WO2009015453A2 - Procédé d'obtention d'un nanocomposite solide - Google Patents

Procédé d'obtention d'un nanocomposite solide Download PDF

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Publication number
WO2009015453A2
WO2009015453A2 PCT/BR2008/000220 BR2008000220W WO2009015453A2 WO 2009015453 A2 WO2009015453 A2 WO 2009015453A2 BR 2008000220 W BR2008000220 W BR 2008000220W WO 2009015453 A2 WO2009015453 A2 WO 2009015453A2
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WIPO (PCT)
Prior art keywords
obtaining
clay
solid
nanocomposite
solid nanocomposite
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PCT/BR2008/000220
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English (en)
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WO2009015453A3 (fr
Inventor
Heloisa Cajon Schumacher
Márcia Maria RIPPEL
Fernando Galemeck
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Universidade Estadual De Campinas - Unicamp
Orbys Desenvolvimento De Tecnologia De Materiais Ltda
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Publication of WO2009015453A2 publication Critical patent/WO2009015453A2/fr
Publication of WO2009015453A3 publication Critical patent/WO2009015453A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C08C1/15—Coagulation characterised by the coagulants used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C08J2321/02—Latex

Definitions

  • the present invention refers to a process for preparing solid nanocomposites from an aqueous dispersion containing non-modified solid layered silicate and polymer latex, wherein said process is applicable, among other things, to the manufacture of adhesives, footwear, athletic articles, tires, and auto parts. Description of the prior art
  • Nanocomposites are hybrid materials which, in one of its components, have nanometric dimensions in at least one of the axes of the particles. Such as in conventional composites, one of the components serves as a matrix where particles from the second material are dispersed.
  • the obtainment of nanocomposites through the incorporation of nanometric charges into polymeric matrices may give rise to materials having higher impact resistance and elastic modulus.
  • the layered silicate reinforced polymer or elastomer shows good mechanical, electrical, and thermal properties, as well as gas and liquid barrier properties, and chemical resistance to oils and solvents, as compared to conventional polymers or elastomers.
  • Layered silicates are phyllosilicates, which group includes montmorillonite, hectorite, saponite, mica, among others.
  • the structure of a layered phyll ⁇ sfl ⁇ cate is formed by two tetrahedral silica layers and one octahedral aluminum layer. Due to the isomorphic substitution in the phylosilicate, where, for example,
  • AI J ions are replaced with Si on the SiO 2 layer or sheet, the basal face has a negative charge which is balanced by exchangeable cations, such as Na + , K ⁇ Li + , and Ca ⁇ + .
  • NBR and SBR rubbers containing clays modified with onium ions, such as, for example, a dimethyl hydrogenated double-tailed quaternary amine compound.
  • the mixture of rubber with the organically-modified clay is carried out in Babmury mixers, at 12O 0 C, being subsequently vulcanized at 15O 0 C.
  • the elastomer used is a halogenated elastomer, such as isobutylene containing units derived from styrene, such as para-bromo-methylstyrene.
  • the halogenated elastomer is primarily mixed with a functionalized amine, which can be made in the presence of a solvent, and then mixed with the clay.
  • a second elastomeric component may be added, such as natural rubber, SBR, NBR, PI, SIBR, EPM, EPDM, or even a thermoplastic resin.
  • the mixture is carried out in a Bambury mixer, at between 120 and 300 0 C.
  • the nanocomposite is subsequently vulcanized.
  • the amount of exfoliating agent may range from 0.1 to 20 phr.
  • the exfoliated clay is mixed with the elastomer in the melt state, in a ratio which may range from 0. 1 to 50% by mass.
  • the nanocomposite mixture may still contain a second elastomer, such as natural rubber, polybutadiene rubber, nitrile rubber, etc. The obtained nanocomposite is then vulcanized.
  • Document CN 1563181 owned by Huanan Technical University, discloses a nanocomposite prepared with rubber, organically-modified layered silicate, a monomer or monomer mixture, and an initiator. This process consists in adding modified layered silicate and reactive monomer in a rubber mixture and, it necessary, adding an initiator.
  • These are examples which demonstrate the use of clays organically modified with onium salts (ammonium, phosphonium, etc.)
  • the modification with such substances causes certain inconveniences related, for example, with the thermal instability of quaternary ammonium salts and the toxicity of phosphonium salts.
  • JP200332775 1 discloses the production of a rubber composition containing rubber, a charge and a nanocomposite from rubber and clay, wherein the clay is dispersed in a diene-type rubber.
