WO2008045077A1 - Nanoargiles expansées et procédé de fabrication de telles nanoargiles expansées - Google Patents

Nanoargiles expansées et procédé de fabrication de telles nanoargiles expansées Download PDF

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Publication number
WO2008045077A1
WO2008045077A1 PCT/US2006/040051 US2006040051W WO2008045077A1 WO 2008045077 A1 WO2008045077 A1 WO 2008045077A1 US 2006040051 W US2006040051 W US 2006040051W WO 2008045077 A1 WO2008045077 A1 WO 2008045077A1
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Prior art keywords
acid
nanoclay
clay
producing
intercalant
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PCT/US2006/040051
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English (en)
Inventor
Kivanc Isik
Gokhan Andi
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Kivanc Isik
Gokhan Andi
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Publication date
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Priority to PCT/US2006/040051 priority Critical patent/WO2008045077A1/fr
Publication of WO2008045077A1 publication Critical patent/WO2008045077A1/fr

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    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • 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
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • 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
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like

Definitions

  • the present invention relates generally to nanoclays. More specifically, the present invention relates to a method of producing expanded clays using carboxylic acid salts and soluble organic acids.
  • Nanocomposites are a new class of composite materials that contain nano-level inorganic particulates such as silica (as described in the paper to Motomatsu, et al. titled “Microstructure of acrylic polymer-silica nanocomposite surface by scanning force microscopy”) and clay (as described in the paper to Kawasumi, et al. titled “Preparation and mechanical properties of Polypropylene-clay hybrids”) in polymer structures.
  • the first clay/polymer nanocomposites based on Nylon-6 (as described in the publication to Okada, et al. titled “Synthesis and properties of nylon 6/clay hybrids, Polymer based molecular composites”) were produced on 1989 in Toyota research laboratories of Japan.
  • Figure 1 shows a typical 2:1 layered silicate the layer is made up of a central octahedral sheet, usually occupied by aluminum or magnesium, sandwiched ISG-3061055
  • MMT is naturally a hydrophilic material, which makes it difficult to exfoliate in a polymer matrix. Therefore, surface treatment of silicate layers is necessary to render its surface more hydrophobic, which facilitates exfoliation. Generally, this can be done by ion-exchange reactions between the cationic onium ions in the form of ammonium or phosphonium functional group (R 4 N + X ' or R 4 P + X " ) and the Na + cations in the clay structure. The ion exchange and intercalation alkyl chain in the interlayer expands the basal spacing between the silicate layers.
  • U.S. Patent No. 6,414,069 to Pinnavaia uses an intercalating agent CH 3 (CH 2 ) ⁇ NH3 + in the exchange reaction with metal ion salts in the layered structure of montmorillonite clay (MMT) and organically modified MMT is then dispersed in diglycidyl ether of bisphenol-A to form epoxy/layered clay nanocomposite.
  • MMT montmorillonite clay
  • the basal spacing of MMT is increased to 18 0 A.
  • the mixture of MMT with epoxy resin forces the polymeric molecules into the clay layers and a nanocomposite structure is formed after curing at 75 0 C.
  • the interlayer distance (basal spacing) of clay is between 13-18 0 A, which allows the epoxy to polymerize within and further exfoliate the layered structure of the clay.
  • Japanese Patent No. 8-22946 discloses commercial inorganic/organic polymer composite material in nanoscale dispersion.
  • the composite material is synthesized by dispersing [H 3 N + (CH 2 ) H COO " ] -montmorillonite in Nylon-6, in which amino carboxylic acid is provided as an intercalating agent and the polymers are formed between the layers of the amino acid intercalated clay by condensing caprolactam monomers to Nylon-6 polymer.
  • the amino carboxylic acid intercalating agent renders the modified clay compatible for Nylon-6.
  • these modified montmorillonite is unsuitable for nonpolar polymers such as polyethylene and polypropylene.
  • Japanese Patent Publication No. 8-53572 provides other organic onium ions as intercalating agents to mix with layered silicate that can easily disperse in polyolefin resin.
  • the organic onium ions can only enlarge the interlayer distances to an amount between
  • the present invention in one embodiment, teaches the production of nanoclays that are highly dispersible in polymers and have an interlayer distance of at least 3O 0 A.
  • the present invention in another embodiment, teaches a method to produce a clay/organic salt/organic acid complex.
  • layered clay is hydrated with water to prepare swelled clay.
  • the swelled clay is mixed with an alkali salt of a fatty acid and heated to a temperature of at least 50 0 C, to prepare a clay/organic salt complex.
  • a soluble polar organic acid is added to the clay/organic salt complex at a temperature of at least 5O 0 C, to prepare the clay/organic salt/organic acid complex wherein the soluble polar organic acid is hydrogen bonded to the clay/organic salt complex.
  • Another embodiment of the present invention teaches a method to produce nanoclay comprising the steps of: (a) preparing a first intercalant, (b) swelling clay with water, (c) adding the first intercalant with the swelled clay at a temperature of at least 5O 0 C, preferably from 50-
  • the layered silicate completely precipitates after 6 hours at the temperature between 50-60 0 C and pH in the range of 1.8-3.4.
