WO1997031057A1 - Polymer composite and a method for its preparation - Google Patents

Polymer composite and a method for its preparation Download PDF

Info

Publication number
WO1997031057A1
WO1997031057A1 PCT/US1997/002639 US9702639W WO9731057A1 WO 1997031057 A1 WO1997031057 A1 WO 1997031057A1 US 9702639 W US9702639 W US 9702639W WO 9731057 A1 WO9731057 A1 WO 9731057A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite
inorganic
polymer
intercalant
thermoset
Prior art date
Application number
PCT/US1997/002639
Other languages
French (fr)
Inventor
Kevin L. Nichols
Chai-Jing Chou
Original Assignee
The Dow Chemical Company
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
Priority to US1220696P priority Critical
Priority to US60/012,206 priority
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Publication of WO1997031057A1 publication Critical patent/WO1997031057A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances

Abstract

A polymer composite comprises a polymer matrix having, dispersed therein, layers of an inorganic material derived from a multilayered inorganic material such as clay intercalated with an inorganic intercalant. The multilayered inorganic material may also be intercalated with an organic material.

Description

POLYMER COMPOSITE AND A METHOD FOR ITS PREPARATION

The present invention relates to a composite comprising a polymer and an inorganic additive, more specifically, layers of a swellable material, and to a method for preparing the polymer composite.

Polymer composites comprising a polymer matrix having one or more additives such as a particulate or fiber material dispersed throughout the continuous polymer matrix are well known. The additive is often added to enhance one or more properties of the polymer.

Useful additives include inorganic layered materials such as talc, clays and mica of micron size.

A number of techniques have been described for dispersing the inorganic layered material into a polymer matrix. It has been suggested to disperse individual layers, for example, platelets, of the layered inorganic material, throughout the polymer. However, without some additional treatment, the polymer will not infiltrate into the space between the layers of the additive sufficiently and the layers of the layered inorganic material will not be sufficiently uniformly dispersed in the polymer.

To provide a more uniform dispersion, as described in U.S. Patent 4,889,885, sodium or potassium ions normally present in natural forms of mica-type silicates and other multilayered particulate materials are exchanged with organic cations (for example, alkylammonium ions or suitably functionalized organosilanes) thereby intercalating the individual layers of the multilayered materials, generally by ionic exchange of sodium or potassium ions. This intercalation can render the normally hydrophilic mica-type silicates organophilic and expand its interlayer distance. Subsequently, the layered material (conventionally referred to as "nanofillers") is mixed with a monomer and/or oligomer of the polymer and the monomer or oligomer polymerized. The intercalated silicate is described as having a layer thickness of 7 to 12A and an interlayer distance of 3θA or above. In WO 93/1 1190, an alternative method for forming a composite is described in which an intercalated layered, particulate material having reactive organosilane compounds is dispersed in a thermoplastic polymer or vulcanizabie rubber

Yet additional composites containing these so-called nanofillers and/or their methods of preparation are described in U S Patents 4,739,007, 4,618,528, 4,528,235, 4,874,728, 4,889,885, 4,810,734, 4,889,885; 4,810,734; and 5,385,776, German Patent 3808623, Japanese Patent J02208358, European Patent applications 0,398,551 , 0,358,415, 0,352,042, and 0,398,551 ; and J. Inclusion Phenomena 5, (1987), 473?483; Clay Minerals, 23, (1988), 27; Polym. Preprints, 32 (April 1991 ), 65-66, Polym Prints, 28, (August 1987), 447-448, and Japan Kokai 76,109,998

However, even with these numerous described composites and methods, it still remains desirable to have an improved composite and method for forming polymer composites derived from a multilayered additive to make composites having improved properties over the polymer alone.

Accordingly, in one aspect, the present invention is a composite comprising a polymer matrix having, dispersed therein, delaminated or exfoliated particles derived from a multilayered inorganic material intercalated with an inorganic intercalant Optionally, an organic intercalant can also be employed. If employed, the optionally employed organic intercalant can be calcined or at least partially removed from the multilayered inorganic material

In another aspect, the present invention is a composite comprising a polymer matrix having dispersed therein delaminated or exfoliated particles derived from a multilayered material which has been intercalated with an organic intercalant only which is subsequently calcined or otherwise at least partially removed from the layered, reinforcing material

In a third aspect, the present invention is a method for forming a composite which method comprises contacting a polymer or a precursor to the polymer with a multilayered inorganic particulate material intercalated with an inorganic polymeric intercalant and, optionally, an organic intercalant If the optionally employed organic intercalant is used, it can be calcined or at least partially removed from the multilayered inorganic material prior to mixing the material with the polymer.

In a preferred embodiment, the polymer is a melt processible, thermoplastic polymer and the method comprises mixing the polymer and intercalated material at conditions to disperse the intercalated material into the polymer.

The polymeric compositions of this invention can exhibit an excellent balance of properties and can exhibit one or more superior properties such as improved heat or chemical resistance, ignition resistance, superior resistance to diffusion of polar liquids and of gases, yield strength in the presence of polar solvents such as water, methanol, or ethanol, or enhanced stiffness and dimensional stability, as compared to composites which contain the same multilayered material which has not previously been intercalated or where no intercalated material is employed.

The composites of the present invention are useful in a wide variety of applications including transportation (for example, automotive and aircraft) parts, electronics, business equipment such as computer housings, building and construction materials, and packaging materials.

In the present invention, the polymer matrix of the composite can be essentially any normally solid polymer, including both thermoset and thermoplastic polymers and vulcanizable and thermoplastic rubbers.

A representative thermoplastic polymer which can be employed to prepare the composites of the present invention is a thermoplastic polyurethane such as derived from the reaction of a diisocyanate such as

1 ,5-naphthalene diisocyanate, 3,3'-dιmethyl-4,4'-dι-phenylmethane diisocyanate, 4,4'- diphenyliso-propylidene diisocyanate, or 4,4'-diιsocyanatodιphenylmethane and linear long- chain diol such as poly(tetra-methylene adipate), poly(ethylene succinate), or polyether diol

Another representative thermoplastic polymer is a polycarbonate such as prepared by the reaction of an aromatic polyol (for example, resorcinol, catechol, hydroqumone, a dihydroxynaphthalene, a dihydroxyanthracene, a bιs(hydroxyaryl) fluorene, a dihydroxyphenanthrene, a dihydroxybiphenyl; and a bis(hydroxyphenyl) propane), more preferably an aromatic diol, with a carbonate precursor (for example, carbonic acid derivative, phosgene, haloformate, or carbonate ester such as dimethyl carbonate or diphenyl carbonate, poly(methane bis(4-phenyl) carbonate), or poly(1 ,1 -ether bis(4-phenyl)carbonate).

