MX2007003179A - Nanocomposite and method of making the same - Google Patents

Abstract

A composition comprising exfoliated silicate platelets;a thermoplastic polymer;and a block copolymer and method of making the same.

Description

NANOCOMPOSIT AND METHOD TO DO THE SAME BACKGROUND OF THE INVENTION Many materials have been added to polymer resins to reinforce them. Such reinforced polymer resins are generally called composite materials or "nanocomposites". A popular type of such reinforcing material is fiber. Flake materials and particulate formed materials have also been used to reinforce polymer matrices. In particular, a type of nanocomposite has emerged in recent years in which the reinforcing material has one or more dimensions in the order of one nanometer. Such a nanocomposite is known in the art as "nanocomposite". One type of nanocomposite has an exfoliated layered silicate as the reinforcing material where the layered structure is disintegrated and individual silicate platelets are dispersed throughout the polymeric resin. The layered silicates are typically composed of stacked silicate platelets. Silicate platelets typically have a thickness in the order of about one nanometer and typically have an aspect ratio of at least about 100. The spaces between these platelets are called gallery spaces. Under the right conditions, the gallery spaces can be filled with monomer, oligomer or polymer. This increases Ref .: 180542 the distance between the silicate platelets, and swells the silicate in layers in a method called intercalation. If the layered silicate becomes too swollen to the extent that at least some of the individual silicate platelets are no longer organized in piles, those individual silicate platelets are said to be "exfoliated".

BRIEF DESCRIPTION OF THE INVENTION In one aspect, the present invention provides a method for making a nanocomposite, the method comprising: combining components comprising: a layered silicate; a thermoplastic polymer; and a block copolymer comprising a block that is compatible with the layered silicate and at least one additional block that is not compatible with the layered silicate; and exfoliating at least 20 weight percent layered silicate to form a plurality of exfoliated silicate platelets dispersed in the thermoplastic polymer, where no additional block contains a segment of 5 consecutive monomer units that is identical to a segment contained in the polymer thermoplastic, where each additional block is immiscible with the thermoplastic polymer, and in where no additional block forms hydrogen bonds or chemical bonds with the thermoplastic polymer. The methods according to the present invention extend the range of processes and materials that can be used to prepare nanocomposite materials. Accordingly, in another aspect, the present invention provides a nanocomposite comprising: exfoliated silicate platelets; a thermoplastic polymer; and a block copolymer comprising a block which is compatible with the layered silicate and at least one additional block which is not compatible with the layered silicate, wherein no additional block contains a segment of 5 consecutive monomer units which is identical to a segment contained in the thermoplastic polymer, wherein each additional block is immiscible with the thermoplastic polymer, wherein no additional block forms hydrogen bonds or chemical bonds with the thermoplastic polymer, and wherein: the nanocomposite is free of any layered silicate , or the weight ratio of silicate platelets exfoliated to the layered silicate is at least 0.2. Unless otherwise indicated, layer separation values d refer to layer separation values determined at 25 ° C.

As used herein, the term "block" refers to a portion of a block copolymer, which comprises many monomer units, having at least one characteristic that is not present in the adjacent portions; the term "block copolymer" refers to a copolymer composed of constitutionally different blocks in a linear sequence; the term "monomer unit" refers to the largest constitutional unit contributed by a single molecule of monomer to the structure of a polymer; the phrase "compatible with layered silicate" means capable of intercalating with the layered silicate; the term "exfoliated silicate tile" refers to an individual silicate tile having a thickness of less than 5 nanometers and having an aspect ratio of at least 10, and is not associated as a stack face to face with at least one other silicate board, regardless of whether the silicate board was made by exfoliating a silicate in layers or by some other method; and the term "immiscible" means to spontaneously form two phases if they are intimately mixed together, where each phase is independently continuous or discontinuous.

DETAILED DESCRIPTION OF THE INVENTION The compositions of the present invention comprise exfoliated silicate platelets; a thermoplastic polymer; and a block copolymer, typically, in the form of a nanocomposite. Silicates in useful layers that can be used as the layered silicate (for example, interleaved and / or exfoliated) according to the present invention include, for example, natural phyllosilicates, synthetic phytosilicates, synthetic phyllosilicates, organic phyllosilicates. modified (for example, organoarci 1 las), and combinations thereof. Examples of natural products include smectite and smectite-type clays such as montmorilloni ta, nontronite, bentonite, beidellite, hectorite, saponite, sauconite, f luorohec tori ta, stevensite, volkonskoi ta, magadiite, kenyaite, halloysite and hydrotalci ta. Suitable synthetic synthetics include, for example, those prepared by means of hydrothermal processes as described in U.S. Patents. Nos. 3,252,757 (Granqui s t); 3,666,407 (Orlemann); 3,671,190 (Neumann); 3,844,978 (Hickson); 3,844,979 (Hickson); 3,852,405 (Granqui s t); and 3,855,147 (Granquist). Clays of commercially available synthetic smectite are commercially available, for example, from Southern Clay Products, Gonzales, Texas, under the trade designation "LAPONITE" which includes, for example, "LAPONITE B" (a synthetic layered silky lucosite), "LAPONITE D "(a synthetic layered magnesium silicate), and" LAPONITE RD "(a synthetic layered silicate). The organoclays are typically smectite or smectite-like clays produced by interacting non-functionalized clay with one or more suitable intercalating agents. These intercalating agents are typically organic compounds, which are neutral or ionic. Useful neutral organic intercalating agents include polar compounds such as amides, esters, lactams, nitriles, ureas, carbonates, phosphates, phosphonates, sulfates, sulfonates, or compounds, and the like. The neutral organic intercalating agents can be monomeric, oligomeric or polymeric. The neutral organic intercalating agents can be intercalated in the layers of the clay by means of hydrogen bonding without completely replacing the original charge balance ions. Useful ionic intercalating agents are typically cationic surfactants such as, for example, onium compounds such as ammonium derivatives (primary, secondary, tertiary and quaternary), phosphonium, or sulfonium of amines, phosphines and aliphatic, aromatic or aliphatic sulfides. Useful onium ions include, for example, quaternary ammonium ions having at least one long chain aliphatic group (eg, octadecyl, myristyl or oleyl) attached to the quaternary nitrogen atom. More details concerning organoclays and methods for their preparation can be found, for example, in the U.S. patents. Nos. 4,469,639 (Thompson et al.); 6,036,765 (Farrow et al.); and 6,521,678Bl (Chaiko). A variety of organoclays is available from commercial sources. For example, Southern Clay Products offers various organoclays under the trade designations "CLOISITE" (derived from layered aluminum magnesium silicate) and "CLAYTONE" (derived from natural sodium bentonite) which includes "CLAYTONE HY", "CALYTONE AF", "CLOISITE 6A" (modifier concentration of 140 meq / 100 g), "CLOISITE 15A" (modifier concentration of 125 meq / 100 g), and "CLOISITE 20A" (modifier concentration of 95 meq / 100 g). Also, organoclays are commercially available from Nanocor, Arlington Heights, Illinois, under the trade designation "NANOMER".