  • the precipitate of layered silicate is further homogenized with water and alcohol solution.
  • the homogenate is further filtered, dried, milled, and sieved to desired nanoclay.
  • the first intercalant is prepared by heating a mixture comprising of fatty acid and alkali base in an aqueous medium at a temperature of at least 5O 0 C, preferably from 50-80 0 C.
  • the fatty acid and alkali base are added at a molar ratio of 1:1.
  • the alkali base can be selected from but not limited to the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and francium hydroxide.
  • the fatty acid has a molecular weight ranging from 200 g/mol to 340 g/mol.
  • the fatty acid can be selected from but not limited to the group consisting butyric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, alpha-linolenic acid, docosahexaenoic acid, eicosapentaenoic acid, arachidonic acid, erucic acid.
  • the second intercalant with long carbon chain is used to further modify expanded layered clays to increase the compatibility with organic polymers.
  • the second intercalant is selected from a group of water soluble organic acids having polar carboxylic groups.
  • Polyacrylic acid (PAA) is a suitable organic acid for second intercalation reaction, because it is water soluble and it contains polar carboxylic groups.
  • the second intercalant has the molecular weight ranging from 87 g/mol to 230,000 g/mol.
  • the second intercalant can be selected from but not limited to the group consisting polyethylene oxide, polypropylene oxide, their amine derivatives polyethyleneoxide- amine, polypropylene oxide-amine, polyacrylic acid, polyvinyl alcohol, polyvinyl alcohol-amine, polyacrylamide, poly-N-vinyl pyrrolidone, polymethacrylic acid or a combination thereof.
  • the second intercalating agent is added to the solution of swelled intercalated clay to increase the amount of intercalation of the organic molecules through the silicate galleries.
  • the second intercalant is added at a pH in the range of
  • the second intercalant is added at the same temperature and pH of step (c).
  • the clay used in the present invention is layered clay.
  • the layered clay can be selected from but not limited to the group consisting montmorillonite, sepiolite, vermiculite, kaolin, mica, and talc.
  • the clay used in the present invention has a cation exchange capacity (CEC) ranging between 40-200 meq/100 g.
  • CEC cation exchange capacity
  • the molar ratio of said first intercalant to cationic exchange capacity of said layered clay is n:(n+l), where n is any number from 1 to 6.
  • the weight ratio of said second intercalant to the layered clay is k: (k+1), wherein k is any number from 1 to 7.
  • the alcohol used in the homogenizing step can be selected from but not limited to the group consisting of a group consisting of methyl, ethyl, propyl, butyl alcohol, and combination thereof.
  • the alcohol to water weight ratio in homogenizing step is m:(l- m), where m is any number from 0.2 to 0.6.
  • the homogenizing step is performed at a temperature in the range of 20-50 0 C.
  • the drying step is carried out at a temperature of at least 8O 0 C.
  • the milling of dried nanoclay is carried out at range of 50-150 rpm.
  • the sieving of milled nanoclay is carried out at range of 75 ⁇ m - 105 ⁇ m mesh.
  • the nanoclay of the present comprises of a structure formula I:
  • M is a divalent metal selected from a group consisting OfMg 2+ , Ca 2+ ;
  • R' is an organic acid selected from a group consisting of Polyacrylic acid, Poly(acrylamide) acid, Carboxylic pyrrolidonic acid, Poly(methacrylic) acid;
  • CL is a layered clay selected from a group consisting of montmorillonite, sepiolite, kaolin, vermiculite, and mica;
  • R is a long chain alkyl
  • R' is hydrogen bonded with free hydroxyl groups of the layered clay.
  • Figure 1 illustrates Phyllosilicate structure of montmorillonite used according to one embodiment of the present invention.
  • Figure 2 illustrates a flowchart for nanoclay production process according to an exemplary embodiment of the present invention.
  • Figure 3 illustrates the mechanism of modification of nanoclays with the first intercalant, intercalation with alkali salts of carboxylic acids according to an exemplary embodiment of the present invention.
  • Figure 4 illustrates the mechanism of modification of nanoclays with the second intercalant, intercalation with soluble organic acids according to an exemplary embodiment of the present invention.
  • Figure 5 illustrates the XRD pattern of natural montmorillonite.
  • Figure 6 illustrates the XRD pattern of natural montmorillonite intercalated with alkali salts of carboxylic acids according to an exemplary embodiment of the present invention.
  • Figure 7 illustrates the XRD pattern of modified montmorillonite intercalated with soluble organic acids according to an exemplary embodiment of the present invention.
  • the process of production of nanoclays described hereinafter is not limited to MMT and the process maybe applied to any other layered clay such as montmorillonite, sepiolite, kaolin, vermiculite, mica, or a combination thereof.
  • Figure 2 illustrates process 100 to produce expanded nanoclays according to an exemplary embodiment of the present invention.
  • Layered clay is swelled with water to produce hydrated layered clay in step S102.
  • Salts of carboxylic acids may be prepared through a process of heating a mixture comprising of carboxylic acid and alkali base in an aqueous medium at a temperature of at least 5O 0 C in step SlOl.
  • the alkali base used may be, but not limited to ISG-3061055
  • the carboxylic acid may be a fatty acid with a molecular weight ranging from 200 g/mol to 340 g/mol.
  • the fatty acid may be, but not limited to butyric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, alpha-linolenic acid, docosahexaenoic acid, eicosapentaenoic acid, arachidonic acid, erucic acid.