Yet other representative examples include thermoplastic polymers and copolymers derived from esters of ethylenically unsaturated methacrylic or acrylic acid such as poly(methyl or ethyl)acrylate, poly(methyl or ethyl)methacrylate, including copolymers of methyl methacrylate and a monovinylidene aromatic such as styrene, copolymers of ethylene and ethyl acrylate, methacrylated and butadiene-styrene copolymers; polymers derived from ethylenically unsaturated monomers such as polyolefins (for example, polypropylene and polyethylene including high density polyethylene, linear low density polyethylene, ultra low linear density polyethylene, homogeneously branched, linear ethylene/α-olefin copolymers, homogeneously branched, substantially linear ethylene/α-olefin polymers, and high pressure, free radical polymerized ethylene copolymers such as ethylene-acrylic acid (EAA) copolymers), highly branched low density polyethylene, and ethylene-vinyl acetate (EVA) copolymers; polymers of monovinylidene aromatics such as polystyrene and syndiotactic polystyrene including copolymers thereof such as impact modified polystyrene, styrene- ethylene copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers and other styrenic copolymers.

Still other representative examples of thermoplastic polymers include polyesters such as poly(ethylene-1 ,5-naphthalate), poly(1 ,4-cyclohexane dimethylene terephthalate), poly(ethylene oxybenzoate), poly(para-hydroxy benzoate), polyethylene terephthalate, or polybutylene terephthalate; polysulfones such as the reaction product of the sodium salt of 2,2-bis(4-hydroxyphenyl) propane and 4,4'-dichlorodiphenyl sulfone; polyetherimides; and polymers of ethylenically unsaturated nitriles such as polyacrylonitrile; poly(epichlorohydrin); polyoxyalkylenes such as poly(ethylene oxide); poly(furan); cellulose- based plastics such as cellulose acetate, cellulose acetate butyrate; silicone based plastics such as poly(dimethyl siloxane) and poly(dimethyl siloxane co-phenylmethyl siloxane); polyether ether ketones; polyamides such as poly(4-amino butyric acid), poly(hexamethylene adipamide), poly(6-aminohexanoic acid), and poly(2,2,2-tri-methyl hexamethylene terephthalamide); polylactones such as poly(pιvalolactone) and poly(caprolactone); poly(aryleno oxides) such as poly(2,6-dimethyl-1 ,4-phenylene oxide); poly(arylene sulfides) such as poly(phenylene sulfide); polyetherimides; acetals; polyvinyl chloride; poly(vinylidene chloride), and blends of two or more of these polymers.

Preferred thermoplastic polymers include the polymers and copolymers of ethylene and/or propylene, polymers and copolymers of a monovinylidene aromatic compound, more preferably styrene, polycarbonates, and thermoplastic polyurethanes or mixtures thereof. Preferred ethylene polymers and copolymers include linear low density polyethylenes, low density polyethylenes and the homogeneously branched linear and substantially linear ethylene copolymers with a density (ASTM D-792) of 0.85 to 0.92 g/cm3, more preferably of 0.85 to 0.90 0.92 g/cm3, and a measured melt index (ASTM D-1238 (190/2.16)) of 0.1 to 10 g/minutes; substantially linear, functionalized, ethylene copolymers, particularly a copolymer of ethylene with vinyl acetate containing from 0.5 to 50 weight percent units derived from vinyl acetate, are especially preferred, especially copolymers of ethylene with vinyl acetate having a melt index of 0.1 to 10 g/10 minutes; and copolymers of ethylene with acrylic acid containing from 0.5 to 25 weight percent units derived from acrylic acid.

Representative vulcanizable and thermoplastic rubbers which may be useful in the practice of the present invention include rubbers such as brominated butyl rubber, chlorinated butyl rubber, polyurethane elastomers, fluoroelatomers, polyester elastomers, butadiene/acrylonitrile elastomers, silicone elastomers, rubbers derived from conjugated dienes such as poly(butadiene), poly(2,3-dimethylbutadiene), poly(butadiene-pentadiene), and poly(isobutylene), ethylene-propylene-diene terpolymer (EPDM) rubbers and sulfonated EPDM rubbers, poly(chloroprene), chlorosulphonated or chlorinated poly(ethylenes), and poly(sulfide) elastomers. Other examples include block copolymers made up of segments of glassy or crystalline blocks such as poly(styrene), poly(vinyl-toluene), poly(t-butyl styrene), or polyester and elastomeric blocks such as poly(butadiene), poly(isoprene), ethylene-propylene copolymers, ethylene-butylene copolymers, or polyether ester, for example, poly(styrene)- poly(butadiene)-poly(styrene) block copolymers.

Thermoset resins differ from thermoplastic polymers in that they become substantially infusible or insoluble irreversibly since they are cured (cross-linked) as opposed to the thermoplastics which are typically not cross-linkable and soften when exposed to heat and are capable of returning to original conditions when cooled. Representative examples of thermoset polymers which may be useful in the practice of the present invention include thermoset phenolic resins such as thermosettable resins containing resorcinol, p-tertiary- octylphenol, cresol, alkylated phenolic novalac, phenolic polyvinyl butyral, and phenolic cresol and an aldehyde such as formaldehyde, acetaldehyde or furfural; thermoset polyimide resins such as those curable resins based on pyromellitic dianhydride, 3,3',4,4'-benzophenone- carboxylic dianhydride and meta-phenylenediamine; thermoset epoxides or epoxy resins such as the resins containing the reaction product bisphenol A or derivatives thereof, for example, the diglycidyl ether of bisphenol A, or a polyol such as glycerol with epichlorohydrin and a cross-linking or curing agent such as a polyfunctional amine, for example, polyalkylenepolyamine; thermoset polyester resins such as the reaction products of an unsaturated dicarboxylic acid such as maleic or fumaric acid (which may be used in combination with a saturated acid such as phthalic or adipic acid) with a dihydric alcohol such as ethylene, propylene, diethylene and dipropylene glycol which cure upon using an ethylenic unsaturated curing agent such as styrene or diallyl phthalate, including thermosettable allyl resins including resins derived from diallyl phthalates, for example, diallyl orthophthalate, diallyl isophthalate, diallyl fumarates and diallyl maleates; thermoset polyurethanes including those derived from the reaction of a diisocyanate, for example, toluene diisocyanate, methylene diphenyl diisocyanate, or isophorone diisocyanate, or a polymeric isocyanate with a polyhydric alcohol such as polypropylene glycol and, if required, an additional cross-linking agent such as water; thermoset urea resins; melamine resins, furan resins, and vinyl ester resins including epoxy (meth)acrylates.