Typically, the layered silicates have a layer separation d that can be determined by means of well-known techniques such as X-ray diffraction (XRD) and / or transmission electron microscopy (TEM). During the method of the present invention the layer separation d typically increases as the intercalation between individual silicate layers by the block copolymer continues until the layers separate so much that they are considered exfoliated and no layer separation can be observed. by means of XRD or TEM. Useful thermoplastic polymers include, for example, polylactones such as, for example, poly (pivalolac tone) and poly (caprolac tone); polyurethanes such as, for example, those derived from the reaction of diisocyanates such as 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 4,4 ' -diphenylmethane diisocyanate, 3, 3'-dimet i 1 - 4, 4'-diphenylmethane diisocyanate, 3,3'-dimeti 1 - 4, 4'-bi-phenyl-1-diisocyanate, 4'4'-di-phenyl-1-di-propionate iden diisocyanate, 3, 3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimeti 1,4-, 4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidin diisocyanate, toluidin diisocyanate, hexamethylene diisocyanate, or 4, 4 '-diisocyanatodiphenylmethane with linear long-chain diols such as poly (tetramethylene adipate), poly (ethylene adipate), poly (1,4-butyl adipate), poly (ethylene succinate), poly (succinate) of 2, 3-buti log), polyether diols and the like; polycarbonates such as poly (methane bis (4-phenyl) carbonate), poly (1, 1-bi-s (4-pheny1) carbonate), poly (di-phenyl-bis (4-pheny1) carbonate), poly (1, 1 -cic lohexan-bi s (4-f eni 1) carbonate), or poly (2, 2 - (bis-4-hydroxy-phenyl) propan) carbonate; po 1 i sul fonas; polyether ether ketones; polyamides such as, for example, poly (4-aminobutyric acid), poly (hexamethyl and len-adipamide), poly (6-aminohexanoic acid), poly (m-xylylene-adipamide), poly (p-xi 1 i) sebacamide), poly (m-phenylene-softalamide), and poly (p-phenylene terephthalamide); polyesters such as, for example, poly (ethylene azelate), po 1 i (et i 1 en-1, 5-naphthal to), poly (ethylene-2,6-naphthalate), poly (1,4-cyclohexane dimethylene tereph talate), poly (ethylene oxybenzoate), poly (para-hydroxy benzoate), poly (1,4-cyclohexylidene dimethylene terephthalate) (cis), poly (1,4-cyclohexylidene dimethylene terephthalate) (trans), polyethylene terephthalate, and polybutylene terephthalate; poly (arylene oxides) such as, for example, poly (oxide) 2, 6-dimethyl-l, 4-phenylene) and poly (2,6-di-phenylene-1, 1-phenylene oxide); poly (arylene sulfides) such as, for example, polyphenylene sulfide; polyetherimides; vinyl polymers and their copolymers such as, for example, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, lead polyvinyl chloride, and ethylene-vinyl acetate copolymers; acrylic polymers such as, for example, poly (ethyl acrylate), poly (n-butyl acrylate), poly (methyl methacrylate), poly (ethyl methacrylate), poly (n-butyl methacrylate), poly (methacrylate) n-propyl), polyacrylamide, polyacrylonitrile, polyacrylic acid, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers; acrylonitrile copolymers (e.g., poly (acrylonitrile-co-butadiene-co-styrene) and poly (styrene-co-acrylonitrile)); styrenic polymers such as, for example, polystyrene, poly (styrene-co-maleic anhydride) polymers and their derivatives, copolymers of methyl methacrylate-styrene, and copolymers of methacrylated butadiene-styrene; polyolefins such as, for example, polyethylene, polybutylene, polypropylene, chlorinated low density polyethylene, poly (4-methyl-1-pentene); ionomers; poly (epichlorohydrins); polysulfones such as, for example, the reaction product of the sodium salt of 2,2-bis (4- hydroxyphenyl) ropano and 4, 4'-dichlorodiphenyl sulfone; furan resins such as, for example, poly (furan); cellulose ester plastics such as, for example, cellulose acetate, cellulose acetate butyrate, and cellulose propionate; plastic protein; polyarylene ethers such as, for example, polyphenylene oxide; polyimides; polyvinylidene halides; polycarbonates; aromatic polyketones; polyacetals; polysulfonates; polyester ionomers; and polyolefin ionomers. Copolymers and / or combinations of these aforementioned polymers can also be used. Useful elastomeric polymer resins (ie, elastomers) include thermoplastic and thermoset elastomeric polymer resins, eg, polybutadiene, polyisobutylene, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, sulfonated ethylene-propylene-diene terpolymers, polychloroprene, poly (2,3-dimethylbutadiene), poly (butadiene-co-pentadiene), chlorosulfonated polyethylenes, polysulfide elastomers, silicone elastomers, poly (butadiene-co-nitrile), hydrogenated nitrile-butadiene copolymers, acrylic elastomers, copolymers of ethylene-acrylate. Thermoplastic elastomeric polymer resins include block copolymers, made of vitreous or crystalline block blocks such as, for example, polystyrene, poly (vinyl toluene), poly (t-butyl styrene), and polyester, and elastomeric blocks such as polybutadiene, polyisoprene, ethylene-propylene copolymers, ethylene-butylene copolymers, polyether ester and the like, for example, block copolymers poly (styrene-butadiene-styrene) marketed by Shell Chemical Company, Houston, Texas, under the trade designation "KRATON". Copolymers and / or mixtures of these aforementioned elastomeric polymer resins can also be used. Useful polymeric resins also include fluoropolymers, that is, at least partially fluorinated polymers. Useful fluoropolymers include, for example, those that can be prepared (for example, by free radical polymerization) from monomers comprising chlorotrifluoroethylene, 2-chloropentafluoro propene, 3-chloropentafluoropropene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, 1-hydropentafluoro propene, 2-hydropentafluoropropene, 1,1-dichlorofluoroethylene, dichlorodifluoroethylene, hexafluoropropylene, vinyl fluoride, a perfluorinated vinyl ether (for example, a perfluoro (alkoxy vinyl ether) such as CF3OCF2CF2CF2OCF = CF2, or a perfluoro (alkyl vinyl ether) as perfluoro (methyl vinyl ether) or perfluoro (propyl vinyl ether)), curing site monomers such as, for example, nitrile-containing monomers (eg, CF2 = CFO (CF2) LCN, CF2CFO [CF2CF (CF3) O] q (CF20) and CF (CF3) CN, CF2 = CF [0CF2CF (CF3)] r0 (CF2) t CN, or CF2 = CFO (CF2) uOCF (CF3) CN where L = 2 -12; q = 0-4; r = 1-2; y = 0-6; t = 1-4; yu = 2-6), bromine-containing monomers (eg, Z-Rf-Ox-CF = CF2, wherein Z is Br or I, Rf is a substituted or unsubstituted C1-C12 fluoroalkylene, which may be perfluorinated and may contain one or more oxygen atoms of the ether, and x is 0 or 1); or a combination thereof, optionally in combination with additional non-fluorinated monomers such as, for example, ethylene or propylene. Specific examples of such fluoropolymers include polyvinylidene fluoride; copolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride; copolymers of tetrafluoroethylene, hexafluoropropylene, perfluoropropyl vinyl ether, and vinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymers; tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymers (e.g., tetrafluoroethylene perfluoro (propyl vinyl ether)); and combinations thereof. Useful commercially available thermoplastic fluoropolymers include, for example, those marketed by Dyneon, LLC, Oakdale, Minnesota, under the trade designations "THV" (eg, "THV 220", "THV 400G", "THV 500G", "THV 815", and" THV 610X ")," PVDF "," PFA "," HTE "," ETFE ", and" FEP "; those marketed by Atofina Chemicals, Philadelfia, Pennsylvania, under the trade designation "KYNAR" (for example, "KYNAR 740"); those commercialized by Solvay Solexis, Thorofare, New Jersey, under the commercial designations "HYLAR" (for example, "HYLAR 700") and "HALAR ECTFE". Block copolymers are generally formed by successively polymerizing different monomers. Useful methods for forming block copolymers include, for example, anionic, coordination, cationic, and free radical polymerization methods. Block copolymers useful in the practice of the present invention comprise at least two chemically distinct blocks, each block comprising at least 5 monomeric units. The block copolymer is selected such that it comprises a block that is compatible with the layered silicate and at least one additional block that is not compatible with the layered silicate, that is, the block is not intercalated with the layered silicate. . In addition, no additional block contains a segment of 5 consecutive monomer units that is identical to a segment contained in the thermoplastic polymer, each additional block is immiscible with the thermoplastic polymer, and no additional block forms hydrogen bonds or chemical bonds with the thermoplastic polymer .