  • the reaction mechanism to produce clay/organic salt complex is illustrated in Figure 3.
  • the divalent ion on the clay surface forms a complex with the carboxyl group that enlarges the space between the two galleries of natural montmorillonite.
  • the alkali metal that has one valent electron bonds to the oxygen atom on the clay layer. Since the distance between the clay layers are increased after this modification, the penetration of organic acids with high molecular weight is promoted for further intercalation.
  • the process of intercalating soluble organic acids (second intercalant) in clay/organic salt complex produced in step S103 yields the production of clay/organic salt/organic acid complex in step S104.
  • Soluble organic acids used as second intercalants may be, but not limited to polyacrylic acids (PAA).
  • PAA polyacrylic acids
  • the acidic character of PAA lowers the pH of the fatty acid salt/layered clay complex solution. At this low pH condition, exchange of alkali metals (generally, Na + or K + ) by H + occurs and hydroxyl groups on the clay surfaces are formed.
  • Figure 4 illustrates the reaction mechanism of intercalation of soluble organic acid to clay/organic salt complex. The penetration of long carbon chained PPA is promoted by the formation of hydrogen bonds between the hydroxyl group on the clay surface and carboxyl group in the structure of PPA.
  • Expanded nanoclays are precipitated from the clay/organic salt/organic acid complex solution produced by step S104.
  • Post processing of the precipitate clay/organic salt/organic acid complex produced in step S105 may be necessary to produce desired expanded nanoclays.
  • Post processing steps, represented by step S106, of the present invention may include, but not limited to further homogenization, filtration, drying, milling, sieving, and a combination thereof.
  • the precipitate produced in step S105 is homogenized with an alcohol and water solution.
  • the alcohol to water weight ratio homogenizing solution may be m:(l-m), where m is any number from 0.2 to 0.6.
  • the alcohol may be an aliphatic alcohol such as methanol, ethanol, propanol, butanol, or combination thereof. Homogenizing may be performed at a temperature in the range ISG-3061055
  • the filtrate of homogenate may be dried at a temperature of at least 8O 0 C. Milling of dried filtrate is carried out at range of 50-150 rpm.
  • the nonoclay may be obtained after sieving of milled nanoclay. The sieving is carried out at range of 75 ⁇ m - 105 ⁇ m mesh.
  • the present invention includes no hazardous chemicals to be used and to be released as waste products during the process. Less water consumption is another advantage indicating the environmental sensitivity of nanoclay production by this method.
  • the developed chemical process allows producing nanoclays with increased layer distances that are more organic and compatible with plastic materials than the present nanoclays.
  • the thermal stability of the organic molecules in the nanoclay structure will promote the usage of this unique filler at elevated temperatures and in high-temperature melting plastics.
  • the present invention includes a chemical modification process of clays that comprises two intercalation reactions; first with the alkali salts of carboxylic acids and second with the intercalation of high molecular weight organic acids.
  • the enlargement of clay galleries is improved by using water soluble acids containing carboxyl groups.
  • Use of alkali salts of fatty acid increases volume between the silicate layers for the organic acid penetration.
  • the use of alkali salts of fatty acid as the first intercalant promotes the intercalation of long organic molecules by modifying the silicate surfaces for hydrogen bonding between the hydroxyl groups on the surface and carboxyl group in the organic acid structure.
  • This invention provides nanoclays with high quality basal spacing and hydrophobic behavior. These nanoclays may be used in high temperature applications.
  • Fatty acid is mixed with Potassium hydroxide (KOH) in the molar ratio of 1:1.
  • KOH Potassium hydroxide
  • the mixture is heated to temperatures of at least 5O 0 C to facilitate the formation of fatty acid salt, which is the first intercalant to be used for producing nanoclay.
  • Montmorillonite (MMT) is hydrated with water. The series of reactions in this first step is summarized in below:
  • Polyacrylic acid is one of the most suitable organic acids for second intercalation reaction, because it is water soluble and it contains polar carboxylic groups. It is added to the solution of carboxylic salt/MMT complex with a weight ratio of MMT to polyacrylic acid, k: (k+1), where k varies from 1 to 7, under pH conditions 1.8-3.4.
  • the polyacrylic acid finds enough free space to intercalate into the clay galleries that was previously increased by carboxylic salt intercalant.
  • the acidic media promotes the formation of hydrogen bonds between the silicate layers and water soluble polyacrylic acid.
  • the XRD pattern of polyacrylic acid modified nanoclay is shown in Figure 7. Further intercalation increases the number of silicate layers with the d-spacing around 4O 0 A and the minor peaks of 3.61° and 5.37° become invisible in the pattern. Addition to this the basal spacing is increased from 40.91 0 A to
  • the present invention provides for an expanded nanoclay and method for intercalating natural layered clay using two intercalants without using the conventional ion exchange step.
  • This invention has the advantages that the consumption of water and production of hazardous chemicals is reduced. By eliminating the ion exchange reactions, no hazardous waste is added to the environment in the process of nanoclay production. This invention provides a more economic way of nanoclay production. ISG-3061055