  • the amount of clay is from 1 -50% by mass in the nanocomposite.
  • the amount of charge is from 1 -99 parts by mass in 100 parts by mass of the sum of nanocomposite and rubber.
  • Rubber company disclose the preparation of rubber nanocomposites.
  • Document JP2004250473 discloses the preparation of a rubber composition produced by mixing a rubber, containing epoxy groups, with layered clay organized through ionic bonding of an organic compound, having any one of carboxy, amino and, thiol groups.
  • Document JP2004250245 discloses a nanocomposite produced from rubber with clay organically-modi fied with a compound containing a thiol group and an amino group in its molecule.
  • Document JP2004155912 also discloses the preparation of a rubber from rubber and clay, wherein clay is organized through ionic bonding with an ammonium compound, which has a carboxyl group and a chain with 6 to 30 carbons in its molecule, and a halogenated butyl rubber.
  • Document JP2003221473 discloses a rubber composition consisting of a nanocomposite from rubber and clay. The composition is prepared by mixing a compound, having a maleic anhydride group with a clay treated with primary and/or secondary ammonium ion having six or more carbons, with a solid rubber by means of ionic bonding.
  • Document JP2003221452 discloses a nanocomposite-like masterbatch rubber composition consisting of rubber, carbon black, and mineral clay organically treated with a secondary and/or tertiary ammonium ion via ionic bonding.
  • Document JP2003055514 relates to a nanocomposite-like rubber composition containing butyl rubber having a specific phosphonium salt structure, with a phenyl group as a functional group, and modified clay with onium salt.
  • WO02070589 owned by the Southern Clay company discloses the preparation of polymer nanocomposites through the destabilization of a dispersion of polymer and clay.
  • the preparation procedure consists in mixing a dispersion of polymer in latex form with a dispersion of clay. To this mixture a fiocculant agent is added. The flocculated material is separated by filtration, centrifugation, or evaporation.
  • Polymers which can be used include polyester, polyurethane, PVC, styrene-butadiene, acrylic rubber, poly-isoprene, etc.
  • the polymer dispersion may occur in an aqueous medium, in an organic medium, or in a mixture of both, at a concentration of up to 80% by mass. In all examples described in the document (WO02070589) synthetic commercial latexes, in concentration of 50% by mass, are used. Clay dispersion may occur in an aqueous medium, at a concentration in the range of 1 to 10% by mass.
  • the clay dispersion is added to the latex dispersion and the obtained mixture is flocculated by the addition of quaternary ammonium salts and amines or, alternatively, the clay dispersion itself may contain a quaternary ammonium salt, double metallic layered hydroxides, or inorganic salts.
  • the clay dispersion containing quaternary ammonium salt is designated by the authors of the patents as organoclay. In this case latex flocculation requires even minutes to occur.
  • the amount of flocculation agent ranges from 1 to 10% by mass.
  • Another method described by this document refers to the preparation of a clay dispersion with a quaternary ammonium compound, wherein this compound is at a concentration 3 times higher than the ion exchange capacity of clay.
  • the obtained dispersion contains a portion of the quaternary ammonium compound which is not bounded to the clay.
  • This dispersion is then mixed with a polymer dispersion, preferably in latex form, forming the flocculated nanocomposite.
  • the maximum amount of clay on prepared nanocomposites is of 30% by mass, that is, about 43 phr. However, in the examples described in the patent the maximum amount of clay on nanocomposites is of 5.7% with respect to the mass of the polymer.
  • documents which describe the preparation of elastomeric nanocomposites from latex and aqueous dispersion of clay followed by coagulation are those owned by Exxon Research
  • Document TW419496 refers to the preparation of a montmorillonite dispersion in water, followed by the addition of a surfactant (alkyltrimethylammonium salt, dodecyltrimethylammonium bromide). Next, monomers (styrene, isoprene) are added by carrying out polymerization of the styrene- isoprene latex intercalated into the clay, and subsequently coagulated with methanol and dried.
  • a surfactant alkyltrimethylammonium salt, dodecyltrimethylammonium bromide
  • the solid nanocomposite is then mixed, by melting, with a SBR copolymer, together with zinc oxide, stearic acid, and tetramethylthiuram disulfide (accelerator) in a mixer at 13O 0 C followed by cross-linking.