Useful block copolymers may have any number of blocks greater than or equal to two (for example, copolymers in di-, tri-, tetrablock), and may have any form such as, for example, linear, star, comb or ladder . In general, at least one block has an affinity with the chosen layered silicate (which includes organoclay). This block can be hydrophilic or hydrophobic in nature (for example, by using organoclays). Hydrophilic blocks typically have one or more polar moieties such as, for example, acids (e.g., -C02H, -S03H, -P03H); -OH; -SH; primary, secondary or tertiary amines; N-substituted or unsubstituted ammonium amides and lactams; N-substituted or unsubstituted thioamides and thiolactams; anhydrides; linear or cyclic ethers and polyethers; isocyanates; cyanates; nitriles; carbamates; ureas; thioureas; heterocyclic amines (e.g., pyridine or imidazole)). Useful monomers that can be used to introduce such groups include, for example, acids (eg, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and include methacrylic acid functionality formed via the catalysed acid deprotection of monomeric units of t-butyl methacrylate as described in US Patent No. "2004/0024130" (Nelson et al.)); acrylates and methacrylates (for example, 2-hydroxyethyl acrylate), acrylamide and methacrylamide, N-substituted and N, N-disubstituted acrylamides (for example, Nt-butylacrylamide, N, N- (dimethylamino) ethylacrylamide, N, N-dimethylacrylamide, N, -dimethylmethacrylamide), N-ethylacrylamide, N-hydroxyethylacrylamide, N-octylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-ethyl-N-dihydroxyethylacrylamide), aliphatic amines (eg, 3-dimethylaminopropylamine, N, -dimethylethylene diamine); and heterocyclic monomers (e.g., 2-vinylpyridine, 4-vinylpyridine, 2- (2-aminoethyl) pyridine, 1- (2-aminoethyl) pyrrolidine, 3-aminoquinuclidine, N-vinyl pyrrolidone, and N-vinyl caprolactam). Hydrophobic blocks typically have one or more hydrophobic moieties such as, for example, aliphatic and aromatic hydrocarbon moieties such as those having at least 4, 8, 12, or even 18 carbon atoms; fluorinated aliphatic and / or aromatic fluorinated hydrocarbon portions, such as, for example, those having at least 4, 8, 12, or even 18 carbon atoms; and silicone portions. Useful monomers for introducing such blocks include, for example, hydrocarbon olefins such as, for example, ethylene, propylene, isoprene, styrene, and butadiene; cyclic siloxanes such as, for example, decamethylcyclopentasiloxane and decamethyltetrasiloxane; fluorinated labels such as, for example, tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, difluoroethylene, and chlorofluoroethylene; non-fluorinated alkyl acrylates and methacrylates such as, for example, butyl acrylate, isooctyl methacrylate lauryl acrylate, stearyl acrylate; fluorinated acrylates such as, for example, perfluoroalkylsulfonamidoalkyl acrylates and methacrylates having the formula H2C = C (R2) C (0) 0-XN (R) S02Rf wherein: Rf is -C6F13, -C4F9, or -C3F7R is hydrogen, C 1 -C 0 alkyl, C 6 -C 10 aryl; and X is a divalent linker group. Examples include Such monomers can be readily obtained from commercial sources or can be prepared, for example, according to the procedures in U.S. Pat. Sol. Pub. No. 2004/0023016 (Cernohous et al.). Examples of useful block copolymers having hydrophobic and hydrophilic blocks include poly (isoprene-block-4-vinylpyridine); poly (isoprene-block-methacrylic acid); poly (isoprene-block- N, N- (dimethylamino) ethyl acrylate); poly (isoprene-block-2-diethylaminostyrene); poly (isoprene-glycidyl methacrylate block); poly (isoprene-block-2-hydroxyethyl methacrylate); poly (isoprene-block-N-vinylpyrrolidone); poly (isoprene-block-methacrylic anhydride); poly (isoprene-block- (methacrylic anhydride-methacrylic acid)); poly (styrene-block-4-vinylpyridine); poly (styrene-block-2-vinylpyridine); poly (styrene-block-acrylic acid); poly (styrene-block-methacrylamide); poly (styrene-block-N- (3-aminopropyl) methacrylamide); poly (styrene-block- N, N- (dimethylamino) ethyl acrylate); poly (styrene-block-2-diethylaminostyrene); poly (styrene-block-glycidyl methacrylate); poly (styrene-block-2-hydroxyethyl methacrylate); poly (styrene-block-copolymer of N-vinylpyrrolidone); poly (styrene-block-isoprene-block-4-vinylpyridine); poly (styrene-block-isoprene-block-glycidyl methacrylate); poly (styrene-block-isoprene-block-methacrylic acid); poly (styrene-block-isoprene-block- (methacrylic anhydride-methacrylic acid)); poly (styrene-block-isoprene-block-methacrylic anhydride); poly (butadiene-block-4-vinylpyridine); poly (butadiene-block-methacrylic acid); poly (butadiene-block- N, N- (dimethylamino) ethyl acrylate); poly (butadiene-block-2-diethylaminostyrene); poly (butadiene-block-glycidyl methacrylate); poly (butadiene-block-2-hydroxyethyl methacrylate); poly (butadiene-block-N-vinylpyrrolidone); poly (butadiene-block-methacrylic anhydride); poly (butadiene-block- (methacrylic anhydride-methacrylic acid); poly (styrene-block-butadiene-block-4-vinylpyridine); poly (styrene-block-butadiene-block-methacrylic acid); poly (styrene-block) -butadiene-block- N, N (dimethylamino) ethyl acrylate); poly (styrene-block-butadiene-block-2-diethylaminostyrene); poly (styrene-block-butadiene-block-glycidyl methacrylate); poly (styrene-block) butadiene-block-2-hydroxyethyl methacrylate), poly (styrene-block-butadiene-block-N-vinylpyrrolidone), poly (styrene-block-butadiene-block-methacrylic anhydride), poly (styrene-block-butadiene-block) (methacrylic anhydride-methacrylic acid)) and hydrogenated forms of poly (butadiene-block-4-vinylpyridine), poly (butadiene-block-methacrylic acid), poly (butadiene-block-N, N- (dimethylamino) ethyl) acrylate), poly (butadiene-block-2-diethylaminostyrene), poly (butadiene-block-glycidyl methacrylate), poly (butadiene-block-2-me hydroxyethyl tacrilate), poly (butadiene-block-N-vinylpyrrolidone), poly (butadiene-block-methacrylic anhydride), poly (butadiene-block (methacrylic anhydride co-methacrylic acid)), poly (isoprene-block-4-vinylpyridine) ), poly (isoprene-block-methacrylic acid), poly (isoprene-block-N, N- (dimethylamino) ethyl acrylate), poly (isoprene-block-2-diethylaminostyrene), poly (isoprene-) glycidyl block-methacrylate), poly (isoprene-block-2-hydroxyethyl methacrylate), poly (isoprene-block-N-vinylpyrrolidone), poly (isoprene-block-methacrylic anhydride), poly (isoprene-block (methacrylic anhydride - co-methacrylic acid), poly (styrene-block-isoprene-block-glycidyl methacrylate), poly (styrene-block-isoprene-block-methacrylic acid), poly (styrene-block-isoprene-block-methacrylic anhydride -co) - methacrylic acid), styrene-block-isoprene-block-methacrylic anhydride, poly (styrene-block-butadiene-block-4-vinylpyridine), poly (styrene-block-butadiene-block-methacrylic acid), poly (styrene-block) -butadiene-block- N, - (dimethylamino) ethyl acrylate), poly (styrene-block-butadiene-block-2-diethylaminostyrene), poly (styrene-block-butadiene-block-glycidyl methacrylate), poly (styrene-) block-butadiene-block-2-hydroxyethyl methacrylate), poly (styrene-block-butadiene-block-N-vinylpyrrolidone), poly (styrene-block-butadiene-block-methacrylic anhydride), poly (styrene-block-butadiene-block- (methacrylic anhydride-methacrylic acid), poly (MeFBSEMA-block-methacrylic acid) (wherein "MeFBSEMA" is refers to 2- (N-methyl perfluorobutanesulfonamido) ethyl methacrylate, for example, as available from 3M Company, Saint Paul, Minnesota), poly (MeFBSEMA-t-butyl methacrylate block), poly (styrene-block-methacrylate) of t-butyl-block- MeFBSEMA), poly (styrene-block-methacrylic anhydride block-MeFBSEMA), poly (styrene-block-methacrylic acid-block-MeFBSEMA), poly (styrene-block- (methacrylic anhydride-methacrylic acid) -block-MeFBSEMA) ), poly (styrene-block- (methacrylic anhydride-methacrylic acid-co-MeFBSEMA)), poly (styrene-block- (t-butyl methacrylate -co- MeFBSEMA)), poly (styrene-block-isoprene-) t-butyl block-methacrylate-block-MeFBSEMA), poly (styrene-isoprene-block-methacrylic anhydride-block-MeFBSEMA), poly (styrene-isoprene-block-methacrylic acid-block-MeFBSEMA), poly (styrene-block -isoprene-block- (methacrylic anhydride-methacrylic acid) -block-MeFBSEMA), poly (styrene-block-isoprene-block- (methacrylic anhydride-methacrylic acid-co-MeFBSEMA)), poly (styrene-block) -isoprene-block- (t-butyl methacrylate -co-MeFBSEMA)), poly (MeFBSEMA-block-methacrylic anhydride), poly (MeFBSEMA-block- (acid) or methacrylic-methacrylic anhydride), poly (styrene-block- (t-butyl methacrylate -co-MeFBSEMA)), poly (styrene-block-butadiene-block-t-butyl methacrylate-block-MeFBSEMA), poly (styrene-butadiene-block-methacrylic anhydride-block-MeFBSEMA), poly (styrene-butadiene-block-methacrylic acid-block-MeFBSEMA), poly (styrene-block-butadiene-block- (methacrylic anhydride-methacrylic acid) ) -block-MeFBSEMA), poly (styrene-block-butadiene-block- (methacrylic anhydride -co-acid) methacrylic -co- MeFBSEMA)), and poly (styrene-block-butadiene-block- (t-butyl methacrylate -co-MeFBSEMA)). In general, the block copolymer should be chosen so that at least one block is capable of intercalating with the layered silicate. For natural and synthetic clays, this typically means that at least one block must be hydrophilic; although in the case of organoclays the block can be hydrophilic or hydrophobic. The choice of remaining blocks of the block copolymer will typically be governed by the nature of any polymeric resin with which the layered silicate and block copolymer will subsequently be combined. Although the additional blocks must be immiscible with the thermoplastic polymer, at least one (e.g., all) of the additional blocks is typically selected to be more compatible with the thermoplastic polymer than the clay itself. For example, oleophilic blocks such as polyolefins, poly (alkyl acrylates), styrenics, polysiloxanes, and fluoropolymers are typically useful with oleophilic thermoplastic polymers such as polyolefins, styrenics, and fluoropolymers. Any amount of block copolymer can be used; however, typically the block copolymer is included in an amount in a range of 0.01 to 10 parts or more by weight per part of the layered silicate included in the first mix. More typically, the block copolymer is included in an amount in a range of 0.05 to 2 parts or more by weight per part of the layered silicate included in the first mixture. A solvent may, optionally, be combined with the block copolymer and layered silicate, for example, to aid in the intercalation and / or delamination of the layered silicate. Useful solvents include, for example, organic solvents, water, supercritical C02, and combinations thereof. Examples of organic solvents include esters (e.g., ethyl acetate, butyl acetate, beta-ethoxyethyl acetate, beta-butoxy-beta-ethoxyethyl acetate, methyl cellosolve acetate, cellosolve acetate, diethylene glycol monoacetate, methoxytriglylacetate, and acetate) sorbitol), ketones (eg, methyl isobutyl ketone, 2-butanone, acetonylacetone, and acetone), aromatic hydrocarbons (eg, benzene, toluene, and xylene), aliphatic hydrocarbons (eg, cyclohexane, heptane, octane, dean , and dodecane), nitriles (e.g., ac etoni tri lo), ethers (e.g., tetrahydrofuran, dioxane, and diglyme), alcohols (e.g., methanol, ethanol, isopropanol, butanol, octanol, decanol, buti lcarbi tol, methylcarbi tol, diethylene glycol, dipropylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diacetone alcohol), halocarbons (for example, carbon tetrachloride, methylene chloride, trifluorotoluene, and chloroform), and combinations thereof. However, if a solvent is used its content in the mixture comprising block copolymer and interlayer layered silicate and / or exfoliated silicate platelets is typically reduced to a low level, although this is not a requirement. For example, mixtures and / or nanocomposite materials according to the present invention can be essentially free of (ie, contain less than one percent of) solvent. Methods for removing solvent include, for example, oven drying and evaporation under reduced pressure. Optionally, the composition may further contain one or more additives such as, for example, surfactants, fire-proofing agents, fillers, ultraviolet absorbers, antioxidants, tackifier resins, colorants, fragrances, or antimicrobial agents. Although the compositions according to the present invention are typically prepared and processed in a fluid state (eg, as a material melted or in optional solvent), can also be used as solids; for example after cooling and / or after removing any optional solvent. The compositions according to the present invention can be made according to any suitable method. In one example method, the layered silicate, thermoplastic polymer, block copolymer, and a solvent capable of swelling the layered silicate and dissolving the thermoplastic polymer and the block copolymer are mixed, and then the solvent is evaporated (e.g. , in an oven or a rotary evaporator). In another example method, the components of the present composition are ground in a kneader or extruder. Such equipment is well known and / or readily available commercially; Typically equipped with devolatilization capabilities (eg, vacuum holes) and / or zones with temperature control. The equipment may have a single hole (distinct from any vacuum holes) for inserting and removing material, or it may have separate inlet and outlet holes as in the case of a high viscosity extruder or processor. If the components of the composition comprise a solvent, then the solvent is typically removed under partial vacuum during grinding. For example, as described in the U.S. patent application. presented concurrently entitled "METHOD TO MAKE A COMPOSITION AND NANOCOMPOSITES FROM IT" (Nelson et al.), lawyer reference No. 60060US002. An example of a suitable high viscosity processor (i.e., a kneader), typically provided with vacuum equipment, is a high viscosity processor marketed under the trade designation "DISCOTHERM B" by List USA, Inc., Acton, Massachusetts. Another example of a suitable mixer, equipped with a vacuum system, is that marketed by IKA Works, Inc., Wilmington, North Carolina, under the trade designation "MKD 0.6 - H 60 HIGH PERFORMANCE MEASURING MACHINE". Another example of a suitable high performance kneader is commercially available under the trade designation "SRUGO SIGMA KNEADER" from Srugo Machines Engineering, Netivot, Israel. This mixer can be connected to a vacuum equipment by means of vacuum holes in the mixer. Useful extruders include, for example, single screw extruders and multiple screw extruders and reciprocating extruders. Examples of suitable extruders include those marketed by Coperion Buss AG, Pratteln, Switzerland, under the trade designation "MKS", for example, "MKS 30". The degree of intercalation and / or exfoliation of the layered silicate can be largely controlled through variables including, for example, concentration or composition of components, pressure (ie, vacuum) in the mixing apparatus, the profile of process temperature (eg, isothermal or sloping), screw design, order of addition of materials, the level of shear applied and / or index, and the duration of the mixing process. For example, intercalation and / or exfoliation can typically be improved by increasing the temperature or reducing the rate of solvent removal (for example, by reducing the degree of an applied vacuum). When selecting the temperature the physical properties and chemical properties of the solvent, layered silicate, and block copolymer should be considered, for example, such that the decomposition of the layered silicate and / or block copolymer can be maintained at a level relatively low Such variables can be modified in a continuous or gradual manner, or they can be maintained at a constant level. To assist processing, the temperature of the kneader or extruder is typically maintained above the vitreous transition temperature and / or melting temperature of the block copolymer, although this is not a requirement. Whichever method is used, it must be of sufficient duration to ensure that at least 20, 30, 40, 50, 60, 70, 80 or even at least 90 percent by weight of the layered silicate is exfoliated to form a plurality of exfoliated silicate platelets dispersed in the thermoplastic polymer. The methods according to the present invention can be carried out in a batch process or in a continuous manner. The compositions prepared according to the present invention are dispersions; typically, isotropic dispersions of exfoliated silicate platelets in the thermoplastic polymer. The block copolymer is typically associated with the exfoliated silicate platelets and serves as a dispersion aid such that the exfoliated silicate platelets can be dispersed in the thermoplastic resin. The amount of exfoliated silicate platelets in the composition can be any, but typically it is in a range of 0.1 to 10 weight percent, more typically in a range of 0.5 to 7 weight percent, and even more typically in a range of 1 to 5 weight percent, based on the total weight of the composition. Similarly, in some embodiments, the weight ratio of silicate platelets exfoliated to the layered silicate in the composition may be at least 0. 2, 0. 5, 1, 2, 3, 4, 5, 1 0, 5 0 or more, although smaller weight ratios may also be used. For example, in the methods according to the present invention, the layered silicate can be at least 4 0, 5 0, 0, 0, or even at least 9 5 percent exfoliated, based on the initial weight of the layered silicate used. In some cases, substantially all of the layered silicate can be exfoliated. The nanocomposite materials prepared in accordance with the present invention are useful, for example, in the manufacture of barrier films or bottles, and flame retardant materials. The objects and advantages of this invention are further illustrated by the following non-limiting examples, but the particular materials and amounts thereof mentioned in these examples, as well as other conditions and details, should not be construed as excessive limitations of this invention.

