10/257487, incorporated herein in its entirety by reference. The protonic acids which can be employed in the practice of the present invention include any acid which will replace the surface sodium ions with a proton, such as, for example, hydrobromic acid, hydrochloric acid, hydrofluoric acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, phosphorus acid, p-toluenesulfonic acid, trichloroacetic acid, dichloroacetic acid, chloroacetic acid, acetic acid, benzoic acid, stearic acid, 1,4- butanedicarboxylic acid, citric acid, benzenesulfonic acid, and dinitrobenzoic acid. Preferred protonic acids are hydrochloric acid, nitric acid, p-toluenesulfonic acid; more
preferred are hydrochloric acid and p-toluenesulfonic acid; and most preferred is hydrochloric acid. The protonic acid is used in an amount which is sufficient to produce enough silanol sites to react with alcohol molecules [ROH] to render the platy silicate organophilic . In general, the protonic acid is used in an amount of from about 10 percent to about 100 percent, preferably from about 50 percent to about 100 percent, more preferably from about 75 percent to about 100 percent and, most preferably, from about 90 percent to about 100 percent, to convert the alkali metal silicate into the silicic acid form. The alcohols which can be employed in the practice of the present invention include primary, secondary or tertiary alcohols, including aliphatic and aromatic alcohols and any other compounds containing an alcohol group capable of reacting with the acid-treated layered platy silicate. Preferred alcohols are methanol, ethanol, n- butanol, the most preferred being ethanol. While the amount of alcohols used depends on a variety of factors, including the specific inorganic layered material employed and the desired end-uses of the nanocomposites, in general, the alcohols can be present in an amount of from about 1 wt. percent to about 30 wt . percent, more preferably, from about 3 wt. percent to about 20 wt. percent and, most preferably, from about 3 wt. percent to about 10 wt percent, based on the weight of the modified magadiite.
The polymers which can be employed in the practice of the present invention for preparing the nanocomposite include, for example, polypropylene, polyethylene, polyesters, polycarbonates, epoxies and polyurethanes .
In general, the modified inorganic layered material of the present invention can be prepared by contacting a layered inorganic material with an acid and then contacting the acid-treated layered inorganic material with an alcohol. This treatment can be carried on under reflux conditions at the boiling point of the alcohol, but it can also be advantageously conducted at room temperature by dispersing the acid-treated layered inorganic platy material in alcohol or mixture of alcohols . The layered inorganic material of the present invention can be dispersed the polymer matrix, in melted or liquid form. The following working examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
Example 1
PREPARATION OF H+ MAGADIITE Several acidified magadiites (H+magadiites) were prepared by adding a platy sodium magadiite to an acid solution as described in Table 1. The resulting acidified magadiite was filtered and washed with water to remove excess acid. The wet cake was dried in air at room temperature or at temperatures under 100 C.
Example 2
Alcohol Treatment The acidified magadiite (dry) prepared in Example 1 was added directly to a liquid alcohol and stirred at room temperature or was refluxed at the boiling temperature of the alcohol for sufficient time to render the product organophilic .
C. Preparation of Polymer Nanocomposite The polymer used was polypropylene having a melt index of 0.7. Compounding of experimental samples was completed in a HAAKE™ torque rheometer at 165°C, for 10 minutes, with a blending speed of 60 RPM. The treated H+magadiite and polymer were mixed dry before being added into the rheometer mixing head. Time of mixing was started when the polymer material was in a melt by visual observation. After removal from torque rheometer, the composites were cooled at room temperature, and ground to less than #5 mesh particles for modulus testing. Compounded test samples were molded into type V specimens with a gage of 1.5 inches. Molding conditions were 170°C for 4 minutes at 500 psi during pre-heat; and 4 minutes at 30 Kpsi and 170°C. Cool time was 10 minutes at 30 Kpsi. A type V specimen is a specimen with a V shape and used for testing by ASTM methods. Modulus testing was completed per ASTM D882. The results are shown in Table 1. The data in Table 1 show that the compounded test samples containing the alcohol-treated H+ magadiite exhibited increased modulus compared with the compounded test samples containing untreated H+ magadiite or with sodium magadiite. Moreover, the alcohol-treated H+-magadiite nanocomposites exhibited modulus comparable to amine treated H+-magadiites .
TABLE 1 Tensile Relative SAMPLES Modulus Modulus (psi) Increase
H+Magadiite, wet, Decylamine, Toluene 229136 1.0415 treated H+Magadiite, wet, Octylamine, Toluene 237181 1.0781 treated
H+Magadiite, wet, Ethanol Refluxed 314547 1. 429 8
H+Magadiite, wet, Decylamine, Toluene 240972 1 .0953 treated
H+Magadiite, wet, Butanol Refluxed 280826 1 .2765
H+Magadiite, wet, Hexylamine, Toluene 311870 1 .4176 treated
H+Magadiite, NN 1,3 Phenylenedimaleimide 284739 1 .2943
IN Sulfuric acid treated Na-Magadiite 287913 1. .3087
IN Phosphoric acid treated Na-Magadiite 283573 1. .2890
IN Nitric acid treated Na-Magadiite 281006 1. .2773
IN Acetic acid treated Na-Magadiite 291925 1. .3269
Na-Magadiite 269381 1, .2245
Montell polypropylene PD-191 220000 220000 1
Claims
1. A layered inorganic material possessing organophilic properties and comprising acid-treated layered platy silicate functionalized with organic molecules having alcohol functionality.
