JP2002531640A - Polymer / clay nanocomposites with improved gas barrier properties, including clay materials having a mixture of two or more organic cations, and methods of making the same - Google Patents

Abstract

  (57) [Summary] The present invention provides an improved gas permeability comprising (i) a melt-processable matrix polymer and (ii) a layered clay material having incorporated therein a mixture of at least two organic cations. Polymer / clay nanocomposites. The invention also relates to a method of making a nanocomposite and an article made from the nanocomposite.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention generally relates to a mixture of organic cations (interca).
lated) polymer / clay nanocomposites comprising a clay material and having improved gas barrier properties. The invention further relates to articles made from the nanocomposites and methods of making the nanocomposites.

[0002] Polymer nanocomposites based on background layered clay invention, for improved properties exhibited by the nanocomposites are leaning much attention. Layered clay materials to maximize the improvement of some properties, including improved barrier properties (gas permeability), and to minimize the deleterious effects of some properties, including elongation at break It is desirable to maximize the cleavage of this into single platelet-like particles. Ideally, the clay material is exfoliated into platelet-shaped particles having a thickness of less than about 20 nm to achieve transparency comparable to clay-free polymers. To date, polymer / clay nanocomposites that meet this expectation are only produced by incorporating organically treated clay during the synthesis of monomers into polymers. However, the amount of clay that can be incorporated into the polymer and still exhibit exfoliation of layered clay is limited, and some mechanical properties, such as elongation at break, are often considerable with the addition of clay. Is well known.

Researchers have recognized the value of inventing a melt compounding method that provides a delaminated clay composite. That is, the melt compounding method offers greater flexibility in polymer selection and clay filling and the potential for cost reduction. However, with many polymer / clay blends, the melt compounding methods explored to date include:
Sufficient delamination of platelet-shaped particles has not been provided.

[0004] Polyesters such as poly (ethylene terephthalate) (PET) are widely used in bottles and containers used in carbonated beverages, fruit juices and certain food products. Useful polyesters have a high inherent viscosity (IV), which allows the polyester to be formed into a parison and then molded into a container. Due to their limited barrier properties against oxygen, carbon dioxide, etc., PET containers are not usually used for foods that require a long shelf life. For example, the permeation of oxygen into PET bottles containing beer, wine and certain food products causes these products to spoil. By utilizing a multilayer structure comprising one or more barrier layers and one or more structural layers of PET, the PE
Attempts have been made to improve the barrier properties of T-containers. However, the multilayer structure has not found widespread use because of the high cost, the large thickness of the required barrier layer, and the poor adhesion of the barrier layer to the structural layer, and has been found to be a container for beer. Not suitable for use.

There are many examples in the patent literature for polymer / clay nanocomposites made from monomers and treated clays. For example, US Pat. No. 4,739
No. 007 discloses a nylon-6 / clay nanocomposite from caprolactam and alkylammonium treated montmorillonite. U.S. Patent No. 4,
No. 889,885 describes the polymerization of various vinyl monomers such as methyl methacrylate and isoprene in the presence of sodium montmorillonite.

[0006] Some patents have less than 60% by weight intercalated.
) Blend clay materials with a wide variety of polymers including polyamides, polyesters, polyurethanes, polycarbonates, polyolefins, vinyl polymers, thermosets, and the like. Such a high loading of modified clay is impractical and useless for most polymers because the melt viscosity of the blend rises to a level where it cannot be molded.

WO 93/04117 discloses a melt blend of a wide range of polymers with up to 60% by weight of dispersed platelet-shaped particles. WO 93/04118 discloses a nanocomposite consisting of a melt-processable polymer and clay intercalated with up to 60% by weight of an organic onium salt. The use of clay into which a mixture of onium ions has been inserted is neither intended nor disclosed.