EXAMPLES Unless otherwise indicated, all parts, percentages, relationships, etc. in the examples and the remainder of the specification are by weight, and all reagents used in the examples were obtained, or are available, from suppliers of general chemical substances such as, for example, Sigma-Aldrich Company, Saint Louis, Missouri , or they can be synthesized by conventional methods. The following abbreviations are used in all jobs: Abbreviation Description P (S-VP) AB diblock copolymer, poly (styrene-block-4-vinylpyridine), synthesized with the use of an agitated tubular reactor process generally as described in Example 1 of U.S. Pat. No. 6,448,353 (Nelson et al.); Mn = 20 kg / mol; PDI = 1.8; 95/5 weight ratio of styrene to 4-vinylpyridine monomer units. P (I-GMA) AB diblock copolymer, poly [isoprene-block-glycidyl methacrylate]; synthesized with the use of a stirred tubular reactor, generally as described in Example 4 of U.S. Pat. No. 6,448,353 (Nelson et al.), Except that glycidyl methacrylate was used in place of 4-vinylpyridine; Mn = 30 kg / mol; PDI = 4.00; 94/6 Weight ratio of isoprene to glycidyl methacrylate monomer units. P (I-S-VP) ABC triblock copolymer, poly [isoprene-block-styrene-block-4-vinylpyridine]; synthesized with the use of a stirred tubular reactor, generally as described in Example 4 of U.S. Pat. No. 6,448,353 (Nelson et al.) / Except that styrene was added to the mixture; Mn = 35 kg / mol; PDI = 2.0; 20/75/5 weight ratio of PI / PS / PVP isoprene to styrene to 4-vinylpyridine monomer units. P (I-VP) AB diblock copolymer, poly (isoprene-block-4-vinylpyridine), synthesized with the use of a stirred tubular reactor, generally as described in example 8d of U.S. No. 6,448,353 (Nelson et al.); Mn = 30 kg / mol; PDI = 2.1; 96/4 weight ratio of isoprene to 4-vinylpyridine monomer units. P (S-GMA) AB diblock copolymer, poly [styrene-block-glycidyl methacrylate], synthesized with the use of an agitated tubular reactor process, generally as described in Example 4 of U.S. Pat. No. 6,448,353 (Nelson et al.); Mn = 40 kg / mol; PDI = 2.2; 98/2 weight ratio of styrene to glycidyl methacrylate monomer units.

