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WO2005068365A1 - Materiaux en couches intercalees un particulier de nano-argiles - Google Patents

Materiaux en couches intercalees un particulier de nano-argiles Download PDF

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Publication number
WO2005068365A1
WO2005068365A1 PCT/IN2004/000008 IN2004000008W WO2005068365A1 WO 2005068365 A1 WO2005068365 A1 WO 2005068365A1 IN 2004000008 W IN2004000008 W IN 2004000008W WO 2005068365 A1 WO2005068365 A1 WO 2005068365A1
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WO
WIPO (PCT)
Prior art keywords
hydroxyl
clay
exfoliated
nanoclay
poly
Prior art date
Application number
PCT/IN2004/000008
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English (en)
Inventor
Sujit Banerji
Anand Kumar Kulshreshtha
Karumanchi Venkateswara Rao
Anil Vitthal Patil
Ajit Kumar Maiti
Sodagudi Francis Xavier
Original Assignee
Indian Petrochemicals Corporation Limited
Reliance Industries Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Indian Petrochemicals Corporation Limited, Reliance Industries Ltd. filed Critical Indian Petrochemicals Corporation Limited
Priority to PCT/IN2004/000008 priority Critical patent/WO2005068365A1/fr
Publication of WO2005068365A1 publication Critical patent/WO2005068365A1/fr

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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 present invention relates to intercalated layered materials.
  • the present invention relates to exfoliated nanoclays and processes for the preparation thereof. More particularly, the present invention relates to a process for the preparation of exfoliated nanoclays by contacting and thereby intercalating a layered silicate clay material such as bentonite by sorption of an aqueous intercalant.
  • the intercalant solution enters inside clay and causes it to interact with water present inside the clay mineral.
  • the resulting clay is put in a heat sink, dried and tested by x-ray diffraction. This results in producing exfoliated nanoclays from layered mineral clays.
  • Nanoclay is the latest layered clay for making plastics nanocomposites which have superior mechnical properties, barrier properties and flame resistance over conventional plastics and yet their optical properties remain intact because the addition level of nanoclay is in 1 to 6% range.
  • In market the availability of nanoclay is very expensive [$55/lb] and it is marketed as masterbatches to mask their identity.
  • Nanoclays are surface modified montmorillonite minerals available for a range polymer resins from commodity polyolefins to specialty polyamides. Incorporation into these resins forms a nanocomposite plastic. Because Nanoclays are used at low addition levels, significant property improvement is achieved with lighter weight parts. Nanoclays have a platey morphology.
  • the layered clays originated from volcanic ash. Common clays are naturally occurring minerals. The term “Bentonite” was applied for the first time to a particular kind of clay discovered near Fort Benton, Wyoming. This clay displays strong colloidal properties and when in contact with water, increases its volume several fold by swelling, giving rise to a thixotropic, gelatinous substance, but the other clay minerals such as illite and kaolinite may be present.
  • the composition of montmorillonite [MMT] itself varies from one bentonite to another, but lies in the range of 75-95%.
  • Layered smectite- type MMT a hydrous alumina silicate mineral whose lamellae are constructed from octahedral alumina sheets sandwiched between two tetrahedral silicate sheets, exhibits a net negative charge on the lamellar surface, which enables them to adsorb cations, such as Na+ or Ca++.
  • Compatibility with various polymers is accomplished by modifying the silicates with alkylammonium cations via an ion exchange reaction [[Y.; Kurauchi T.T., Kamigaito, O.J Mater. Res.
  • the organic cations contain various functional groups that react with the polymers and reinforce adhesion between the particles and the matrix, thus producing nanocomposites with excellent dispersion quality in organic solvents.
  • the surfactant chain length gets larger, the charge density of the clay and the spacing between the clay layers increase.
  • AMCOL International Corporation has been active in seeking patent protection in this field and Nanocor is the beneficial holder of over two dozen US patents.