[0008] US Pat. No. 5,552,469 discloses certain clay and water-soluble polymers,
For example, it describes the production of intercalates derived from polyvinylpyrrolidone, polyvinyl alcohol and polyacrylic acid.
The use of clays into which organic cations have been inserted is explicitly excluded.

[0009] Japanese Patent Application Laid-Open No. 9-176461 discloses a polyester bottle in which the polyester contains unmodified montmorillonite. The incorporation of clay into polyesters by melt blending is disclosed; however, the use of clays with a mixture of organic cations is not disclosed unless otherwise contemplated.

Clays into which mixtures of organic cations, typically onium ions, have been inserted have been used as rheology modifiers for certain coating applications; however, their use in polymer / clay nanocomposites has been No attempt has been made or disclosed. The following references relate to chemically modified organoclay (clay / organic cation insertion) materials: U.S. Pat. Nos. 4,472,538; 4,546,126. The specification;
No. 6,929; No. 4,739,007; No. 4,777,20.
No. 6, No. 4,810,734; No. 4,889,885; No. 4,894,411; No. 5,091, 462; No. No. 5,102,948; No. 5,153,062; No. 5,16
5,440,460; 5,164,460; 5,248,72
No. 0; No. 5,382,650; No. 5,385,776; No. 5,414,042; No. 5,552,469; International Patent Application Publication Nos. 93/04117; 93/04118; 93
No./11190; No. 94/11430; No. 95/06090
No. 95/14733; D.C. J. Greenland, J .;
Colloid Sci. 18, 647 (1963); Sugahara
et al. , J. et al. Ceramic Society of Japan 10 0, 413 (1992); P. B. Massersmith et al. , J
. Polymer Sci. Polymer Chem. , 33 , 1047 (1
995); O. Sriakhi et al. , J. et al. Mater. Chem
. 6 , 103 (1996).

[0011] Thus, as described above, there is a need for polymer nanocomposites comprising clay materials with improved barrier properties and articles made therefrom.

[0012] SUMMARY organic cation of the invention, is preferably a mixture of onium ions is inserted clay, films, for commercial applications, including bottles and containers, sufficient delamination properties for improved properties and transparency And a polymer / clay nanocomposite having a molecular weight has been found to be useful for producing by a melt compounding method. The polymer nanocomposites of the present invention are particularly useful for forming packaging materials having improved gas barrier properties. Containers made from these polymer composites
It is ideally suited for protecting consumer products such as foods, soft drinks and medicines.

[0013] The present invention also provides a barrier layer having sufficient oxygen barrier and transparency for a wide range of applications, such as multilayer bottles and containers, including beer bottles.
It seeks to provide a cost-effective method.

According to the objects of the present invention, as specifically expressed and outlined herein, the present invention provides, in one embodiment, (i) a melt processable matrix polymer and (Ii) a polymer having improved gas permeability comprising a layered clay material into which a mixture of at least two organic cations has been incorporated.
Related to clay nanocomposites.

In another embodiment, the invention provides (i) producing an intercalated layered clay material by reacting an expandable layered clay material with a mixture of at least two organic cations; ii) A method for preparing a polymer / clay nanocomposite comprising incorporating the inserted layered clay material into the matrix polymer by melt treating the matrix polymer with the inserted clay.

In yet another embodiment, the present invention provides a polymer having improved gas permeability.
A method for producing a clay nanocomposite, comprising: (i) reacting an expansive layered clay material with a mixture of at least two organic cations to produce an inserted layered clay material; and (ii) removing the clay material. , Added to the polymer-forming component,
And (iii) a production method comprising a step of subjecting those components to polycondensation polymerization in the presence of a clay substance.

Further advantages of the invention will be set forth in part in the following detailed description, or may be obvious from the description, or may be learned by practice of the invention. Would. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is understood that both the foregoing general description and the following detailed description, by way of illustration, illustrate preferred embodiments of the invention and are not intended to limit the invention as claimed. I want to.