P (t-BMA- AB diblock copolymer, MeFBSEMA) poly [t-butyl-block-2- (N-methylperfluorobutan sulfonamido) ethyl methacrylate] methacrylate]; synthesized with the use of an agitated tubular reactor process, generally as described in Example 4 of the U.S. patent application. Publ. 2004/0023016 (Cernohous et al.); Mn = 65 kg / mol; PDI = 1.7; 80/20 weight ratio of t-butyl methacrylate to 2- (N-methylperfluorobutansulfonamido) eti1 methacrylate monomer units. OCl Organically modified montmorillonite clay available under the trade designation "CLOISITE 20A" from Southern Clay Products (modified with methyl, tallow (-65% Ci8; -30% Ci6; -5% Ci4), 'quaternary ammonium chloride; OCl XRD as purchased showed a d-layer separation of 2.41 nanometers (nm) OC2 Organically modified montmorillonite clay available under the designation Products, Gonzales, Texas (modified with dimethyl, benzyl, hydrogenated tallow (-65% Cie; ~ 30% Ci6; -5% Ci4), quaternary ammonium chloride; is believed to have a d-layer separation of 1.92 nm. of organically modified montmorillonite available under the trade designation "CLOISITE 25A" from Southern Clay Products (modified with dimethyl hydrogenated tallow (-65% Co.; -30% Ci6; -5% Ci4); 2-ethylhexyl quaternary ammonium methyl sulfate; it is believed to have a d-layer separation of 1.86 nm. Organically modified montmorillonite clay available under the trade designation "CLOISITE 30B" from Southern Clay Products (modified with methyl, tallow (-65% Ci8; -30% Ci6; ~ 5% C14), bis-2-hydroxyethyl, quaternary ammonium chloride); it is believed to have a d-layer spacing of 1.85 nm. A 65.9 weight percent copolymer hexafluoropropylene; available under the trade designation "FC 2145" from Dyneon, LLC. PP Polypropylene available under the trade designation "ESCORENE 1024" from Exxon Mobil Corp., Irving, Texas. HDPE High density polyethylene, available under the trade designation "ALATHON M6020" from Equistar Chemical Co. , Houston Texas . TPO Thermoplastic polyolefin, available under the trade designation "FLEXATHENE TP1300HC" from Equistar Chemical Co. , Houston Texas.