  • US 6,399,690 (2002) granted the above said company describes preparation of layered compositions with multicharged onium ions as exchange cations and their application to prepare intercalated and nanocomposites.
  • WO 97/31973 discloses producing a composite material by mixing potassium ionomer in which an ethylene methacrylate copolymer is either partially or completely neutralized with an organic polymer.
  • US Patent Nos. 4,739,007 and 5,164,460 disclose polyamide and polyimide composite materials respectively containing layered clay mineral intercalated with organic salts. In all the above patents, the intercalant were organic solvents. The organic pretreatment of the clay adds to the cost of the clay, even though the clay are relatively cheap. Need for intercalated and exfoliated clays has been growing as the field of Nanocomposites is at an embryonic stage of development today. A decade ago nanocomposite technology was a concept with great potential. Today, it is a reality.
  • smectic mineral clay e.g., bentonite, of local or international origin
  • the purpose of this invention is to increase unrestricted availability of nanoclays to plastic producers and plastics processors-small as well as large-to create vast, untapped markets for plastics.
  • the present invention thus relates to production of nanoclays for creating new markets for polymer nanocomposites from all types of plastics [biopolymers. thermoplastics, engineering plastics, thermosets, fibers, etc.] and boosting the per capita consumption of plastics without posing and threat to environment.
  • the present invention provides exfoliated nanoclay which comprises layered clay [e.g., sodium bentonite] and an intercalation material sorbed between layers of said layered clay.
  • said intercalation material is present in a concentration of from 10 to 100 % by weight based on the dry weight of said layered clay.
  • said intercalation material is pure or an aqueous solution of a hydroxyl-rich molecule.
  • said hydroxyl-rich molecule has the general formula:
  • said hydroxyl - rich molecule is selected from the group consisting of one or more of water, ethanol, butanol or C4 alcohol, ethylene glycol, glycerol, poly (ethylene) glycol and poly (vinyl alcohol).
  • Said hydroxyl - rich molecule preferably comprises aqueous poly (ethylene) glycol (0-20%) having a molecular weight in the range of 400 to
  • said hydroxyl - rich molecule comprises poly (vinyl alcohol) having a molecular weight in the range of 400 to 2000000.
  • said hydroxyl - rich molecule comprises glycerol in an amount of up to 10 %, preferably up to 5%, more preferably from 2 to 6%.
  • said hydroxyl - rich molecule comprises ethanol in an amount of up to 10 %.
  • said hydroxyl - rich molecule comprises about 6% butanol and 18% ethanol.
  • said hydroxyl - rich molecule comprises aqueous methanol with the water content being from 95 to 99.5% .
  • said layered clay comprises a phyllosilicate.
  • said phyllosilicate is a smectite clay, particularly, a bentonite such as sodium bentonite
  • said bentonite comprises of from 5 to 700% by weight, preferably, 5 to 10 to 15% by weight of water.
  • the present invention also provides a process for the preparation of exfoliated nanoclays which comprises intercalating between the adjacent layers of a layered clay an aqueous intercalation solvent or solution followed by swelling with or without agitation to produce intercalated clay, and treating said intercalated clay in a heat sink, freezing, freeze-drying or thermal shock to obtain exfoliated nanoclays.
  • concentration of said intercalating solution is in range 0-20%.
  • said treatment in a heat sink is carried out for 4-48 hours.
  • Any swellable layered materials that sufficiently sorbs the intercalant monomer to increase the interlayer spacing between adjacent phyllosilicate plastelets to at least about 5 A preferably, to at least about 10 A (when the phyllosilicate is measured dry) may be used in the practice of the present invention.
  • Useful swellable layered materials include phyllosilicates, such as smectite clay, minerals, e.g., montmorillonite, particularly, sodium montmorillonite, magnesium montmorillonite and/or calcium montmorillonite; nontronite; beidellite; volkonskoite; hectorite; saponite; sauconite; sobockite; stevensite; svinfordite; vermiculite; and the like.