DETAILED DESCRIPTION OF THE INVENTION The present invention will be more readily understood by reference to the following detailed description of the invention and the examples provided herein. It is to be understood that this invention is not limited to the particular methods and conditions, which are described as specific methods and / or operating conditions for processing the polymer articles, but may, of course, vary accordingly. . It is also to be understood that the terminology used herein is for describing particular embodiments only and is not intended to be limiting.

As used in this specification and the appended claims, the singular forms (“a”, “an”)
It should also be noted that unless otherwise indicated by context, the context includes "a" and "the"), unless the context clearly dictates otherwise.

Ranges are expressed herein as from “about” or “approximately” one particular value and / or to “about” or “approximately” another particular value. When describing such a range, another embodiment includes from one specific value and / or to the other specific value. Similarly,
It is to be understood that when a value is expressed as an approximate number, by use of the antecedent "about," that particular value forms another embodiment.

Definitions As used herein, the terms used have the following meanings: “Layered clay”, “Layered clay material” or “clay material” means any organic or inorganic material A substance or a mixture thereof, such as a smectite clay mineral in the form of a plurality of adjacent bonded layers. Layered clay comprises platelet-shaped particles and is typically expandable.

By “platelet-shaped particles”, “platelets” or “particles” is meant a single or aggregated, unbonded layer of a layered clay material. These layers can be in the form of single platelet-like particles, ordered or unordered small aggregates of platelet-shaped particles (tactoids) and small aggregates of tactoids.

“Dispersed” or “dispersed” is a general term that describes the various levels or degrees of separation of platelet-shaped particles. Higher levels of dispersion include, but are not limited to, "inserted" and "peeled."

“Intercalated” or “intercalated material (interc
"alate)" refers to an intercalant disposed between adjacent platelet-shaped particles or tactoids of the layered material so as to increase the interlayer void between adjacent platelet-shaped particles or tactoids. Containing layered clay material.
In the context of the present invention, the intercalating agent is preferably two or more different types of organic cations.

“Exfoliate” or “exfoliat”
ed) "means that the platelets are dispersed almost solely throughout the support material, such as a matrix polymer. Typically, "exfoliated" is used to indicate the highest degree of dispersion of platelet-shaped particles.

“Exfoliation” refers to a method of forming exfoliated material from an inserted or otherwise less dispersed state of separation.

“Nanocomposite” or “nanocomposite composition” means a polymer or copolymer having dispersed therein a number of single platelets obtained from a layered clay material.

“Matrix polymer” means a thermoplastic or melt-processable polymer in which platelet-shaped particles are dispersed to form a nanocomposite. However, in the present invention, the platelet-shaped particles are mostly delaminated in the matrix polymer to form a nanocomposite.

[0029] Description of embodiments the present invention generally speaking relates to melt compounding process for preparing polymer / clay nanocomposite compositions, also the clay particles two or more organic cations, preferably an organic cation It relates to certain polymer / clay nanocomposite compositions that are treated with a mixture of salts. The polymer / clay nanocomposites of the present invention exhibit unexpectedly lower gas permeability, especially oxygen permeability, than other laminated polymer / clay nanocomposites made by melt blending methods. The method of the present invention can also be used to produce a wide variety of polymer / clay nanocomposite compositions.

In the prior art, the peak intensity measured by X-ray analysis of the polymer / platelet composite and the basal spacing value, ie the degree of separation of the platelet-like particles based on the lack of the main basal spacing Is defined. X-ray analysis by itself often allows quantification of the level of dispersion achieved, although often times it is not clear whether the platelet-like particles are dispersed alone in the polymer. As such, while only X-ray analysis provides information about well-ordered aggregates, such aggregates are only a small fraction of the platelet-like particles present. Moreover, in polymer nanocomposites, X-ray analysis alone does not accurately predict the dispersion of platelet-shaped particles in the polymer and the resulting improvement in gas barrier properties. The TEM image of the polymer / platelet composite is
The platelet-like particles incorporated in at least one polymer are composed of a single platelet (exfoliated), an unaligned agglomerate of platelets, a well-ordered or stacked aggregate of platelets ( Tactoids), expanded agglomerates of stacked platelets (inserted tactoids), and aggregates of (but not limited to) tactoids.