  • SBR copolymer a solid nanocomposite
  • tetramethylthiuram disulfide accelerator
  • US5883173 discloses the preparation of a solid nanocomposite (NCP) from latex, formed by in situ polymerization or from a previously formed latex. In in situ polymerization the process is the same as described in document TW419496.
  • the preparation of a solid NCP from the pre- formed polymer involves primarily dissolving the functional ized polymer (isobutylene-co-paramethyl isoprene triethylammonium copolymer) in a solvent (tetrahydrofiiran), subsequently adding water, a nonylphenol derived surfactant, hexadecanol, and stirring overnight. Then, dried montmorillonite is added and ultrasound is applied in order to coagulate the NCP, which is vacuum-dried.
  • the functional ized polymer isobutylene-co-paramethyl isoprene triethylammonium copolymer
  • a solvent tetrahydrofiiran
  • NCP is prepared by adding clay (smectite) in hot water (6O 0 C) and subsequently adding rubber latex (for example, SBR or NR), but also includes synthetic latexes composed of isoprene, butadiene, isoprene and butadiene, isoprene-styrene, butadiene- styrene, butadiene-acrylonitrile, isoprene-butadiene, isoprene- acrylonitrile monomers) to form a mixture in which a cationic polymeric quaternary amine or ethylene polyamine solution is added, in order to intercalate or exfoliate the clay, with ion exchange and aiding in the coagulation of NCP.
  • clay smectite
  • rubber latex for example, SBR or NR
  • synthetic latexes composed of isoprene, butadiene, isoprene and butadiene, isoprene-sty
  • Coagulation may also be promoted through the addition of an acid solution or acid salt in order to reduce pH.
  • the nanocomposite may still be prepared by adding a clay/latex mixture to a sulfuric acid solution followed by the addition of cationic polymeric quaternary amine, whereby coagulated NCP is obtained, which is dried.
  • clay is added directly to the natural latex (20.3%TS, pH 10.8) diluted with demineralized water and containing the antioxidant Irganox. This mixture is gradually added to a sulfuric acid solution pH 3-4, together with a cationic polymeric quaternary amine solution. The obtained precipitate is centrifuged, washed, and dried at 66° C.
  • This document also describes the production of rubber compositions which include the produced NCPs, diene-type rubber (polybutadiene, polyisoprene, or styrene/butadiene copolymer), charges (carbon black, silica, etc.) and a coupling agent. Those compositions are subsequently vulcanized with sulfur compounds.
  • Document EP 1321489 discloses the preparation of an elastomeric nanocomposite from cationic latex, which can be styrene-butadiene, styrene-isoprene, isoprene, butadiene, isoprene- butadiene, butadiene-acrylonitrile, and isoprene-acrylonitrile.
  • the clay (montmorillonite) is dispersed in water, at 8O 0 C and under strong stirring, to which dispersion cationic latex is added, which coagulates forming the solid NCP.
  • the described process involves the addition of rubber latex (SBR, SVBR, NBR or carboxylated NBR) to an aqueous suspension of bentonite clay (2%), followed by stirring.
  • This mixture is then coagulated with a coagulating solution which may be hydrochloric acid, calcium chloride, or triethylenetetraammonium chloride, at concentrations between 1 and 2%.
  • a coagulating solution which may be hydrochloric acid, calcium chloride, or triethylenetetraammonium chloride, at concentrations between 1 and 2%.
  • patent CN 1238353 claims that the coagulant should be added on the latex and clay dispersion, that the preparation of the clay and latex mixture should be made using microwave or ultra-sound, and that substances able to cause the coupling of the rubber and clay macromolecules should be added to the clay mixture.
  • nanocomposites from nanocompounds mixed with modifying agents, such as quaternary ammonium salt or silane.
  • modifying agents such as quaternary ammonium salt or silane.
  • a nanocompound is obtained by adding latex on an aqueous dispersion of clay. This mixture is coagulated in an electrolytic solution, whereby the nanocompound is obtained.
  • the dried nanocompound is mixed with modifying agents (quaternary ammonium salt or silane), vulcanizing agents, and other additives and vulcanized, whereby the nanocomposite is obtained. Therefore, authors of the Chinese document
  • CN 1238353 do not obtain nanocomposites by using what they call LCM (Latex Compound Method) with subsequent coagulation, without making the use of the post-addition of a quaternary surfactant, which is a widely-known procedure and described in the state of art and with vulcanization.
  • LCM Latex Compound Method
  • the clay now positively-charged, as a result of the excess of positive charges from the polyelectrolyte, is mixed with an anionic latex, wherein the mixture coagulates due to the opposed charges of clay and latex.