Of these polymers, the preferred thermoplastic polymers are polycarbonates, homo- and copolymers of styrene, nylons, polyesters, thermoplastic polyurethanes, and homo- and copolymers of ethylene and propylene; and the preferred thermoset polymers include the epoxy and urethane resins.

The inorganic layered material which may be used as the reinforcing agent can be any swellable material which can be intercalated with an inorganic and an organic intercalant. Representative examples of inorganic layered materials which may be used in the practice of the present invention include phyllosilicates such as montmόrillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite, and kenyaite; or vermiculite. Other representative examples include illite minerals such as ledikite; the layered double hydroxides or mixed metal hydroxides such as Mg6AI34(OH)188(CO3)1 7H2O (see W.T. Reichle, J. Catal., 94 (1985), 547), which have positively charged layers and exchangeable anions in the interlayer spaces; chlorides such as ReCI3 and FeOCI, chalcogenides such as TiS2, MoS2, and MoS3; cyanides such as Ni(CN)2; and oxides such as H2Si205, V5O13, HTiNbO5, Cr05V05S2, W02V28O7, Cr3O8, MoO3(OH)2, VOPO4-2H2O, CaPO4CH3-H2O, MnHAsO4-H2O, or Ag6Mo10OM,. Other layered materials or multi-layer aggregates having little or no charge on the surface of the layers may also be used in this invention provided they can be intercalated with swelling agents which expand their interlayer spacing. Mixtures of one or more such materials may also be employed.

Preferred layered materials are those having charges on the layers and exchangeable ions such as sodium, potassium, and calcium cations, which can be exchanged, preferably by ion exchange, with ions, preferably cations such as ammonium cations, or reactive organosilane compounds, that cause the multi-lamellar or layered particles to delaminate or swell. Typically, the negative charge on the surface of the layered materials is at least 20 milliequivalents, preferably at least 50 milliequivalents, and more preferably from 50 to 120 milliequivalents, per 100 grams of the multilayered material. Particularly preferred are smectite clay minerals such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite, and kenyaite, with hectorite and montmorilonite having from 20 milliequivalents to 150 milliequivalents per 100 grams material being more preferred. Most preferred layered materials are phyllosilicates.

The multilayered material may be intercalated with an inorganic intercalant and an organic intercalant. The inorganic intercalant can be an inorganic polymeric substance or an inorganic solid having a colloidalparticle size. Representative polymeric substances are substances obtained by hydrolyzing a polymerizable metallic alcoholate such as Si(OR)4, AI(OR)3, Ge(OR)4, Si(OC)2H5)4, Si(OCH3)4, Ge(OC3H7), or Ge(OC2H5)4, either alone or in combination. Representative colloidal sized particles of an inorganic compound which can be used include the colloidal sized particles of the hydrolyzed form of SiO2 (for example, Si(OH) or silica sol), Sb2O3, Fe2O3, AI2O3, TiO2, ZrO2 and SnO2 alone or in any combination.

Most preferably, the grain size of the colloidal inorganic should preferably be in a range of from 5, more preferably from 10, most preferably from 20, to 250, more preferably 12θA. While it may be possible to intercalate the unmodified form of the inorganic material between the layers of the multilayered particulate material, the inorganic intercalant is preferably modified at its surface by a cationic inorganic compound or a metallic alcoholate different than the polymerizable metallic alcoholate. Representative cationic inorganic compounds which may be used to surface treat the inorganic intercalant are titanium compounds, zirconium compounds, hafnium compounds, iron compounds, copper compounds, chromium compounds, nickel compounds, zinc compounds, aluminum compounds, manganese compounds, phosphorus compounds, and boron compounds. Metallic chlorides such as TiCI4, metallic oxychlorides such as ZrCOCI2, and nitrate chloride are preferred. Representative metallic alcoholates which can be used to the treat the surface of the inorganic intercalant are Ti(OR)4, Zr(OR)4, PO(OR)3, or B(OR)3 alone or combination, with Ti(OC3H7)4, Zr(OC3H7)4, PO(OCH3)3, PO(OC2H5)3, B(OCH3)3, B(OC2H5)3 being preferred.

The organic intercalant can be any organic material which displaces, totally or in part, the ions originally on the surface of the multilayered material. In general, the intercalant contains a functional group which interacts with the negative charges on the surface of that material. In addition, the intercalant preferably also contains a functional group reactive with the matrix polymer or possesses some property such as cohesive energy, a capacity for dispersive, polar, or hydrogen-bonding interactions or other specific interactions, such as acid/base or Lewis-acid/Lewis-base interactions, to promote the intermingling ("compatibility") of the matrix polymer and multilayered material.

The organic intercalant can be a water soluble polymer, a reactive organosilane compound, an onium compound such as an ammonium, phosphonium or sulfonium salt, an amphoteric surface active agent, or a choline compound.

Representative examples of water-soluble polymers which can be employed as the organic intercalant in the practice of this invention are water soluble polymers of vinyl alcohol (for example, poly(vinyl alcohol); polyalkylene glycols such as polyethylene glycol; water soluble cellulosics polymers such methyl cellulose and carboxymethyl cellulose, the polymers of ethylenically unsaturated carboxylic acids such as poly(acrylic acid), and their salts, or polyvinyl pyrrolidone. Representative examples of onium compounds include quaternary ammonium salts (cationic surface active agents) having octadecyl, hexadecyl, tetradecyl, dodecyl or like moieties; with preferred quaternary ammonium salts including octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, dihexadecyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt, or ditetradecyl dimethyl ammonium salt .