Without being bound by any theory, the degree of improvement in gas barrier (permeability) depends on the specific ratio between the resulting particle platelets and the aggregates, which are dispersed or evenly distributed. It is believed to depend on the degree and degree of alignment perpendicular to the permeate flow.

According to the present invention, in order to obtain an improvement in gas permeability, the representative majority of the platelet-shaped particles of the composite material are delaminated, preferably highly delaminated, in the matrix polymer. As a result, the majority, preferably at least about 75%, and perhaps at least about 90% or more of the platelet-like particles are estimated from a single platelet and TEM image, It is preferred that the thickness be dispersed in the form of agglomerates having a minimum dimension of less than about 20 nm, preferably less than about 10 nm. Most preferred are polymer / platelet nanocomposites that contain more single platelets and less ordered or unordered aggregates. Significant levels of incomplete dispersion (ie, the presence of large agglomerates and tactoids larger than about 20 nm) not only decrease the potential for improved barrier properties on platelet-shaped particles, Adversely affect other properties inherent in the polymer resin, such as strength, toughness and thermal stability.

Further, without being bound by a particular theory, the cleavage of platelet-like particles based on melt blending, ie, mixing with a polymer, requires an advantageous mixing free energy, which is determined by the mixing enthalpy and It is believed to be provided by the mixed entropy. Melting the clay with the polymer makes the mixing entropy negative due to the reduced number of conformations that the polymer chains have when present in the region between the two layers of the clay. For example, with melt-processable polyesters, it is believed that insufficient mixing is obtained because the mixing entropy is insufficient to overcome the negative mixing entropy. On the other hand, good dispersion is usually obtained by using polyamides due to their hydrogen bonding properties. However, the degree of dispersion is often reduced by the negative mixing entropy. Heretofore, it has been attempted to achieve a favorable enthalpy by pretreating the platelet-shaped particles (e.g., by cation exchange with alkylammonium ions) and mixing the platelet-shaped particles with a melt-processable polymer. Efforts have not been successful.

According to the present invention, using clays into which the organic cation mixture has been inserted gives good dispersion in the resulting nanocomposite during melt processing with the polymer,
It has been found that most result in single platelet-like particles, improving the gas permeability of the nanocomposite. A mixture of organic cations (ie, a mixed chain (tether
By using)), for example, a balance between polar and non-polar groups can be achieved without introducing difficulties in the synthesis. That is, mixing known, readily available cations (chains) is also easier than designing and synthesizing new ones.

Also, without being bound by any particular theory, typically, even though the polymer chains may have different properties (eg, hydrophobic, polar, hydrogen bonding, etc.), a mixture of organic cations (eg, It is believed that using mixed chains) can help the polymer to lower the enthalpy of mixing by giving the materials different polarities to interact with different parts of the polymer chain . To achieve this advantage, the chains should have sufficient mobility and entropy to adopt a convenient conformation, which would extend the clay corridor and exfoliate into single platelet-like particles. Help. By further theory, a mixture of cations (two or more straps) may prefer to associate with a particular polymer over each other. The above relationship is mainly related to enthalpy. However, other theories are also plausible.