The following procedures were used in the examples: PREPARATION OF FILM FOR XRD AND TEM ANALYSIS Analysis was carried out via XRD and TEM in films of 1 mm thickness. To form the films, each material to be analyzed was placed between untreated polyester linings with a thickness of 0.051 mm, which in turn were placed between 2 aluminum plates (each with a thickness 3.2 mm) to form a pile. Two shims (each with a thickness of 1 mm) were placed on each of the two sides of the stack in such a way that when pressing the assembled pile the mixture did not come into contact with either of the two shims. Each stack was placed in a heated hydraulic press available under the trade designation "WABASH MPI MODEL G30H-15-LP" from Wabash MPI, Wabash, Indiana. Both the upper press plate and the lower press plate were heated to 193 ° C. The stack was pressed for 1 minute at 1500 psi (10 MPa). The hot stack was then moved to a press cooled with low pressure water for 30 seconds to cool the stack. The pile was disassembled and the linings were removed from both sides of the film disk that resulted from pressing the mixture.

X-ray diffraction (XRD) X-ray scattering data with reflection geometry were collected with the use of a four-circle diffractometer (available under the trade designation "HUBER (424 / 511.1)" from Huber Diffraktionstechnik GmbH, D83253 Rimsting, Germany), K-alpha copper radiation, and scintillation detector record of scattered radiation. The incident beam was collimated to a circular aperture of 0.70 mm. Sweeps were carried out in a reflection geometry of 0.5 to 10 degrees (2 teta) with the use of a step size of 0.05 degrees and a dwell time of 10 seconds. A sealed tube X-ray source and 40 kV and 20 mA X-ray generator settings were used. Data analysis and peak position definition were determined with the use of X-ray diffraction analysis software available under the trade designation "JADE" from MDI, Inc., Livermore, California.

Transmission electron microscopy (TEM) TEM was carried out with the use of a transmission electron microscope operated at 200 kV, available under the trade designation "JEOL 200CX" from JEOL USA, Peabody, Massachusetts.