  • Other useful layered materials include micaceous minerals, such as illite and mixed layered illite/ smectite minerals, such as rectorite, tarosovite, ledikite and admixtures of illites with the clay minerals named above.
  • the present invention is carried out to fulfill the requirement for a cost effective intercalated, more preferably exfoliated bentonite clay and nanocomposites thereof with at least one polyolefin polymer such as polypropylene.
  • the composites disclosed in this invention can be used for a myriad number of applications, such as furniture, automobile components, body parts, etc, and can be left to the imagination of the moulder.
  • Smectite clays contain absorbed rnolecular water (H O), which is loosely held.
  • the hydrolysis process which occurs during weathering, involves two kinds of hydrogen - bound as either as OH or H 2 O, which is found in two different types of crystallographic sites.
  • the crystalline water is lost at higher temperatures than the absorbed interlayer water.
  • Glycerol is often used as a lubricant because its high viscosity and ability to remain fluid at low temperatures make it valuable without modification.
  • the exfoliated phyllosilicate platelets are dispersed in it.
  • the viscosity of the nanocomposite may be decreased by addition of water, alcohol, or glycols, and increased by increased loading of phyllosilicated platelets.
  • Pastes of such nanocomposite compositions may be used in packing pipe joints, in gas lines, or in similar applications.
  • soaps are added to glycerol to increase its viscosity and improve its lubricating ability.
  • Mixture of glycerine and glucose is employed as a nondrying lubricant in the die-pressing of metals.
  • glycerol is frequently used in connection with so-called textile oils, in spinning, knitting, and weaving operations.
  • Intercalation Penetration of any chemical, monomer or polymer in between adjacent layers of clay. "Intercalation”: A process for forming an Intercalate.
  • Exfoliation A process for forming an Exfoliate from an Intercalate.
  • Exfoliate or “Exfoliated”: Individual platelets of an Intercalated layered Material so that the adjacent platelets of the Intercalated Layered Material can be dispersed individually throughout a carrier material, such as a matrix polymer.
  • Interlacement Polymer or "Intercalant”: An oligomer or polymer that is sorbed between platelets of the layered material to form an Intercalant.
  • Bentonite A rock name given to the clay ore, which consists of smectite clay and impurities such as gravel, shale, and limestone.
  • Smectite A mineral clay that has the ability to swell in water. The most commercially important forms are hectorite and montmorillonite
  • the small particle sizes and melt dispersion potential of nanoclays allow thin sections to maintain clarity with filler loadings as high as 5%.
  • Montmorillonite The most available form of clay, classified as a magnesium aluminum silicate having a dioctahedral structure and a platy or sheetlike morphology.
  • Gallery The spacing between parallel layers of montmorillonite clay platelets. The spacing changes depending upon which polymer or surface treatment occupies the space.
  • Intercalate An organic or semiorganic chemical capable of entering the smectite clay gallery and bonding to the surface.
  • Intercalate Treated clay that has a complex formed between the clay surface and an organic molecule.
  • ""Intercalate” or “Intercalated” A Layered Material that includes oligomer and / or polymer molecules disposed between adjacent platelets o the layered material to increase the interlayer spacing between the adjacent platelets to at least 10 angstroms.
  • Interlayer spacing Also known as the gallery.
  • Layered Material An an inorganic material, such as a smectite clay mineral, that is in the form of a plurality of adjacent, bound layers and has a maximum thickness, for each layer, of about 100 Angstroms.
  • Platelets A thermoplastic or thermosetting polymer in which the Exfoliate is dispersed to form a Nanocomposite.
  • Nanocomposites A new class of plastics derived from the incorporation of nanoscale particles into polymers.