To maximize the rate of exfoliation of the clay in the molten polymer treated with onium ions, the matrix polymer (or oligomer or polymer reactant) and the onium ions ion-exchanged on the surface of the clay platelets It is essential to have good compatibility between In other words, the choice of onium ions is based on the compatibility of the monomers, oligomers and polymers of the matrix with the onium ions. Without being bound by any particular theory, it is believed that the formation of clay exchanged with mixed onium ions enhances the compatibility of the corridor between adjacent platelets with the matrix polymer. Also, the mixed onium ion is a nanomer
could increase the range of compatibility of the anomer) with the matrix polymer. In order to prevent the disintegration of the clay particles exfoliated during the polymerization of ethylene glycol and DMT in the PET synthesis process, the clay into which the mixed onium ions have been inserted can be used in the PET polymerization process. The polarity of the matrix polymer, for example PET, decreases with increasing degree of polymerization. The original exfoliated clay in ethylene glycol may not be compatible with PET matrix polymers that use a single, highly polar onium ion. However, by incorporating low polar surfactants (onium ions) as well as high polar onium ions in the clay corridor prior to delamination in ethylene glycol, the collapse of the corridor during PET polymerization (platelet realignment) ) Is avoided.

By using the mixed onium ion exchange clay, the amount of certain high molecular weight onium ions can be reduced and the process of reducing the particle size can be facilitated (onium bound to the platelet surface) Ion weight can be reduced). For example, ETHOQUAD which is an ethoxylated ammonium ion
The 18/25 exchanged nanomer has a high molecular weight. Complete ETHOQUAD
For the 18/25 exchanged nanomer, the silicate content in the nanomer would be less than 50% by weight. Also, complete onium ion exchange nanomers are less likely to be dehydrated. ETHOQUAD 18/25: ODA (octadecyl ammonium)
Of ETH in the finally treated clay by using a molar ratio of 50:50
The amount of OQUAD 18/25 is reduced to 50% by weight, the onium ion-intercalated clay can be easily dehydrated, and the onium ion-intercalated clay is in a dry powder form rather than a viscous material. ETHOQUAD 18/25 / O
The DA-mixed clay is better dispersed and exfoliated in the matrix polymer after extrusion than any of the individually treated ETHOQUAD 18/25 insert clay and ODA insert clay, respectively. The better the delamination, the better the O ₂ barrier will be.

More particularly, the present invention relates to a polymer composite comprising a melt-processable polymer and up to about 25% by weight of an expandable layered clay material into which a mixture of at least two organic cations, preferably onium ions, has been inserted. About. The inserted clay material has platelet-like particles dispersed in the polymer, which are dispersed in the polymer. The polymer nanocomposite is preferably 60% by weight of phenol and 1,1,1.
In a mixture of 40% by weight of 2,2-tetrachloroethane, a concentration of 0.5 g / 100 ml (
Solution), measured at 25 ° C., with an I.D. of at least 0.5 dL / g. V. Is a nanocomposite of a polyester polymer or copolymer having

In one embodiment, the method for producing a polymer nanocomposite of the present invention comprises:
C.) Producing an intercalated layered clay material and (2) incorporating the intercalated clay material into the polymer by melt processing the polymer with the intercalated layered clay material. Melt processing includes melt and extrusion compounding. There are two advantages to using extrusion compounding to mix the intercalated clay and polymer. First of all, extruders can handle the high viscosities exhibited by nanocomposites. In addition, the melt mixing approach to producing nanocomposites can avoid the use of solvents. Low molecular weight liquids can often be costly to remove the nanocomposite from the resin.

The first step of the method of the present invention is to produce an intercalated layered clay material by reacting the expandable layered clay with a mixture of organic cations, preferably ammonium compounds. The method for producing the organoclay (intercalated clay) can be performed in a batch, semi-batch or continuous manner.

In another embodiment, the method of the present invention comprises the steps of (i) producing an intercalated layered clay material, (ii) adding the modified clay to a component mixture that forms the desired polymer, and iii) conducting the polycondensation polymerization in the presence of the modified clay. The molecular weight of the polymeric material can be determined by a number of known means, such as chain extension, reactive extrusion (rea)
active extrusion, extrusion red down (extrusion)
let-down, solid state polymerization or annealing (annealing under inert gas flow, vacuum annealing, red-down in melt reactor)
Etc.) or by a combination of any of these means.

The resulting nanocomposite can then be processed into the desired barrier film or container using processing procedures well known in the art.