Representative examples of the amphoteric surface-active agent which can be employed in this invention include surfactants having an aliphatic amine cationic moiety and a carboxyl, sulfate, sulfone or phosphate as the anionic moiety. Representative examples of choline compounds include [HOCH2CH2N(CH3)3]+OH-, C5Hl4CINO, C5H14NOC4H5O6, C6H,4NOC6H7O7- and C5Ht4NOCβH,2O7 .

Representative examples of organosilane compounds include silane agents of the formula: ( v-) '„nSiR( (4 nnmιm)R1 m m

where (-) is a covalent bond to the surface of the layered material, m is 0, 1 or 2; n is 1 , 2 or 3 with the proviso that the sum of m and n is equal to 3; R1 is a nonhydrolyzable organic radical (including alkyl, alkoxyalkyl, alkylaryl, arylalkyl, alkoxyaryl) and is not displaceable during the formation of the composite; R is the same or different at each occurrence and is an organic radical which is not hydrolyzable and displaceable during the formation of the composite which is reactive with the polymer matrix or at least one monomeric component of the polymer. Representative R groups include amino, carboxy, acylhalide, acyloxy, hydroxy, isocyanato ureido, halo, epoxy, or epichlorohydryl. Preferred organosilane intercalants include long chain branched quaternary ammonium salts and/or suitably functionalized organosilane compounds, as disclosed in WO 93/1 1190, pages 9-21.

Organic materials other than those described can also be employed as the organic intercalants provided they can be intercalated between the layers of the multilayered particulate material and subsequently degraded such as by calcination to at least partially remove the intercalant and leave gaps between the layers.

In the practice of the present invention, the multilayered particulate material is intercalated with the inorganic, if employed, and organic intercalants. While the method of intercalation is not particularly critical, in one embodiment of the present invention, prior to intercalating the multilayered material, it is swollen in an aqueous or organic liquid Any aqueous or organic liquid capable of swelling the multilayered material being intercalated can be employed By aqueous liquid it is meant water, including acids and bases as well as some salt solutions. In addition, solutions of water and one or more water-miscible organic liquids such as the lower alkyl alcohols, for example, methanol and butanol, can be employed Representative examples of organic liquids which can be employed include dimethylformamide, dimethylsulfone, halogenated hydrocarbons, for example, methylene chloride, or a liquid hydrocarbon, preferably having from 4 to 15 carbon atoms, including aromatic and aliphatic hydrocarbons or mixtures thereof such as heptane, benzene, xylene, cyclohexane, toluene, mineral oils and liquid paraffins, for example, kerosene and naphtha The polymerizable inorganic intercalant is formed as a solution in a suitable solvent such as ethyl alcohol, or isopropyl alcohol and subsequently hydrolyzed, preferably in the presence of the multilayered material For example, a mixture of the multilayered material, swollen in an appropriate swelling material, and the polymerizable inorganic intercalant can be contacted with a hydrolyzing agent for the polymerizable intercalant to form the inorganic polymer. In general, the hydrolyzation is conducted at a temperature above 70°C. Subsequent to partial or complete polymerization, the organic intercalant can be added The organic intercalant reacts upon the hydrolyzed surfaces of the layered material. In the event a colloidal inorganic intercalant is used the organic intercalant can be added to a dispersion of the colloidal inorganic intercalant. Subsequently, the reaction product of the organic intercalant with the inorganic intercalant is mixed with the swollen multilayered material. While the conditions of such intercalation may vary, in general, it is advantageously conducted at a temperature of from 30°C to 100°C, more advantageously from 60°C to 70°C.

Following intercalation, the intercalated multilayered filler can be dehydrated by conventional means such as centrifugal separation and then dried. While drying conditions most advantageously employed will be dependent on the specific intercalant and multilayered particulate material employed, in general, drying is conducted at temperatures of at least 40°C to 100°C and more advantageously at a temperature of 50°C to 80°C by any conventional means such as a hot air oven The organic intercalant can then optionally be calcined such as by heating to 300°C to 600°C, preferably from 450°C to 550°C. In another embodiment of the present invention, the organic intercalant can be employed to intercalate the multilayered particulate material but the inorganic intercalant is not employed. In this embodiment, the organic intercalant is calcined such as by heating to 300°C to 600°C, preferably from 450°C to 550°C.

Following intercalation and, if conducted, calcination, the intercalant in the multilayered material forms a layer of charge opposite to the charge on the surface of the layers of the multilayered particles with the interlayer spacing being dependent on the intercalants employed and whether the organic intercalant has been calcined or otherwise partially or totally removed. In general, the inter-layer spacing (that is, distance between the faces of the layers as they are assembled in the intercalated material) is from 5 to 60θA (as determined by X-ray diffraction) whereas prior to intercalation the interlayer spacing is usually equal to or less than 4A. This increase in interlayer spacing permits greater penetration of the polymer matrix into the filler. Preferably, the interlayer spacing of the intercalated filler is at least δA, more preferably at least 12A and less than 10θA, more preferably less than 3θA.

Following preparation of the intercalated multilayered material, the intercalated, multilayered material and matrix polymer are combined to form the desired composite.

The amount of the intercalated multilayered material most advantageously incorporated into the polymer matrix is dependent on a variety of factors including the specific intercalated material and polymer used to form the composite as well as its desired properties. Typical amounts can range from 0.001 to 90 weight percent of the intercalated, layered material based on the weight of the total composite. Generally, the composite comprises at least 0.1 , preferably 1 , more preferably 2, and most preferably 4 weight percent and less than 60, preferably 50, more preferably 45 and most preferably 40 weight percent of the intercalated, layered material based on the total weight of the composite.