  • the examples described in this patent are prepared with SBR or PMMA latex dispersions at concentrations of 2.35% by solid content.
  • concentration of clay, a fluoromica, in the aqueous suspension should be of 0.5 m/v, and the concentration of the polyelectrolyte solution should be of 2%.
  • the coagulants used are saline solutions of di- or trivalent metals, in some cases associated with diluted solutions of strong acids.
  • the use of polyelectrolytes may also be included, which raises the cost of the product.
  • These coagulants are already commonly used in coagulation processes known in the industrial field.
  • latex coagulation systems described in the literature and even well-known in the industrial field, which include solutions of electrolytes such as potassium chloride, calcium chloride, magnesium chloride, mixtures of sodium chloride and sulfuric acid, mixtures of sodium chloride, polyamine, and sulfuric acid, mixtures of aluminum sulfate and sulfuric acid, magnesium sulfate, acids such as sulfuric, hydrochloric, nitric, or phosphoric acid, sodium carbonate and sodium sulfate, as well as organic salts such as sodium or potassium acetates, sodium oxalate, sodium tartarate, calcium acetates, or magnesium.
  • electrolytes such as potassium chloride, calcium chloride, magnesium chloride, mixtures of sodium chloride and sulfuric acid, mixtures of sodium chloride, polyamine, and sulfuric acid, mixtures of aluminum sulfate and sulfuric acid, magnesium sulfate, acids such as sulfuric, hydrochloric, nitric, or phosphoric acid, sodium carbonate and sodium sul
  • Some patents owned by big companies also disclose latex coagulation systems, such as from 3 M, which uses onium salts, such as tetrabutylphosphonium hydroxide. The use of quaternary ammonium salts and polyelectrolytes is also described.
  • a dispersion containing clay and polymer latex is firstly obtained.
  • water needs to be removed.
  • a new methodology for preparing polymer nanocomposites through the latex dispersion method was developed, wherein layers from the layered compound, a phyllosilicate, are intercalated and/or fully exfoliated (PI 0301 193-3), without the modification of the clay or addition of any additive.
  • the present invention refers to a process for obtaining solid nanocomposites from the coagulation of latex and clay dispersions prepared by the latex dispersion method, wherein layers from the layered compound, a phyllosilicate, are intercalated and/or fully exfoliated without modification of the clay or addition of any additive, whereby solid polymer (elastomer)-clay nanocomposites are obtained in which the layers of the phyllosilicate are intercalated and/or fully exfoliated.
  • the solid polymer (elastomer)-clay nanocomposite obtained by the process of this invention can be extruded, calendered, compression molded, injection molded, blow molded, molded in various forms including fibers, films, automotive industrial parts, household products, used in the manufacture of innerliners and innertubes for airplanes, automobiles, trucks, etc., due to its impact resistance, low vapor permeability, and resistance to oils and solvents.
  • the present invention refers to a process for obtaining a solid nanocomposite from a dispersion containing non- modified solid layered silicate and polymer latex wherein the solid nanocomposite is obtained through an electrolytic coagulation of the latex and clay dispersion.
  • This invention also refers to a solid nanocomposite obtained by means of the process described in the invention, said nanocomposite having from 60% to 99.999% by mass of polymer and 0.001 % to 40% of non-modified solid layered silicate.
  • This invention still refers to solid articles comprising said solid nanocomposite obtained by means of the process described in the invention, said nanocomposite having from 60% to 99.999% by mass of polymer and 0.001% to 40% of non- modified solid layered silicate.
  • Figure 1 - X-ray diffractograms of Cloisite® clay and natural rubber nanocomposites having 10 phr of Cloisite®, obtained through a coagulation process by the addition of the dispersion of clay and natural latex on the acetic acid solution, according to examples 1 to 4.
  • Figure 2 - X-ray diffractograms of Argel-T clay and the natural rubber nanocomposite having 10 phr of Argel-T, obtained through a coagulation process by the addition of the dispersion of clay and natural centrifuged latex on the acetic acid solution, according to example 5.
  • Brasgel PBS 50 obtained through a coagulation process by the addition of the dispersion of clay and natural centrifuged latex on the acetic acid solution, according to example 6.
  • Viscogel Aco obtained through a coagulation process by the addition of the dispersion of clay and natural centrifuged latex on the acetic acid solution, according to example 7.