The nanocomposites of the present invention may contain less than about 25% by weight of clay, preferably from about 0.5 to about 20% by weight, more preferably from about 0.5 to about 15% by weight, and most preferably. About 0.5 to about 10% by weight. The amount of platelet-shaped particles is ASTM D563
When treated according to 0-94, it is determined by measuring the silicic acid residues in the ash of the polymer / platelet composition. Useful clay materials include natural, synthetic or modified phyllosilicates. Illustrative examples of such natural clays include:
Smectite clays such as montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, beidellite,
There are volconscoite, magadite, keniyaite and the like. Illustrative of such synthetic clays are smectite clays, such as synthetic mica, synthetic saponite, synthetic hectorite, and the like. Illustrative examples of such modified clays include montmorillonite fluoride, mica fluoride, and the like. A preferred clay is Nano
cor, Inc. , Southern Clay Products, Kuni
Available from various companies, including mine Industries, Ltd, and Rheox.

Preferred clay materials are 0.5-2.0 meq / g of mineral (meq / g)
) Is a 2: 1 type phyllosilicate having a cation exchange ability of (1). Most preferred clay materials are smectite clay minerals, especially bentonite or montmorillonite, and more particularly sodium wyoming montmorillonite or sodium wyoming bentonite.

Typically, the layered clay material useful in the present invention is an agglomerate of areas called tactoids, where single platelet-like particles stick together like a trump card. The single platelet-shaped particles of clay are preferably less than about 2 nm thick,
And the diameter ranges from about 10 to about 3000 nm. Preferably, the clay is dispersed in the polymer and the majority of the clay material is present as single platelet-shaped particles, small tactoids and small agglomerates of tactoids. Preferably, the polymer of the invention /
Most of the tactoids and aggregates in the clay nanocomposite will be less than about 20 nm thick in the smallest dimension. Polymer / clay nanocomposite compositions containing higher concentrations of single platelet-shaped particles and less tactoids are preferred.

Further, the layered clay material will typically have from about 0.3 to about 3.0 meq / g, preferably 0.90-1.5 meq / g, more preferably 0.95-1.25 meq.
/ G cation exchange capacity. Clay is present in the corridor between the layers of the clay, containing alkali metals (group IA), alkaline earth metals (
(Group IIA) and mixtures thereof, and can have a wide variety of exchangeable cations, including, but not limited to, cations. The most preferred cation is sodium; however, any cation or combination of cations can be used as long as most of the cations are exchanged for organic cations (onium ions) during the process of the invention. .

Other non-clay substances having the above-mentioned ion exchange capacity and size, such as chalcogens, can also be used as a source of platelet-shaped particles in the present invention. Chalcogens are salts of heavy metals and Group VIA (O, S, Se and Te).
These materials are well known in the art and need not be described at length here.

The organic cation mixture used for insertion into the clay material of the nanocomposite of the present invention is derived from an organic cation salt, preferably an onium salt compound. Organic cation salts useful in the nanocomposites and methods of the present invention can generally be represented as follows:

[0049]

Embedded image

Wherein M is either nitrogen or phosphorus; X ⁻ is a halide, hydroxide or acetate anion, preferably chloride and bromide; and R ₁ , R ₂ , R ₃
And R ₄ are independently organic and oligomeric ligands, or may be hydrogen.

Examples of useful organic ligands include, but are not limited to, a carbon atom 1
~ 22, more preferably a linear or branched alkyl group having 1 to 12 carbon atoms,
It contains benzyl and a condensed ring moiety, wherein the alkyl moiety of the structure is linear or branched having 1 to 100 carbon atoms, and more preferably has at least one ligand having 12 or more carbon atoms. An aryl group such as an aralkyl group which is a substituted benzyl moiety containing a condensed ring residue, phenyl and a substituted phenyl containing a condensed aromatic substituent, a β, γ-unsaturated group having 6 or less carbon atoms, and 2 carbon atoms ~
6, and more preferably alkylene oxide groups having 3 to 5 carbon atoms.
Examples of useful oligomeric ligands include, but are not limited to, poly (
Alkylene oxide), polystyrene, polyacrylate, polycaprolactone, and the like.