Molecular weight and polydispersity The average molecular weight and polydispersity were determined by means of gel penetration chromatography (GPC) analysis. Approximately 25 mg of a sample were dissolved in 10 milliliters (mL) of THF to form a mixture. The mixture was filtered with the use of a polytetrafluoroethylene syringe filter with a pore size of 0.2 microns. Then, approximately 150 microliters of the filtered solution were injected into a column packed with gel 25 cm long by 1 cm in diameter available under the commercial designation "PLGEL-MIXED B" of PolymerLabs, Amherst, Massachusetts, which was part of a GPC system equipped with an autosampler and a pump. The GPC was operated by system at room temperature with the use of THF eluent that moved at a flow rate of approximately 0. 95 mL / minute. A refractive index detector was used to detect changes in concentration. The calculations of number average molecular weight (Mn) and polydispersity index (PDI) were calibrated with the use of narrow polydispersity polystyrene controls that varied in molecular weight from 600 to 6 x 106 g / mol. The actual calculations were made with software (available under the trade designation "CALIBER" from Polymer Labs). 1H RM spectroscopy The relative concentration of each block was determined by 1H Nuclear Magnetic Resonance spectroscopy (1H NMR). The samples were dissolved in deuterated chloroform at a concentration of approximately 10 weight percent and placed in a 500 MHz NMR spectrometer available under the trade designation "UNITY 500 MHZ NMR SPECTROMETER" from Varian, Inc., Palo Alto, California. The block concentrations of relative areas of spectra of characteristic block components were calculated.

Voltage stress measurement and tension modulus Granulated nanocomposite portions were injected at 180 ° C and 70 psi (0.48 MPa) with the use of an injection moulder available under the trade designation "MINI-JECTOR MODEL 45" from Mini- Jector Machinery Corp., Newbury, Ohio. Tension rods were produced for physical properties tests and were made in accordance with the "Standard test method for plastic tensile properties by using microtension samples (2002)" ASTM Dl708-2a. The samples were tested in a voltage tester available under the. commercial designation "INSTRON 5500 R" from Instron Corporation, Canton, Massachusetts. The portions were extracted at a speed of 50.8 mm / min in a room with temperature and controlled humidity at 21.1 ° C and 55 percent relative humidity. The reported results represent an average of 5 individual measurements. The following general procedures are used in the examples: General batch procedure for mixing The components were mixed in a melt mixer available under the trade designation "BRABENDER PLASTI-CORDER MODEL PL2100" (BPM) from Brabender, South Hackensack, New Jersey. The mixer was equipped with a mixer head type 6 with the use of mixing paddles of roller blade. The batch temperature and torque were measured during mixing. The thermoplastic polymer is added to the mixer and allowed to melt at a temperature of 180 ° C and a paddle speed of 50 rpm. Once the temperature is balanced, the block copolymer and layered silicate are added simultaneously. The nanocomposites are mixed for 30 minutes.

General procedure for continuous twin screw extrusion The extrusion was carried out with the use of a 25 mm twin screw, joint rotating extruder, with 41: 1 L / D available under the trade designation "COPERION ZSK-25 WORLD LAB EXTRUDER "by Coperion, Ramsey, New Jersey. The barrel zones for the extruder model used in these examples have a length of 4D (100 mm). Two screw designs can be used.

Design of screw AA in order to create a flow of uniform molten material before the addition of block copolymer and clay materials in barrel zones 2 and 3 the screw design incorporates a distributive mixing section of a total length of 1.76 D (that is, 1.76 times the diameter of the hole), which consists mainly of elements of mixed gear type, under the commercial designation "Z E" available from Coperion. A low to medium shear intensity kneading section is used in the barrel area 4 to incorporate and melt the hand-mixed block copolymer and clay powder additives into the molten resin after its addition to the extruder in the area from barrel 3 through a hole 2 | D open to the atmosphere. The total length of this kneading section is 2.5 D. The temperature of the molten material flow is monitored and recorded in this kneading section by a dip depth thermocouple. A small hole of atmospheric ventilation, with a length of 1 D, at the beginning of the zone of barrel 5 allowed the ventilation of any trapped air from the addition of dust. A 5.5 D kneading section, covering the barrel area 5, 6, and 7, with high-shear advance kneading blocks, is designed for dispersion and exfoliation of the clay in the host resin. This mixing section is sealed at the downward end by three blocks of reverse kneading, with narrow paddles, to ensure that the mixing section is filled with molten material as well as to distribute the exfoliated clay material at all the nanocomposite The melting temperature of the material in this kneading section is monitored and recorded with the use of a dip depth thermocouple. Another 5 D mixing section with advance kneading blocks, with high shear stress, was used in zones 8 and 9 to provide additional shear stress for further exfoliation of the clay particles. This section is not sealed with reverse kneading blocks in order to allow a nitrogen scavenging gas, which is injected into the barrel zone 7, to flow freely in the nearly full mixing zone to the vacuum vent, with a length of 2 D, in the barrel zone 9 to remove any volatile components. A vacuum of 52 torr (6.9 kPa) is extracted in this ventilation hole.

Design of screw B This design is similar to the design of screw A but differs in that the two descending mixing sections use blocks of advance kneading, of intermediate shear, instead of blocks with great shear, with wider vanes, using the design A. Also, the length of these mixing zones is shorter than in the design of screw A due to the use of narrower kneading discs than screw design A. The total lengths of these mixing sections are 3 D and 3 D, respectively, compared to 5.5 D and 5 D for the corresponding mixing sections in the screw design A. In general, screw B has less intensity of shear stress than screw A. The continuous extrusion of the molten resin in the feed zone of the twin screw extruder is carried out by the use of an extruder of 1.25 inch (3.18 cm) simple screw equipped with a general purpose 3.0: 1 compression screw with 24 trajectories, available under the trade designation "KILLION KTS-125" from Davis-Standard, Pawcatuck, Connecticut. Powdered additives were mixed by hand and fed into the barrel area 3 of the twin screw extruder with the use of a gravimetric feeder equipped with two propeller screws available under the trade designation "K-TRON GRAVIMETRIC FEEDER, MODEL KCLKT20" from K -Tron International, Pitman, New Jersey. The molten nanocomposite was measured by means of a 10.3 mL / revolution gear pump available under the trade designation "NORMAG" from Dynisco Extrusion, Hickory, North Carolina, and extruded by means of a tube of 1/2 inch (1.3 cm) in diameter to form strands. This extruded strand was cooled in an 8 ft (2.4 m) water bath available from Berlyn Corporation, Worcester, Massachusetts, and granulated with the use of a strand granulator available under the trade designation "CONAIR MODEL 304" from Reduction Engineering, Kent, Ohio.

EXAMPLES 1-12 The block copolymer, layered silicate and thermoplastic polymer were mixed in amounts as reported in table 1 (below) and extruded according to the General Procedure for Continuous Double Screw Extrusion.

TABLE 1 The extrusion conditions for examples 1-12 are reported in table 2 (below), which also reports the layered silicate form as determined by XRD.

TABLE 2 EXAMPLES 13-17 Examples 13-17 were prepared according to the General Procedure for Continuous Double Screw Extrusion with the use of PP as the thermoplastic polymer. Example 17 was prepared with the use of PP, but without block copolymer or layered aggregate silicate. Table 3 (below) reports the compositions of granulated extruded material and the corresponding physical properties.