  • FIG. 5 - X-ray diffractograms of Cloisite® clay and nitrile rubber nanocomposites having 10 phr of Cloisite®, obtained through a coagulation process by the addition of the dispersion of clay and nitrile latex on the aluminum sulphate solution, according to examples 8 and 9.
  • Figure 6 - X-ray diffractograms of Cloisite® clay and the nitrile rubber composite having 10 phr of Cloisite®, obtained through a coagulation process by the addition of the coagulating agent on the dispersion of clay and nitrile latex, according to example 10.
  • Figure 8 Mass increase in pure nitrile rubber coagula, nanocomposites and composites having 10 phr of clay, by the sorption of an isooctane-toluene mixture, according to examples 8 and 10.
  • Figure 9 shows scanning electron microscopy micrographs of secondary and backscattered electrons of a cross- section of the nanocomposite obtained according to Example I .
  • Figure 10 shows clear-field images of cross- sections of the nanocomposite obtained according to Example 8 obtained by transmission electron microscopy. Nanocomposites were prepared according to procedures described in Examples I to 10. * - Clay sheets parallel to the plane.
  • the present invention refers to a process for obtaining solid nanocomposites from the coagulation of latex and clay dispersions prepared by the latex dispersion method, where layers of the layered compound, a phyllosilicate, are intercalated and/or fully exfoliated without modification of the clay or addition of any additive.
  • Latex and clay dispersions referred to herein are prepared according to teachings disclosed in document PI 0301 193-3.
  • the present process of the invention concerns the production of rubber nanocomposites with clay, through the coagulation of clay and latex dispersions, prepared according the teachings disclosed in document PI 0301 193-3, whereby solid nanocomposites are obtained.
  • the methodology developed and disclosed in document PI0301 193-3 for preparing polymer nanocomposites describes that the layers of the layered compound, a phyllosilicate, are intercalated and/or fully exfoliated in the polymeric matrix, without modification of clay or addition of any additive.
  • the novelty shown in the present invention is the method for coagulating latex and clay dispersions, such as, for example, natural rubber and nitrile rubber latexes, prepared according to teachings disclosed in document PI 0301 193-3, whereby rubber and clay solid nanocomposites are obtained where layers of the phyllosilicate are intercalated and/or fully exfoliated.
  • the solid nanocomposite obtained through this process can be extruded, molded, thermopressed, calendered, and vulcanized.
  • the present invention refers to a process for obtaining a solid nanocomposite from an aqueous dispersion containing non-modified solid layered silicate and polymer latex, wherein said solid nanocomposite is obtained through an electrolytic coagulation of the latex and clay dispersion.
  • the electrolytic coagulation process occurs by means of the addition of the latex and clay dispersion on a coagulating agent solution.
  • the addition of the latex and clay dispersion on a coagulating agent solution occurs under a shearing action over the coagulated latex and clay dispersion.
  • the shearing action is preferably obtained by means of mechanical and/or magnetic and/or manual stirring.
  • Layered silicates to which the present invention refers correspond to clays which, in the case of this invention, are selected from the types consisting of smectite, hectorite, mica, vermiculite, saponite, montmorillonite, or any mixture thereof.
  • the clay used in the present invention is montmorillonite.
  • the polymer latex of the present invention is selected from natural rubber, nitrile rubber, carboxylated nitrile rubber, styrene-butadiene, styrene, carboxylated styrene-butadiene, synthetic polyisoprene, acrylic rubber, or any mixture thereof.
  • the coagulation method described in this process of the invention consists in adding the rubber latex dispersion with clay on the coagulating agent solution, under stirring.
  • Coagulating agents which may be used in this coagulation process include weak and strong acid solutions, such as acetic, hydrochloric, sulfuric acid, salt solutions of monovalent (Na + , K + , NH 4 + ), divalent (Ca 2+ , Mg 2+ ), and trivalent (Al 1 , F-V ) cations, wherein the anion of the salt may be sulphate, chloride, nitrate, phosphate, acetate, among others, and can also be associated with the use of acid solutions from these anions.
  • salts which can be used in the coagulation process described herein are: aluminum sulphate, magnesium sulphate, calcium chloride, aluminum chloride, sodium chloride, and ammonium chloride.
  • Coagulating agents can further be used in mixtures of one or more components, at concentrations comprised between 0.3 and 5 mol.L "1 .
  • the amount of layered clay or material in the rubber nanocomposite of the present invention may range widely, from 0.001 to 40% by mass of the nanocomposite, but preferably, from 0.5 to 30% by mass.