Organic cations that are particularly useful as the organic cation mixture of the present invention include, but are not limited to, alkyl ammonium ions such as dodecyl ammonium, octadecyl ammonium, bis (2-hydroxyethyl) octadecylmethyl ammonium, Includes octadecylbenzyldimethylammonium, tetramethylammonium and the like, and alkyl phosphonium ions such as tetrabutylphosphonium, trioctyloctadecylphosphonium, tetraoctylphosphonium, octadecyltriphenylphosphonium and the like.

Specific examples of suitable ammonium polyalkoxylated compounds include JEFFAMI
Hydrochloride salt of a polyalkoxylated amine available under the trade name NE (from Huntsman Chemical), ie, JEFFAMINE-506, an oligooxyethylene amine having a number average molecular weight of about 1100 g / mol, and a number average molecular weight of about 640 g / mol JE, which is an oligooxypropylene amine having moles
FFAMINE-505 and the trade name ETHOQUAD or ETHOMEEE
N available from Akzo Chemie America, namely ETHOQUAD 18/25, an octadecylmethylbis (polyoxyethylene [15]) ammonium chloride, and ETHOMEEN, an octadecylbis (polyoxyethylene [15]) amine. 18/25, where the number in parentheses indicates the total number of ethylene oxide units. The most preferred organic cation for use in polyesters such as polyethylene terephthalate is a polyalkoxylated ammonium compound.

Many methods are known for modifying layered clays with organic cations,
Any can be used in the method of the invention.

In one embodiment of the invention, the layered clay is dispersed in hot water, most preferably at 50-80 ° C., and the organic cation salts are added separately with stirring or a mixture of organic cation salts (as is). Or dissolved in an alcohol) and then blending the layered clay with a mixture of organic cation salts by a method in which the organic cations are blended for a time sufficient to replace most of the metal cations in the corridor between layers of the clay material. Is to denature. The organically modified layered clay material is then isolated by methods known in the art, including, but not limited to, filtration, centrifugation, spray drying, and combinations thereof.

It is desirable to use a sufficient amount of organic cation salt to allow for the exchange of most metal cations in the corridor of the layered particles for organic cations; With at least about 0.5 equivalents and about 3
Use up to equivalent organic cation salt. The organic cation salt is preferably used in an amount of about 0.5 to 2 equivalents, more preferably about 1.0 to 1.5 equivalents. It is often, but not necessary, desirable to remove most of the metal cation salt and most of the excess organic cation salt by washing or other techniques known in the art.

The particle size of the resulting organoclay can be determined by methods known in the art, including, but not limited to, grinding, milling, hammer milling, jet milling, and combinations thereof. Is refined. It is preferable that the average particle diameter is smaller than 100 μm, more preferably smaller than 50 μm, most preferably smaller than 20 μm.

Although not preferred, the clay may be further treated to promote exfoliation in the composite and / or to improve the strength of the polymer / clay interface. Any process that achieves the above objectives can be used.

Examples of useful treatments include insertion with water-soluble or water-insoluble polymers, organic ligands or monomers, silane compounds, metal or organometallic compounds and / or combinations thereof.

The treatment of the clay can be accomplished prior to addition of the polymer to the clay material, during dispersion of the clay with the polymer, or during a subsequent melt compounding or melt processing step.

Examples of useful pretreatments with polymers and oligomers include US Pat. No. 5,552
Nos., 469 and 5,578,672, which are incorporated herein by reference. Examples of polymers useful for treating mixed organic cation intercalated clays include polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polytetrahydrofuran, polystyrene, polycaprolactone, certain water-dispersible polyesters, nylon-6, and the like. .