2. The layered inorganic material of Claim 1 wherein the organic molecule having alcohol functionality is derived from compounds containing an alcohol group capable of reacting with the acid-treated layered platy silicate.
3. The layered inorganic material of Claim 1 wherein the layered platy silicate is selected from the group consisting of platy magadiite, platy kenyaite, platy octasilicate, platy KHSi205, and platy Na2Si205.
4. The layered inorganic material of Claim 3 wherein the layered platy silicate is synthetic magadiite.
5. The layered inorganic material of Claim 4 wherein the synthetic magadiite comprises more than ninety percent by weight of platy magadiite.
6. The layered inorganic material of Claim 1 wherein the organic molecule having alcohol functionality is derived from the group consisting of aliphatic and aromatic alcohols .
7. The layered inorganic material of Claim 1 wherein the organic molecule having alcohol functionality is derived from the group consisting of primary, secondary and tertiary alcohols.
8. The layered inorganic material of Claim 1 wherein the organic molecule having alcohol functionality is derived from the group consisting of methanol, ethanol and n- butanol .
9. The layered inorganic material of Claim 2 wherein the compound containing an alcohol group is used in an amount of from about 1 wt. percent to about 30 wt. percent, based on the weight of the inorganic layered material .
10. A nanocomposite comprising a polymer matrix having dispersed therein layers of the layered inorganic material of Claim 1.
11. The nanocomposite of Claim 10 wherein the polymer matrix comprises a polymer selected from the group consisting of polypropylene, polyethylene, polyesters, polycarbonates, epoxies, and polyurethanes .
12. A method for preparing the layered inorganic material of Claim 1 which comprises contacting a layered inorganic material with a protonic acid and then contacting the acidified inorganic layered material with an alcohol.
13. The method of Claim 12 wherein the protonic acid is selected from the group consisting of hydrobromic acid, hydrochloric acid, hydrofluoric acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, phosphorus acid, p-toluenesulfonic acid, trichloroacetic acid, dichloroacetic acid, chloroacetic acid, acetic acid, benzoic acid, stearic acid, 1, 4-butanedicarboxylic acid, citric acid, benzenesulfonic acid, and dinitrobenzoic acid.
14. The method of Claim 13 wherein the protonic acid is hydrochloric acid.
15. The method of Claim 12 wherein the alcohol is selected from the group consisting of primary, secondary and tertiary alcohols .
16. The method of Claim 12 wherein the alcohol is selected from the group consisting of methanol, ethanol and n-butanol .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| US48351303P | 2003-06-27 | 2003-06-27 | |
| US60/483,513 | 2003-06-27 |
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| WO2005003029A2 true WO2005003029A2 (en) | 2005-01-13 |
| WO2005003029A3 WO2005003029A3 (en) | 2005-06-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006115729A1 (en) * | 2005-04-22 | 2006-11-02 | Inmat, Inc. | Barrier coating mixtures containing non-elastomeric acrylic polymer with silicate filler and coated articles |
| US8846558B2 (en) | 2008-07-18 | 2014-09-30 | Exxonmobil Research And Engineering Company | Functionalization of the internal surfaces of zeolites with alcohol compounds |
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| US4889885A (en) * | 1987-03-04 | 1989-12-26 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite material containing a layered silicate |
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| CN1272513C (en) * | 2004-10-07 | 2006-08-30 | 李奎仁 | Rod angle requlating fixing connector |
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| DD257629A1 (en) * | 1987-02-18 | 1988-06-22 | Univ Halle Wittenberg | PROCESS FOR PREPARING CRYSTALLINE SILICONE ACID WITH LAYERED TEMPERED CONSTRUCTION |
| US4889885A (en) * | 1987-03-04 | 1989-12-26 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite material containing a layered silicate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7473729B2 (en) | 2003-08-29 | 2009-01-06 | Inmat Inc. | Barrier coating mixtures containing non-elastomeric acrylic polymer with silicate filler and coated articles |
| WO2006115729A1 (en) * | 2005-04-22 | 2006-11-02 | Inmat, Inc. | Barrier coating mixtures containing non-elastomeric acrylic polymer with silicate filler and coated articles |
| US8846558B2 (en) | 2008-07-18 | 2014-09-30 | Exxonmobil Research And Engineering Company | Functionalization of the internal surfaces of zeolites with alcohol compounds |
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| Publication number | Publication date |
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| WO2005003029A3 (en) | 2005-06-23 |
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