  • the amount of clay will be determined by the use or application intended for the rubber nanocomposite.
  • Elastomers and polymers which can be used include, but are not limited to, natural rubber, nitrile rubber, carboxylated nitrile rubber, styrene-butadiene, carboxylated styrene- butadiene, synthetic polyisoprene, acrylic rubber.
  • the process for coagulating the nanocomposite prepared via latex makes feasible the production of elastomeric nanocomposites from its latexes, without the need of introducing an intercalant into clays, making them become organoclays, and without the need of using coagulated rubber and hot mixture processes for obtaining the nanocomposites.
  • Advantages provided by the method for preparation of rubber nanocomposites via coagulation described in this invention are: a) absence of organic solvents; b) clay is not required to be chemically modified nor undergo purifying processes in order to be used in the preparation of nanocomposites, when compared to documents described in the state of art; c) the elastomer does not need to be modified; d) does not make the use of the addition of intercalating agents in order to aid the intercalation of the elastomer into the clay; e) does not make the use of surface modifying agents for obtaining nanocomposites, whether in pre- or post-addition conditions, such as quaternary ammonium salt in order to achieve good properties of resistance to solvents and exfoliation of clay sheets; f) does not make the use of rubber vulcanization through any known method.
  • the present invention still refers to a process for obtaining a solid nanocomposite as described above, wherein said process comprises a step of drying the coagulated nanocomposite dispersion.
  • the present invention also refers to a step of diluting the solid and dried nanocomposite, obtained according the process of the invention, in a polymeric matrix processable in fluid state.
  • the invention also refers to a process for obtaining a solid nanocomposite which comprises a process for obtaining a solid nanocomposite from the coagulation of an aqueous dispersion containing non-modified layered silicate and polymeric latex, as described in the invention.
  • the solid nanocomposite obtained by the process described in the present invention comprises from 60% to 99.999% by mass of polymer and 0.001% to 40% by mass of a non-modified solid layered silicate.
  • solid articles comprising a solid nanocomposite obtained from the coagulation of an aqueous dispersion containing non- modified layered silicate and polymeric latex as described in the invention.
  • Example 1 Preparation of the Coagulated Nanocomposite from Centrifuged Natural Rubber Latex with Sodium Montmorillonite Clay 10 phr.
  • aqueous dispersion of sodium montmorillonite clay (Cloisite®-Na available from Southern Clay Products), prepared according to teachings disclosed in document PI0301 19-3, was added to 145.7 of centrifuged natural rubber latex having a high ammonium content with 64% solids, by mass. The mixture was homogenized and left to rest for 24 hours. About 40.0 g of the clay and latex dispersion were added to 3.0 g of acetic acid solution 10%, by volume, thereby obtaining a coagulated nanocomposite. The coagulated nanocomposite was washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Example 2 the same procedure as described in Example 1, differing only in that coagulation of 40.0 g of the clay and latex dispersion occurred by addition into 10,0 g of acetic acid solution 10%, by volume, thereby obtaining the coagulated nanocomposite.
  • the coagulated nanocomposite was washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Example 3 the same procedure as described in
  • Example 1 except that solid content of the clay and latex dispersion was of 12% by mass. Coagulation of 40.0 g of the clay and latex dispersion occurred by addition into 40,0 g of acetic acid solution 1%, by volume, thereby obtaining a coagulated nanocomposite. The coagulated nanocomposite was washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Example 4 Preparation of the Coagulated Nanocomposite from Raw Natural Rubber Latex with Sodium Montmorillonite Clay 10 phr.
  • An aqueous dispersion of sodium montmorillonite clay (Cloisite®-Na available from Southern Clay Products), prepared according to teachings disclosed in document PI0301 19-3, was added to 125Og of raw natural rubber latex having a high ammonium content with 36% solids, by mass.
  • the flocculated mixture was then added slowlv to 730 mL of acetic acid solution ( 10%, by volume), thereby obtaining the coagulated nanocomposite.
  • the coagulated nanocomposite was washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Example 5 The same procedure as described in
  • Example 1 except that a dispersion of Argel-T clay (Bentonit Uniao Nordeste) was prepared, thereby obtaining the coagulated nanocomposite.