  • Nanocomposite An oligomer, polymer or copolymer having dispersed therein a plurality of individual platelets obtained from an Exfoliated, Intercalated Layered
  • X - Ray Diffraction It is also known as wide-angle x-ray scattering. It is one of the fundamental techniques of Materials Science. It gives a plot of scattered x-ray intensity as a function of scattering angle [two-theta]. XRD is used to determine crystal structure, crystallinity, crystal/amorphous ratio in polymers, metals, catalystd, adsorbents, etc.
  • shear forces may sometimes be necessary to achieve a complete exfoliation of clay into so-called nanoclay.
  • any method which can be used to apply a shear to the intercalant/carrier composition can be used.
  • the shearing action can be provided by any appropriate method, as for example by mechanical means, by thermal shock, by pressure alteration, by freezing or by ultrasonics.
  • any method which can be used to apply a shear to the intercalant/ carrier composition can be used.
  • the shearing action can be provided by any appropriate method, for example, by mechanical means, by thermal shock, by pressure alternation, or by ultrasonics, all known in the art.
  • the composition is sheared by mechanical methods in which the intercalate, with or without the carrier or solvent is sheared by use of mechanical means such as stirrers, Banbury
  • RTM type mixers Brabender RTM type mixers, long continuous mixers, and extruders.
  • Another procedure employs thermal shock in which shearing is achieved by alternatively raising or lowering the temperature of the composition, causing thermal expansions and resulting in internal stresses which cause the shear.
  • shear is achieved by sudden pressure changes in pressure alteration methods; by ultrasonic techniques in which cavitations or resonant vibrations which cause portions of the composition to vibrate or to be excited at different phases and thus subjected to shear.
  • clay is interacted with a solution of a polar molecule, e.g.; water, methanol, ethanol, water-ethanol-butanol, ethylene glycerol, glycerol, poly (vinyl alcohol), poly (ethylene glycol), etc. till its penetration and absorption reaches saturation.
  • a polar molecule e.g.; water, methanol, ethanol, water-ethanol-butanol, ethylene glycerol, glycerol, poly (vinyl alcohol), poly (ethylene glycol), etc. till its penetration and absorption reaches saturation.
  • Such intercalated phyllosilicates easily can be exfoliated into individual phyllosilicate platelets before or during admixture with a liquid carrier or solvent, for example, one or more monohydric alcohols, such as methanol, ethanol, propane, and / or butanol; polyhydric alcohols, such as glycerols and glycols, e.g., ethylene glycol, propylene glycol, butylenes glycol, glycerine and mixtures thereof with water; aldehydes; ketones; carboxylic acids; amines; amides; and other organic solvents.
  • a liquid carrier or solvent for example, one or more monohydric alcohols, such as methanol, ethanol, propane, and / or butanol; polyhydric alcohols, such as glycerols and glycols, e.g., ethylene glycol, propylene glycol, butylenes glycol, glycerine and mixtures thereof with water; alde
  • Intercalated clay is not a nanoclay but is a precursor of it.
  • an intercalated clay is subjected to high shear is an twin-screw extruder, it gets exfoliated to different extents depending upon degrees of applied shear.
  • Exfoliated clay is the true nanoclay as it shows an amorphous, non-crystalline structure and does not need shear to disperse individual clay layers or platelets.
  • exfoliated clay shows a minimum intensity of diffraction peak.
  • intercalated structures that are characterized by parallel registry give rise to X-ray peak at d- spacings in the range 20-30 A.
  • raw mineral clay is spread like a fluidized bed.
  • Nanoclay is made by intercalation of an aqueous solution of hydroxyl- rich molecule into layered smectic clay by an aqueous solution [intercalating solution concentration being in range 0-20%], followed by swelling (with or without agitation), treatment in a heat sink for 4-48 hours, and drying.
  • Exfoliation should be sufficiently thorough to provide at least about 80% by weight, preferably at least about 85% by weight, more preferably at least about 90% by weight, and most preferably at least about 95% by weight delamination of the layers to form two layer tactoids that include three platelets or, more preferably, individual platelet particles that can be substantially homogeneously dispersed in the carrier or solvent.