The intercalated, layered material can be dispersed in the monomer(s) which form the polymer matrix and the monomer(s) polymerized in situ or alternatively, can be dispersed in the polymer, in melted or liquid form. Melt blending is one method for preparing the composites of the present invention, particularly when forming the composite from a thermoplastic polymer. Techniques for melt blending of a polymer with additives of all types are known in the art and can typically be used in the practice of this invention. Typically, in a melt blending operation useful in the practice of the present invention, the polymer is heated to a temperature sufficient to form a polymer melt and combined with the desired amount of the intercalated, multilayered material in a suitable mixer, such as an extruder, a Banbury Mixer, a Brabender mixer, or a continuous mixer.

In the practice of the present invention, the melt blending is preferably carried out in the absence of air, such as in the presence of an inert gas, such as argon, neon, or nitrogen. The melt blending operation can be conducted in a batch or discontinuous fashion but is more preferably conducted in a continuous fashion in one or more processing zones such as in an extruder from which air is largely or completely excluded. The extrusion can be conducted in one zone or step or in a plurality of reaction zones in series or parallel.

Alternatively, the matrix polymer may be granulated and dry mixed with the intercalated, multilayered material, and thereafter, the composition heated in a mixer until the polymer is melted to form a flowable mixture. This flowable mixture can then be subjected to a shear in a mixer sufficient to form the desired composite. This type of mixing and composite preparation is advantageously employed to prepare composites from both thermoplastic and thermoset polymers.

A polymer melt containing the intercalated, multilayered particulate material may also be formed by reactive melt processing in which the intercalated, multilayered material is initially dispersed in a liquid or solid monomer or cross-linking agent which will form or be used to form the polymer matrix of the composite. This dispersion can be injected into a polymer melt containing one or more polymers in an extruder or other mixing device. The injected liquid may result in new polymer or in chain extension, grafting or even cross- linking of the polymer initially in the melt.

Methods for preparing a composite using in situ type polymerization are also known in the art and reference is made thereto for the purposes of this invention. In applying this technique to the practice of the present invention, the composite is formed by mixing monomers and/or oligomers with the intercalated, multilayered material and subsequently polymerizing the monomer and/or oligomers to form the polymer matrix of the composite.

The intercalated, multilayered material is advantageously dispersed under s conditions such that at least 80, preferably at least 85, more preferably at least 90, and most preferably at least 95, weight percent of the layers of the intercalated, multilayered, material delaminate to form individual layers dispersed in the polymer matrix. These layers may be platelet particles having two relatively flat or slightly curved opposite faces where the distance between the faces is relatively small compared to the size of the faces, or needle-like o particles. It is quite probable that the layers of the filler will not delaminate completely in the polymer, but will form layers in a coplanar aggregate. These layers are advantageously sufficiently dispersed or exfoliated in the matrix polymer such that at least 80 percent of the layers are in small multiples of less than 10, preferably less than 5, and more preferably less than 3, of the layers. s The dimensions of the dispersed delaminated layers may vary greatly, but in the case of particles derived from clay minerals, the particle faces are roughly hexagonal, circular, elliptical, or rectangular and exhibit maximum diameters or length from 50 to 2,OOθA. As such, the aspect ratio of length/thickness ranges from 10 to 2,000. The aspect ratio which is most advantageously employed will depend on the desired end-use properties. The o particle faces may also be needle-like.

Optionally, the composites of the present invention may contain various other additives such as nucleating agents, other fillers, lubricants, plasticizers, chain extenders, colorants, mold release agents, antistatic agents, pigments, or fire retardants,. The optional 5 additives and their amounts employed are dependent on a variety of factors including the desired end-use properties.

The composites of this invention exhibit useful properties. For example, they may exhibit enhanced yield strength and tensile modulus, even when exposed to polar media 0 such as water or methanol; enhanced heat resistance and impact strength; improved stiffness, wet-melt strength, dimensional stability, and heat deflection temperature, and decreased moisture absorption, flammability, and permeability as compared to the same polymers which contain the same multilayered material which has not previously been intercalated or where no intercalated material is employed. Improvements in one or more properties can be obtained even though small amounts of intercalated multilayered materials are employed.

The properties of the composites of the present invention may be further enhanced by post-treatment such as by heat treating or annealing the composite at an elevated temperature, conventionally from 80°C to 230°C. Generally, the annealing temperatures will be more than 100°C, preferably more than 110°C, and more preferably more than 120°C, to less than 250°C, preferably less than 220°C, and more preferably less than 180°C.

The composites of the present invention can be molded by conventional shaping processes such as melt spinning, casting, vacuum molding, sheet molding, injection molding and extruding. Examples of such molded articles include components for technical equipment, apparatus castings, household equipment, sports equipment, bottles, containers, components for the electrical and electronics industries, car components, and fibers. The composites may also be used for coating articles by means of powder coating processes or as hot-melt adhesives.

The composite material may be directly molded by injection molding or heat pressure molding, or mixed with other polymers. Alternatively, it is also possible to obtain molded products by performing the in situ polymerization reaction in a mold.

The molding compositions according to the invention are also suitable for the production of sheets and panels using conventional processes such as vacuum or hot- pressing. The sheets and panels can be used to coat materials such as wood, glass, ceramic, metal or other plastics, and outstanding strengths can be achieved using conventional adhesion promoters, for example, those based on vinyl resins. The sheets and panels can also be laminated with other plastic films such as by coextrusion, the sheets being bonded in the molten state. The surfaces of the sheets and panels, can be finished by conventional methods, for example, by lacquering or by the application of protective films.

The composites of this invention are also useful for fabrication of extruded films and film laminates, as for example, films for use in food packaging. Such films can be fabricated using conventional film extrusion techniques. The films are preferably from 10 to 100, more preferably from 20 to 100, and most preferably from 25 to 75, microns thick.