  • the coagulated nanocomposite was washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Example 6 The same procedure as described in Example I , except that a dispersion of Brasgel PBS-50 clay (Bentonit Uniao Nordeste) was prepared, thereby obtaining the coagulated nanocomposite. The coagulated nanocomposite was washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Brasgel PBS-50 clay Bentonit Uniao Nordeste
  • Example 7 The same procedure as described in Example 1 , except that a dispersion of Viscogel Aco 50 clay (Uniao Brasileira de M inera ⁇ ao) was prepared, thereby obtaining the coagulated nanocomposite. The coagulated nanocomposite was washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Viscogel Aco 50 clay Uniao Brasileira de M inera ⁇ ao
  • Example 8 Preparation of the nanocomposite from Nitrile Rubber Latex with Sodium Montmorillonite Clay 10 phr.
  • An aqueous dispersion of sodium montmorillonite clay (Cloisite®-Na available from Southern Clay Products), prepared according to teachings disclosed in document PI0301 19-3, was added to 144,3 g of nitrile rubber latex (25.2% non-volatiles, 3 1 -34% acrylonitrile, and Mooney viscosity of 20-30 MML l +4@ 100°C) with 24% solids, by mass.
  • the dispersion was homogenized and left to rest for 24 h, thereafter being added to 1000 niL of aluminum sulphate solution 0.84% m/v, thus obtaining the coagulated nanocomposite.
  • the coagulated nanocomposite was filtered, washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Example 9 The same procedure as described in Example 6, except that nitrile rubber latex has 25.7% of non- volatiles, 3 1 -34% of acrylonitrile, and a Mooney viscosity of 42-52 MML 1+4 @ 100 0 C.
  • the clay and latex dispersion obtained was added to 1000 niL of aluminum sulphate solution 0.84% m/v, thus obtaining the coagulated nanocomposite.
  • the coagulated nanocomposite was filtered, washed until the pH of the washing water was neutral, pressed and dried to remove all water.
  • Example 10 Preparation of a composite from
  • This example serves to demonstrate that, by adding the coagulating agent on the latex and clay dispersion, a nanocomposite is not obtained, but rather a composite material.
  • An aqueous dispersion of sodium montmorillonite clay (Cloisite®-Na available from Southern Clay Products), prepared according to teachings disclosed in document P10301 19-3, was added to 144.3 g of nitrile rubber latex (25.7% non-volatiles, 31-34% acrylonitrile, and Mooney viscosity of 42-52 MML 1 +4@ 100 0 C) with 24% solids, by mass.
  • the dispersion was homogenized and left to rest for 24 h, thereafter being slowly coagulated with an aluminum sulphate solution 0.84% m/v.
  • nanocomposites prepared with Cloisite and coagulated by adding the latex and clay dispersion on the coagulating agent solution showed an increase on the basal spacing between 1.49 and 1.57 nm, demonstrating the intercalation of the elastomer in the clay.
  • Table 2 shows interlayer distance values of nanocomposites prepared with Argel-T and Viscogel Aco clays and coagulated by adding the latex and clay dispersion on the coagulating agent solution, in which an increase on the basal
  • Sorption tests of an isooctane and toluene mixture ( 1 : 1 ) were carried out with coagulated nitrile rubber nanocomposites, obtained according to examples 8 and 10, as a function of time.
  • a nitrile rubber coagulum without clay coagulated with an aluminum sulphate solution 0.84% m/v was used.
  • Figure 8 shows sorption curves as a function of time.
  • the nitrile rubber coagulum had a mass increase as high as 70%, at which it starts dissolving.
  • the coagulated nanocomposite, prepared according to example 8 showed a reduction on the solvent sorption of 1 5%.
  • the coagulum prepared according to example 10 swelled as much as the pure rubber, what demonstrates the inefficacy of the coagulation carried out by adding the coagulating solution on the clay and latex dispersion.
  • Scanning electron microscopy images, obtained in the secondary electron (SEI) mode, of cross-sections of coagula prepared according to Example 1 are shown in Figure 8.
  • the set of images shown in Figure 9 is representative of patterns observed in various fields of the sample in which distribution of clay on the elastomeric matrix can be seen.
  • This set of images was obtained from cross-sections of coagula from Example 8 and observed by means of transmission electron microscopy in various fields.
  • two predominant domains were observed in the images: 1 - some little aggregates and isolated clay layers, as can be seen in images A and B.
  • Dark lines are the edges of individual clay layers or aggregates from various layers.
  • the spacing measured between layers is in the range from 1 .6 to 2.4 nm, at measured points.