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne un procédé de fabrication de nanoargiles comprenant les étapes de préparation d'un premier sel alcalin d'intercalation d'un acide carboxylique S101, en ajoutant le premier composé d'intercalation à une argile gonflée à une température d'au moins 50°C de sorte que les ions métalliques sur la surface d'argile forment un complexe avec le groupe carboxyle qui élargit l'espace entre les deux galeries d'argile S103. Le procédé comprend en outre l'étape consistant à ajouter un acide organique comme second composé d'intercalation S104 à l'argile modifiée par le premier composé d'intercalation afin de former un complexe argile/sel organique/acide organique. Le complexe argile/sel organique/acide organique peut être soumis à un post-traitement S106 par précipitation, homogénéisation avec une solution comprenant de l'eau et un alcool, filtration, séchage, broyage et tamisage pour produire la nanoargile désirée.
PCT/US2006/040051 2006-10-12 2006-10-12 Nanoargiles expansées et procédé de fabrication de telles nanoargiles expansées WO2008045077A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016185220A1 (fr) * 2015-05-20 2016-11-24 Flexitallic Limited Matériau d'étanchéité
CN107686670A (zh) * 2017-09-05 2018-02-13 重庆卡美伦科技有限公司合川分公司 一种高膨胀性能环保膨润土及其制备方法
CN112374506A (zh) * 2020-11-19 2021-02-19 江苏博联新材料科技有限公司 一种复合膨润土添加剂中间料的改性工艺

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US20030144401A1 (en) * 2001-12-21 2003-07-31 Manoj Ajbani Nanocomposite of elastomer and dispersion therein of intercalated clay prepared in an aqueous medium with functional elastomer

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016185220A1 (fr) * 2015-05-20 2016-11-24 Flexitallic Limited Matériau d'étanchéité
US11345633B2 (en) 2015-05-20 2022-05-31 Flexitallic Investments, Inc. Sealing material
CN107686670A (zh) * 2017-09-05 2018-02-13 重庆卡美伦科技有限公司合川分公司 一种高膨胀性能环保膨润土及其制备方法
CN112374506A (zh) * 2020-11-19 2021-02-19 江苏博联新材料科技有限公司 一种复合膨润土添加剂中间料的改性工艺

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