Claims

WHAT IS CLAIMED IS:
1. A composite comprising a polymer matrix having, dispersed therein, an inorganic layered material intercalated with an organic intercalant and an ionic or non-ionic inorganic intercalant.
2. The composite of Claim 1 wherein the polymer matrix is a thermoset or thermoplastic polymer or a vulcanizable or thermoplastic rubber.
3. The composite of Claim 2 wherein the polymer matrix is a thermoplastic polymer of a polymer or copolymer of ethylene, propylene; a monovinylidene aromatic; a polycarbonate; or a thermoplastic polyurethane or mixtures thereof.
4. The composite of Claim 3 wherein the polymer matrix is a linear low density polyethylene, a low density polyethylene or the homogeneously branched linear and substantially linear ethylene copolymers with a density of from 0.85 to 0.92 g/cm3 and a melt index from 0.1 to 10 g/min; substantially linear, functionalized, ethylene copolymers.
5. The composite of Claim 2 wherein the polymer matrix is a thermoset resin.
6. The composite of Claim 5 wherein the thermoset resin is a thermoset phenolic resin; a thermoset epoxide or epoxy resin; a thermoset polyester resin; a thermoset polyurethane; a thermoset urea resin; melamine resin, furan resin, or vinyl ester resin.
7. The composite of Claim 6 where in the thermoset resin is an epoxy or urethane resin.
8. The composite of Claim 1 wherein the inorganic layered material is a phyllosilicate; an illite mineral, a layered double hydroxide or mixed metal hydroxide, ReCI3 and FeOCI; TiS2, MoS2, MoS3; Ni(CN)2; H2Si2O5, V5O,3, HTiNbO5, Cr05V05S2> W02V28O7, Cr3Oβ, MoO3(OH)2, VOPO4-2H2O, CaPO4CH3-H2O, MnHAsO4-H2O, or Ag6Mo10O33.
9. The composite of Claim 8 wherein the inorganic layered material is montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite, or kenyaite.
10. The composite of Claim 8 wherein the inorganic layered material is a phyllosilicate.
1 1 . The composite of Claim 1 wherein the inorganic intercalant is an inorganic polymeric substance obtained by hydrolyzing a polymerizable metallic alcoholate or a colloidal compound.
12. The composite of Claim 1 1 wherein the inorganic intercalant is a polymeric substance which is the hydrolyzed product of Si(OR)4, AI(OR)3, Ge(OR)4, Si(OC)2H5)4, Si(OCH3)4, Ge(OC3H7), Ge(OC2H5)4 or a mixture thereof.
13. The composite of Claim 11 wherein the inorganic intercalant is colloidal sized particle of the hydrolyzed form of SiO2, Sb2O3, Fe2O3, AI2O3, TiO2, ZrO2 and SnO2 or a mixture thereof.
14. The composite of Claim 13 wherein the inorganic intercalant has a grain size of the colloidal inorganic is from 5 to 25θA.
15. The composite of Claim 11 wherein the inorganic intercalant is modified at its surface by a cationic inorganic compound or a metallic alcoholate different than the polymerizable metallic alcoholate.
16. The composite of Claim 15 wherein the cationic inorganic is a metallic chloride; a metallic oxychloride, a nitrate chloride, Ti(OC3H7)4, Zr(OC3H7)4, PO(OCH3)3, PO(OC2H5)3, B(OCH3)3, or B(OC2H5)3.
17. The composite of Claim 1 wherein the organic intercalant is a wate- soluble polymer, a reactive organosilane, an ammonium, phosphonium or sulfonium salt, an amphoteric surface active agent or a chlorine compound.
18. The composite of Claim 1 wherein the organic intercalant is calcined.
19. A composite comprising a polymer matrix having, dispersed therein, a layered filler intercalated with an organic intercalant which is subsequently calcined or otherwise removed from the layered filler.
20. The composite of Claim 19 wherein the organic intercalant is a water soluble polymer of vinyl alcohol; polyalkylene glycol; water soluble cellulosic polymer; a polymer of an ethylenically unsaturated carboxylic acid or its salt; polyvinyl pyrrolidone; a quaternary ammonium salt; an amphoteric surface-active agent having an aliphatic amine cationic moiety and a carboxyl, sulfate, sulfone or phosphate anionic moiety; [HOCH2CH2N(CH3)3j+OH-, C5H14CINO, C5H14NOC4H5O6, C5H,4NOC6H7O7, C5H14NOC6Hl2O7; or
(-LSiRM n m,R'
where (-) is a covalent bond to the surface of the layered material, m is 0, 1 or 2; n is 1 , 2 or 3 with the proviso that the sum of m and n is equal to 3; R' is a nonhydrolyzable organic radical and is not displaceable during the formation of the composite; R is the same or different at each occurrence and is an organic radical which is not hydrolyzable and displaceable during the formation of the composite which is reactive with the polymer matrix or at least one monomeric component of the polymer.
PCT/US1997/002639 1996-02-23 1997-02-20 Polymer composite and a method for its preparation WO1997031057A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US1220696P true 1996-02-23 1996-02-23
US60/012,206 1996-02-23

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AU21320/97A AU2132097A (en) 1996-02-23 1997-02-20 Polymer composite and a method for its preparation
JP9530309A JP2000505490A (en) 1996-02-23 1997-02-20 Polymer complexes and methods for their preparation
BR9707663A BR9707663A (en) 1996-02-23 1997-02-20 Composite polymer
EP19970906694 EP0882092A1 (en) 1996-02-23 1997-02-20 Polymer composite and a method for its preparation

Publications (1)

Publication Number Publication Date
WO1997031057A1 true WO1997031057A1 (en) 1997-08-28

Family

ID=21753854

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/002639 WO1997031057A1 (en) 1996-02-23 1997-02-20 Polymer composite and a method for its preparation

Country Status (8)