  • image A it is possible to see clay layers parallel to the plane, due to the geometry and gray level of the drawing, which shows that clay is distributed randomly on the matrix, without a preferred orientation.

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Abstract

La présente invention concerne un procédé de préparation de nanocomposites solides, obtenus au moyen de latex élastomères ou thermoplastiques et de composés en couches, synthétiques ou naturels, intercalés ou exfoliés. La particularité du procédé de l'invention est l'obtention de nanocomposites solides par coagulation de dispersions de latex et d'argile sous forme d'agents coagulants, par des moyens thermiques ou mécaniques, ce qui permet d'obtenir des nanocomposites solides de caoutchouc/argile dont le degré d'intercalation et/ou d'exfoliation de l'argile est élevé. Le nanocomposite solide obtenu selon le procédé de l'invention et réparti par vulcanisation a des propriétés mécaniques bien plus élevées que celles de nombreux polymères ou élastomères conventionnels, ainsi que d'excellentes propriétés de résistance aux huiles et aux solvants, ce qui rend son application possible dans les domaines industriels tels que l'équipement et le transport, la fabrication de pneus, de joints dynamiques et statiques, de joints d'étanchéité, d'agents de scellement, de tuyaux, de courroies, entre autres. Cette invention concerne également des articles obtenus à l'aide de ces nanocomposite solides.
PCT/BR2008/000220 2007-07-27 2008-07-28 Procédé d'obtention d'un nanocomposite solide WO2009015453A2 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102861550A (zh) * 2012-09-07 2013-01-09 常州大学 一种合成铁改性膨润土的方法
CN103865114A (zh) * 2014-02-27 2014-06-18 上海工程技术大学 蒙脱土/天然橡胶复合材料及其制备方法
US10465064B2 (en) * 2016-09-23 2019-11-05 Baker Hughes, A Ge Company, Llc Wear resistant and high temperature resistant elastomer nanocomposites
US10717879B2 (en) 2015-09-30 2020-07-21 Dow Global Technologies Llc Shelf-stable aqueous composition and process of making the same
CN116426254A (zh) * 2023-04-18 2023-07-14 西南石油大学 一种水基钻井液用纳米封堵剂制备方法及水基钻井液

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GB2360290A (en) * 2000-03-14 2001-09-19 Ind Tech Res Inst Modified clay minerals and polymer composites comprising the same
US20020086932A1 (en) * 2000-10-26 2002-07-04 Industrial Technology Research Institute Polymer nanocomposites and the process of preparing the same
EP1440998A1 (fr) * 2003-01-27 2004-07-28 Elementis Specialties, Inc. Composites à base de caoutchouc naturel contenant de l'argile smectite et leurs utilisations
WO2005030850A1 (fr) * 2003-10-01 2005-04-07 Universidade Estadual De Campinas - Unicamp Procede d'elaboration de polyester a intercalation ou exfoliation avec un materiau nanocomposite hybride en argile

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2360290A (en) * 2000-03-14 2001-09-19 Ind Tech Res Inst Modified clay minerals and polymer composites comprising the same
US20020086932A1 (en) * 2000-10-26 2002-07-04 Industrial Technology Research Institute Polymer nanocomposites and the process of preparing the same
EP1440998A1 (fr) * 2003-01-27 2004-07-28 Elementis Specialties, Inc. Composites à base de caoutchouc naturel contenant de l'argile smectite et leurs utilisations
WO2005030850A1 (fr) * 2003-10-01 2005-04-07 Universidade Estadual De Campinas - Unicamp Procede d'elaboration de polyester a intercalation ou exfoliation avec un materiau nanocomposite hybride en argile

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102861550A (zh) * 2012-09-07 2013-01-09 常州大学 一种合成铁改性膨润土的方法
CN103865114A (zh) * 2014-02-27 2014-06-18 上海工程技术大学 蒙脱土/天然橡胶复合材料及其制备方法
CN103865114B (zh) * 2014-02-27 2015-08-26 上海工程技术大学 蒙脱土/天然橡胶复合材料及其制备方法
US10717879B2 (en) 2015-09-30 2020-07-21 Dow Global Technologies Llc Shelf-stable aqueous composition and process of making the same
US10465064B2 (en) * 2016-09-23 2019-11-05 Baker Hughes, A Ge Company, Llc Wear resistant and high temperature resistant elastomer nanocomposites
CN116426254A (zh) * 2023-04-18 2023-07-14 西南石油大学 一种水基钻井液用纳米封堵剂制备方法及水基钻井液

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