  • Mechanical shearing methods may be employed such as by extrusion, injection molding machines, Banbury RTM. type mixers Brabender. RTM type mixers and the like. Shearing can also be achieved by introducing the layered material and intercalant monomer at one end of an extruder (single or double screw) and receiving the sheared material at the other end of the extruder.
  • the temperature of the layered material/intercalant monomer composition, the length of the extruder, residence time of the composition in the extruder and the design of the extruder are several variables which control the amount of shear to be applied for exfoliation. Exfoliation did not occur unless the bentonite clay included water in an amount of at least about 5% by weight, based on the dry weight of the clay, preferably at least about 10% to about 15% water, to about 700%. The water can be included in the clay as received, or can be added to the clay prior to or during intercalant, melt or solution contact.
  • Polymer-layered silicate nanocomposites are plastics containing low levels of dispersed platy minerals with at least one dimension in the nanometer range.
  • the most common mineral is Montmorillonite clay, which forms a very large part [80 - 95%] of Bentonite clay. Its aspect ratio exceeds 300, giving rise to enhanced barrier and mechanical properties. In general, every one weight-percent of these "nanoclays" creates a 10% property improvement.
  • Their interaction with resin molecules alter the morphology and crystallinity of the matrix polymer, leading to improved processability in addition to the benefits to barrier, strength and stability.
  • nanoclays can provide in comparison to both their conventional filler counterparts and base polymer include: Mechanical properties e.g. strength, modulus and dimensional stability. Decreased permeability to gases, water and hydrocarbons ⁇ Thermal stability and heat distortion temperature Flame relardancy and reduced smoke emissions Chemical resistance Surface appearance Electrical conductivity ⁇ Optical clarity in comparison the conventionally filled polymers. Reinforcing polymers at the molecular level with inorganic fillers can bring about property improvements that are truly exceptional.
  • Thermoplastic resins and rubbers for use as matrix polymers in the practice of this invention may vary widely. Illustrative of useful thermoplastic resins, which may be used alone or in admixture, are polyactones such as poly (pivalolactone), poly
  • polyurethanes derived from reaction of diisocyanates such as 1, 5-naphthalene siisocyanate; p-phenylene d ⁇ socyanate, m-phenylene diisocyanate,
  • Nulcanizable and thermoplastic rubbers useful as matrix polymers in the practice of this embodiment of the invention may also vary widely.
  • Illustrative of such rubbers are brominated butyl rubber, chlorinate butyl rubber, polyurethane elastomers, fluoroesastomers, polyester elastomers, polyvinylchloride, butadiene/acrylonitrile elastomers, silicone elastomers, poly (isobutylene), poly (isobutylene), ethylene- propylene copolymers, ethylene-propylene-diene terpolymers, sulfonated ethylene- propylene-diene terpolymers, poly (chloroprene), poly (2, 3-dimethylbutadiene), poly (butadiene-pentadiene), chlorosulphonated poly (ethylenes), poly (butadiene- pentadiene), chlorosulphonate poly (ethylenes), poly (sulfide) elast
  • Thermosetting resins useful as matrix polymers include, for example, the polyamides; polylkylamides; polyesters; polyurethanes; polycarbonates; polyepoxides; and mixtures thereof.
  • Most preferred thermoplastic polymers for use as a matrix polymer are thermoplastic polymers such as polyamides, polyesters, and polymers of alpha-beta unsaturated monomers and copolymers.
  • X-ray diffractogram of treated clay showed a broad hump which confirmed exfoliation and a near absence of crystal structure in it
  • Bentonite clay [5 gms] from Kutch region of Bengal was immersed in 100 cc pure water which was then kept surrounded with solid carbon dioxide for 6-8 hours. It was then thawed at ambient temperature till ice formed surrounding clay became water.