Country Link
EP (1) EP0882092A1 (en)
JP (1) JP2000505490A (en)
KR (1) KR19990087161A (en)
CN (1) CN1214711A (en)
AU (1) AU2132097A (en)
BR (1) BR9707663A (en)
CA (1) CA2247148A1 (en)
WO (1) WO1997031057A1 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071988A (en) * 1996-12-31 2000-06-06 Eastman Chemical Company Polyester composite material and method for its manufacturing
US6084019A (en) * 1996-12-31 2000-07-04 Eastman Chemical Corporation High I.V. polyester compositions containing platelet particles
US6162857A (en) * 1997-07-21 2000-12-19 Eastman Chemical Company Process for making polyester/platelet particle compositions displaying improved dispersion
EP1076077A1 (en) * 1999-08-13 2001-02-14 EMS Chemie AG Polyamide resin composition
US6337046B1 (en) 1997-12-22 2002-01-08 Eastman Chemical Company Process for producing containers from polymer/platelet particle compositions
EP1219672A1 (en) * 1999-08-09 2002-07-03 Sekisui Chemical Co., Ltd. Thermoplastic resin foam and process for producing the same
WO2004101691A2 (en) * 2003-05-02 2004-11-25 Dow Global Technologies Inc. Coating and filler compositions comprising platy layered silicate pigments
WO2005087854A2 (en) * 2003-10-10 2005-09-22 Dow Global Technologies Inc. Composite of exfoliated clay in soot and the preparation thereof
WO2006060716A1 (en) * 2004-12-02 2006-06-08 Cryovac, Inc. Intercalated layered silicate
WO2006110137A1 (en) * 2005-04-08 2006-10-19 Dow Global Technologies, Inc. Composite of exfoliated clay in soot and the preparation thereof
WO2007065860A1 (en) * 2005-12-06 2007-06-14 Akzo Nobel N.V. Nanocomposite material comprising rubber and modified layered double hydroxide, process for its preparation and use thereof
US7514490B2 (en) * 1997-08-08 2009-04-07 Nederlandse Oganisatie Voor Toegepastnatuurwetenschappelijk Onderzoek Tno Nanocomposite material
WO2009043861A1 (en) * 2007-10-03 2009-04-09 Akzo Nobel N.V. Composite material, process for preparing the composite material, and use thereof
US7531613B2 (en) 2006-01-20 2009-05-12 Momentive Performance Materials Inc. Inorganic-organic nanocomposite
US7541076B2 (en) * 2006-02-01 2009-06-02 Momentive Performance Materials Inc. Insulated glass unit with sealant composition having reduced permeability to gas
US7569653B2 (en) * 2006-02-01 2009-08-04 Momentive Performance Materials Inc. Sealant composition having reduced permeability to gas
US7605205B2 (en) 2005-11-07 2009-10-20 Exxonmobil Chemical Patents, Inc. Nanocomposite compositions and processes for making the same
US7625976B2 (en) 2006-01-09 2009-12-01 Momemtive Performance Materials Inc. Room temperature curable organopolysiloxane composition
US7674857B2 (en) 2005-11-18 2010-03-09 Momentive Performance Materials Inc. Room temperature-cured siloxane sealant compositions of reduced gas permeability
US8257805B2 (en) 2006-01-09 2012-09-04 Momentive Performance Materials Inc. Insulated glass unit possessing room temperature-curable siloxane-containing composition of reduced gas permeability
AU2007209945B2 (en) * 2006-02-01 2012-10-25 Momentive Performance Materials Inc. Sealant composition having reduced permeability to gas
US8597741B2 (en) 2005-11-18 2013-12-03 Momentive Performance Materials Inc. Insulated glass unit possessing room temperature-cured siloxane sealant composition of reduced gas permeability

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7682691B2 (en) * 2002-02-06 2010-03-23 Sekisui Chemical Co., Ltd. Resin composition of layered silicate
JP2006077059A (en) * 2004-09-07 2006-03-23 Shiseido Co Ltd Resin composition and resin molded product
US20090297568A1 (en) * 2005-08-19 2009-12-03 Grah Michael D Intercalated layered silicate
KR100750292B1 (en) * 2006-08-28 2007-08-10 한국화학연구원 Organophilic layered silicates containing polycarbonate and preparing method thereof
KR100840104B1 (en) 2006-12-29 2008-06-19 동일고무벨트주식회사 Method of manufacturing ethylene propylene diene monomer rubber-organic clay nanocomplex and weather strip for automobile using nanocomplex manufactured by the same
US9175161B2 (en) * 2010-08-01 2015-11-03 Instituto Technológico Del Embalajte, Transporte Y Logística (Itene) Polymer nanocomposite comprising polylactic acid reinforced with the modified phyllosilicate
CN102924666A (en) * 2012-10-15 2013-02-13 深圳大学 Polymer/clay nano-composite material, preparation method thereof and nano-GFRP (Glass Fiber Reinforced Polymer) composite material
CN104118066B (en) * 2014-08-29 2016-07-27 河南易成新能源股份有限公司 The method of manufacturing a resin diamond wire nanohybrid
CN108609153A (en) * 2016-12-29 2018-10-02 深圳光启空间技术有限公司 Envelope material, envelope, aerostat and preparation method for envelope material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004117A1 (en) * 1991-08-12 1993-03-04 Allied-Signal Inc. Melt process formation of polymer nanocomposite of exfoliated layered material
WO1993011190A1 (en) * 1991-11-26 1993-06-10 Allied-Signal Inc. Polymer nanocomposites formed by melt processing of a polymer and an exfoliated layered material derivatized with reactive organo silanes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004117A1 (en) * 1991-08-12 1993-03-04 Allied-Signal Inc. Melt process formation of polymer nanocomposite of exfoliated layered material
WO1993011190A1 (en) * 1991-11-26 1993-06-10 Allied-Signal Inc. Polymer nanocomposites formed by melt processing of a polymer and an exfoliated layered material derivatized with reactive organo silanes