TABLE 3 EXAMPLES 18-20 Examples 18-20 were carried out in accordance with the General Batching Procedure for Mixing. The resulting melt mixture was removed from the melt mixer, cooled to room temperature, pressed into a film, and analyzed by XRD. Table 4 (below) reports the compositions and layered silicate form.

TABLE 4 EXAMPLE 21 P (I-VP) (100 g) was dissolved in 800 g of THF. 0C1 (100 g) was added to this solution. The solution was dried in an intermittent vacuum oven at 80 ° C for 12 hours until all the THF had been removed. The resulting masterbatch had a 1: 1 weight ratio of P (I-VP): 0C1. A variable speed two-roll mill obtained from Kobelco Stewart Bolling, Hudson, Ohio, was used to mix 30 g of the master batch with 300 g of FE. The rollers had a diameter of 6 inches (15 cm) and a length of 12 inches (30 cm), and the roller speed was 31 revolutions per minute (rpm). The masterbatch was added after the FE was bound on the roller and mixed by cutting the strip and removing the roll bench until the resulting mixture had a uniform appearance (approximately 10 minutes). The roller speed was 31 rpm. The resulting mixtures of the mill were pressed on a film and analyzed by means of XRD, which showed an increase in layer separation d to 3. 5 nm, which indicates intercalation. Those skilled in the art can make various modifications and alterations of this invention without departing from the scope and spirit of this invention, and it should be understood that this invention should not be excessively limited to the illustrative embodiments set forth herein. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (22)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A method for making a nanocomposite, characterized in that it comprises: combining components comprising: a layered silicate; a thermoplastic polymer; and a block copolymer comprising a block that is compatible with the layered silicate and at least one additional block that is not compatible with the layered silicate; and exfoliating at least 20 weight percent of the layered silicate to form a plurality of exfoliated silicate platelets dispersed in the thermoplastic polymer, wherein no additional block contains a segment of 5 consecutive monomer units which is identical to a segment contained in the thermoplastic polymer, wherein each additional block is immiscible with the thermoplastic polymer, and wherein no additional block forms hydrogen bonds or chemical bonds with the thermoplastic polymer.
2. 2. The method according to claim 1, characterized in that the thermoplastic polymer comprises a polyolefin, a fluoropolymer, or polystyrene.
3. 3. The method according to claim 1, characterized in that the thermoplastic polymer is selected from the group consisting of polyethylene and polypropylene.
4. 4. The method according to claim 1, characterized in that the layered silicate is at least 40 percent exfoliated.
5. 5. The method according to claim 1, characterized in that the layered silicate is at least 70 percent exfoliated.
6. The method according to claim 1, characterized in that at least 95 weight percent of the layered silicate is exfoliated.
7. The method according to claim 1, characterized in that the components further comprise a solvent.
8. 8. The method of compliance with the claim 1, characterized in that the block copolymer comprises a diblock polymer.
9. The method according to claim 1, characterized in that the block copolymer is selected from the group consisting of poly (styrene-block-4-) vinylpyridine), poly (styrene-block-isoprene-block-4-vinylpyridine), poly (styrene-block-butadiene-block-4-vinylpyridine), poly (isoprene-block-4-vinylpyridine), poly (butadiene-block) 4-vinylpyridine), hydrogenated versions of poly (butadiene-block-4-vinylpyridine), poly (styrene-block-isoprene-block-4-vinylpyridine), poly (styrene-block-butadiene-block-4-vinylpyridine), and poly (isoprene-block-4-vinylpyridine).
10. 10. The method according to claim 1, characterized in that the layered silicate comprises montmorillonite, nontronite, bentonite, beidellite, hectorite, saponite, sauconite, fluorohectorite, stevensite, volkonskoite, magadiite, kenyaite, halloysite, hydrotalcite, a silicate in synthetic layers, or a combination thereof.
11. 11. The method according to claim 1, characterized in that the layered silicate comprises an organoclay.
12. The method according to claim 1, characterized in that the weight ratio of the block copolymer to the layered silicate included in the first mixture is in the range of 0.01 to 10, inclusive.
13. The method according to claim 1, characterized in that the weight ratio of the block copolymer to the layered silicate included in the first mix is in the range of 0.05 to 2, inclusive.
14. 14. A nanocomposite characterized in that it comprises: exfoliated silicate platelets; a thermoplastic polymer; and a block copolymer comprising a block that is compatible with the layered silicate and at least one additional block that is not compatible with the layered silicate, wherein no additional block contains a segment of 5 consecutive monomer units which is identical to a segment contained in the thermoplastic polymer, wherein each additional block is immiscible with the thermoplastic polymer, wherein no additional block forms hydrogen bonds or chemical bonds with the thermoplastic polymer, and wherein: the nanocomposite is free of any layered silicate, or the ratio in The weight of silicate platelets exfoliated to the layered silicate is at least 0.2.
15. 15. The nanocomposite according to claim 14, characterized in that the thermoplastic polymer is selected from the group consisting of polyolefins and fluoropolymers.
16. 16. The nanocomposite according to claim 14, characterized in that the thermoplastic polymer is selected from the group consisting of polyethylene and polypropylene.
17. 17. The nanocomposite according to claim 14, characterized in that the block copolymer comprises a diblock polymer.
18. 18. The nanocomposite according to claim 14, characterized in that the block copolymer is selected from the group consisting of poly (es ti reno-bloque- 4 -vini lpi ridina), poli (es ti reno-bl oque- soprene -block- 4 -vini lpyridine), poly (is tireno-block-butadiene-block-4-vini lpyridine), poly (isoprene-block-4-vinylpyridine), poly (butadiene-block-4-vinylpyridine), versions hydrogenated poly (butadiene-block-4-vinylpyridine), poly (styrene-block-isoprene-block-4-vinylpyridine), poly (styrene-block-butadiene-block-4-vinylpyridine), and poly (isoprene-block) 4-vinylpyridine).
19. The nanocomposite according to claim 14, characterized in that at least a portion of the silicate platelets comprises a layer of a layered silicate selected from the group consisting of montmorillonite, nontronite, bentonite, beidellite, hectorite, saponite, sauconite, fluorohectorite, stevensite, volkonskoite, magadiite, kenyaite, halloysite, hydrotalcite, and silicates in synthetic layers.
20. 20. The nanocomposite according to claim 14, characterized in that the weight ratio of the block copolymer to the silicate platelets is in the range of 0.01 to 10, inclusive.
21. 21. The nanocomposite according to claim 14, characterized in that the exfoliated silicate platelets comprise from 1 to 5 weight percent, inclusive, of the nanocomposite.
22. 22. The nanocomposite according to claim 14, characterized in that it comprises at least a portion of a film or bottle.