  • Bentonite was converted into exfoliated nanoclay by an ingenius scheme under which hydroxyl-rich molecules, e.g. slip layer-by-layer into the interlayer gallery. Once there, these molecules associate with and solubilize water molecules present between adjacent layers. This treatment was performed in a heat sink. The intercalant forcibly separates clay layers which, after getting dismantled, never reassemble. Bentonite clay was kept immersed in a [0-20%] aqueous solution of chosen intercalant till swelling occurs in clay. Then, it was placed in a heat sink. When intercalant was removed, the clay was washed and dried.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention concerne des nano-argiles exfoliées et un processus de préparation de ces nano-argiles exfoliées à partir d'argile smectique en couches ordinaires (telles que les argiles minérales bentonite). La procédure par laquelle l'exfoliation survient dans l'argile est obtenue par l'insertion d'éléments intercalés (agents chimiques/gonflants/solvants/monomères/polymères). Ces éléments intercalaires peuvent former ou ne pas former un composé avec l'argile et après un intervalle de temps approprié peuvent être conservé dans un puits de chaleur. Ce processus perturbe la régularité de l'agencement des couches. Par ce processus il est possible d'obtenir des nano-argiles partiellement ou complètement exfoliées. Comme cette invention n'est pas une exfoliation directe, il n'existe pas d'espacement dans les piles complètement désordonnées de nano-argile. Des nano-argiles conviennent très bien pour améliorer les propriétés de thermoplastiques et de matrices thermodurcies par la formation de nanocomposites. Dans l'exemple montré ci-dessus, la résistance à la rupture dans des nanocomposites PP augmente de 350 % par rapport à celle obtenu par utilisation de'Cloisite 20A', malgré une légère réduction de la résistance au choc.
PCT/IN2004/000008 2004-01-13 2004-01-13 Materiaux en couches intercalees un particulier de nano-argiles WO2005068365A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2882997A1 (fr) * 2005-03-10 2006-09-15 Olmix Sarl Procede d'exfoliation d'argiles intercalees
CN104971894A (zh) * 2015-07-21 2015-10-14 安吉县宇宏粘土化工有限公司 一种分级筛选的膨润土生产工艺
EP3029122A4 (fr) * 2013-08-01 2017-05-10 Nichias Corporation Feuille composée de minéral argileux exfoliés et son procédé de production
CN108083289A (zh) * 2017-11-30 2018-05-29 广东华材实业股份有限公司 一种纳米层状矿物材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749569A (en) * 1985-04-08 1988-06-07 The Gillette Company Extrudable antiperspirant composition
US5837763A (en) * 1995-06-07 1998-11-17 Amcol International Corporation Compositions and methods for manufacturing waxes filled with intercalates and exfoliates formed with oligomers and polymers
US6126734A (en) * 1996-05-29 2000-10-03 Amcol International Corporation Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composite materials containing same and methods of modifying rheology therewith

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749569A (en) * 1985-04-08 1988-06-07 The Gillette Company Extrudable antiperspirant composition
US5837763A (en) * 1995-06-07 1998-11-17 Amcol International Corporation Compositions and methods for manufacturing waxes filled with intercalates and exfoliates formed with oligomers and polymers
US6126734A (en) * 1996-05-29 2000-10-03 Amcol International Corporation Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composite materials containing same and methods of modifying rheology therewith

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2882997A1 (fr) * 2005-03-10 2006-09-15 Olmix Sarl Procede d'exfoliation d'argiles intercalees
EP3029122A4 (fr) * 2013-08-01 2017-05-10 Nichias Corporation Feuille composée de minéral argileux exfoliés et son procédé de production
US10563104B2 (en) 2013-08-01 2020-02-18 Nichias Corporation Sheet composed of exfoliated clay mineral and method for producing same
CN104971894A (zh) * 2015-07-21 2015-10-14 安吉县宇宏粘土化工有限公司 一种分级筛选的膨润土生产工艺
CN108083289A (zh) * 2017-11-30 2018-05-29 广东华材实业股份有限公司 一种纳米层状矿物材料及其制备方法

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