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071988A (en) * 1996-12-31 2000-06-06 Eastman Chemical Company Polyester composite material and method for its manufacturing
US6084019A (en) * 1996-12-31 2000-07-04 Eastman Chemical Corporation High I.V. polyester compositions containing platelet particles
US6162857A (en) * 1997-07-21 2000-12-19 Eastman Chemical Company Process for making polyester/platelet particle compositions displaying improved dispersion
US7514490B2 (en) * 1997-08-08 2009-04-07 Nederlandse Oganisatie Voor Toegepastnatuurwetenschappelijk Onderzoek Tno Nanocomposite material
US6337046B1 (en) 1997-12-22 2002-01-08 Eastman Chemical Company Process for producing containers from polymer/platelet particle compositions
EP1219672A1 (en) * 1999-08-09 2002-07-03 Sekisui Chemical Co., Ltd. Thermoplastic resin foam and process for producing the same
EP1219672A4 (en) * 1999-08-09 2002-10-30 Sekisui Chemical Co Ltd Thermoplastic resin foam and process for producing the same
EP1076077A1 (en) * 1999-08-13 2001-02-14 EMS Chemie AG Polyamide resin composition
WO2004101691A2 (en) * 2003-05-02 2004-11-25 Dow Global Technologies Inc. Coating and filler compositions comprising platy layered silicate pigments
WO2004101691A3 (en) * 2003-05-02 2005-05-06 Jamel F Attal Coating and filler compositions comprising platy layered silicate pigments
WO2005087854A2 (en) * 2003-10-10 2005-09-22 Dow Global Technologies Inc. Composite of exfoliated clay in soot and the preparation thereof
WO2005087854A3 (en) * 2003-10-10 2005-10-27 Dow Global Technologies Inc Composite of exfoliated clay in soot and the preparation thereof
JP2007508229A (en) * 2003-10-10 2007-04-05 ダウ グローバル テクノロジーズ インコーポレイティド Exfoliated clay conjugates and their preparation in soot
AU2005311657B2 (en) * 2004-12-02 2011-09-08 Cryovac, Inc. Intercalated layered silicate
US8568808B2 (en) 2004-12-02 2013-10-29 Cryovac, Inc. Intercalated layered silicate
WO2006060716A1 (en) * 2004-12-02 2006-06-08 Cryovac, Inc. Intercalated layered silicate
CN101120047B (en) 2004-12-02 2012-10-24 克里奥瓦克公司 Intercalated layered silicate
WO2006110137A1 (en) * 2005-04-08 2006-10-19 Dow Global Technologies, Inc. Composite of exfoliated clay in soot and the preparation thereof
US7605205B2 (en) 2005-11-07 2009-10-20 Exxonmobil Chemical Patents, Inc. Nanocomposite compositions and processes for making the same
US7674857B2 (en) 2005-11-18 2010-03-09 Momentive Performance Materials Inc. Room temperature-cured siloxane sealant compositions of reduced gas permeability
US8597741B2 (en) 2005-11-18 2013-12-03 Momentive Performance Materials Inc. Insulated glass unit possessing room temperature-cured siloxane sealant composition of reduced gas permeability
WO2007065860A1 (en) * 2005-12-06 2007-06-14 Akzo Nobel N.V. Nanocomposite material comprising rubber and modified layered double hydroxide, process for its preparation and use thereof
US7625976B2 (en) 2006-01-09 2009-12-01 Momemtive Performance Materials Inc. Room temperature curable organopolysiloxane composition
US8257805B2 (en) 2006-01-09 2012-09-04 Momentive Performance Materials Inc. Insulated glass unit possessing room temperature-curable siloxane-containing composition of reduced gas permeability
US7531613B2 (en) 2006-01-20 2009-05-12 Momentive Performance Materials Inc. Inorganic-organic nanocomposite
US7541076B2 (en) * 2006-02-01 2009-06-02 Momentive Performance Materials Inc. Insulated glass unit with sealant composition having reduced permeability to gas
AU2007209945B2 (en) * 2006-02-01 2012-10-25 Momentive Performance Materials Inc. Sealant composition having reduced permeability to gas
US7569653B2 (en) * 2006-02-01 2009-08-04 Momentive Performance Materials Inc. Sealant composition having reduced permeability to gas
WO2009043861A1 (en) * 2007-10-03 2009-04-09 Akzo Nobel N.V. Composite material, process for preparing the composite material, and use thereof

Also Published As

Publication number Publication date
CA2247148A1 (en) 1997-08-28
BR9707663A (en) 1999-04-13
CN1214711A (en) 1999-04-21
KR19990087161A (en) 1999-12-15
EP0882092A1 (en) 1998-12-09
JP2000505490A (en) 2000-05-09
AU2132097A (en) 1997-09-10

Similar Documents

Publication Publication Date Title
Okada et al. Twenty years of polymer‐clay nanocomposites
Chen et al. Epoxy layered-silicate nanocomposites
Bikiaris et al. Compatibilisation effect of PP-g-MA copolymer on iPP/SiO2 nanocomposites prepared by melt mixing
Choi et al. Synthesis of exfoliated PMMA/Na-MMT nanocomposites via soap-free emulsion polymerization
Ratna et al. Nanocomposites based on a combination of epoxy resin, hyperbranched epoxy and a layered silicate
Ray et al. Polymer/layered silicate nanocomposites: a review from preparation to processing
Choi et al. Morphology and curing behaviors of phenolic resin-layered silicate nanocomposites prepared by melt intercalation
Salahuddin et al. Nanoscale highly filled epoxy nanocomposite
Swain et al. Effect of ultrasound on HDPE/clay nanocomposites: rheology, structure and properties
Zeng et al. Poly (methyl methacrylate) and polystyrene/clay nanocomposites prepared by in-situ polymerization
Ishida et al. General approach to nanocomposite preparation
US6034164A (en) Nanocomposite materials formed from inorganic layered materials dispersed in a polymer matrix
Vaia et al. Lattice model of polymer melt intercalation in organically-modified layered silicates
CN1254512C (en) Material for insulating substrate, printed circuit board, laminate, copper foil with resin, copper-clad laminate, polymide film, film and prepreg for TAB
US6423768B1 (en) Polymer-organoclay composite compositions, method for making and articles therefrom
Kornmann et al. Nanocomposites based on montmorillonite and unsaturated polyester
US6486252B1 (en) Nanocomposites for high barrier applications
US7220484B2 (en) Polymeric nanocomposites comprising epoxy-functionalized graft polymer
Giannelis Polymer layered silicate nanocomposites
Kim et al. Preparation and characteristics of nitrile rubber (NBR) nanocomposites based on organophilic layered clay
LeBaron et al. Polymer-layered silicate nanocomposites: an overview
JP3034027B2 (en) Composite and manufacturing method thereof
Vu et al. Clay nanolayer reinforcement of cis‐1, 4‐polyisoprene and epoxidized natural rubber
Tanaka et al. Polymer nanocomposites as dielectrics and electrical insulation-perspectives for processing technologies, material characterization and future applications
Liu et al. Morphology and fracture behavior of intercalated epoxy/clay nanocomposites

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 97193270.0

Country of ref document: CN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN YU AM AZ BY KG KZ MD RU TJ TM

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997906694

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: PA/a/1998/006832

Country of ref document: MX

ENP Entry into the national phase in:

Ref document number: 2247148

Country of ref document: CA

Ref document number: 2247148

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1019980706554

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1997906694

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1019980706554

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1019980706554

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1997906694

Country of ref document: EP