Examples of useful pretreatments with organic reagents or monomers include those disclosed in EP-A-780,340, which is incorporated herein by reference. Examples of organic reagents and monomers useful for inserting the expansive layered clay include dodecylpyrrolidone, caprolactone, caprolactam, ethylene carbonate, ethylene glycol, bishydroxyethyl terephthalate, dimethyl terephthalate, and the like, or mixtures thereof.

Examples of useful pre-treatments with silane compounds include WO 93/11190.
Included are the processes disclosed in US Pat. Examples of useful silane compounds include (3-glycidoxypropyl) trimethoxysilane, 2
-Methoxy (polyethyleneoxy) propylheptamethyltrisiloxane, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and the like.

If desired, during or prior to the formation of the composite by melt mixing, the dispersion aid may be used to assist in promoting exfoliation of the treated or untreated expandable layered particles in the polymer. An agent may be present. Many such dispersing aids are known and cover a wide variety of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents, and the like, or combinations thereof.

It is recognized that, based on the total composition, the dispersing aid and / or pretreatment compound can make up a significant amount of the total composition, in some cases up to about 30% by weight. It should be. It is preferred to use as little dispersing aid / pretreatment compound as possible, but the amount of dispersing aid and / or pretreatment compound can be as much as eight times the amount of platelet-shaped particles.

For the present invention, any melt-processable polymer or oligomer can be used. Specific examples of the melt-processable polymer include polyester, polyetherester, polyamide, polyesteramide, polyurethane, polyimide, polyetherimide, polyurea, polyamideimide, polyphenylene oxide, phenoxy resin, epoxy resin, polyolefin, and polyolefin. There are acrylates, polystyrene, polyethylene-co-vinyl alcohol (EVOH) and the like or combinations and blends thereof. Preferred polymers are linear or nearly linear, but polymers of other structures, including branched, star, cross-linked, and dendritic, can be used if desired.

Preferred polymers include materials suitable for use with polyesters in forming multilayer structures, including polyesters, polyamides, polyethylene-co-vinyl alcohols (such as EVOH) and similar or related polymers, and the like. And / or their copolymers. Preferred polyesters are poly (ethylene terephthalate) (PET) or copolymers. A preferred polyamide is poly (m-xylylene adipamide).

Suitable polyesters comprise at least one disalt base and at least one glycol. The primary disalt base is terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Various isomers of naphthalenedicarboxylic acid and mixtures thereof can be used, but 1,4-, 1,5
The-, 2,6- and 2,7-isomers are preferred. The 1,4-cyclohexanedicarboxylic acid can be in the form of a cis, trans, or cis / trans mixture.
In addition to these acid forms, lower alkyl esters or acid chlorides can also be used.

The matrix polymers of the present invention can be made from one or more of the following dicarboxylic acids and one or more of the following glycols:

The dicarboxylic acid component of the polyester can be optionally modified with up to about 50 mol% of one or more different dicarboxylic acids. Such auxiliary dicarboxylic acids include dicarboxylic acids having 6 to about 40 carbon atoms, more preferably aromatic dicarboxylic acids, preferably having 8 to 14 carbon atoms,
Dicarboxylic acids selected from aliphatic dicarboxylic acids having preferably 4 to 12 carbon atoms and alicyclic dicarboxylic acids preferably having 8 to 12 carbon atoms are included. Examples of suitable dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, phenylene (oxyacetic acid) ), Succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like. Polyesters may also be made from two or more of the above dicarboxylic acids.

Typical glycols used in polyesters include those containing from 2 to about 10 carbon atoms. Preferred glycols include ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol and the like. The glycol component is optionally present at about 50 mol%, preferably about 25 mol%, more preferably about 1 mol%.
Up to 5 mol% of different diols can be modified with one or more. Such auxiliary diols include cycloaliphatic diols, preferably having 6 to 20 carbon atoms, or preferably aliphatic diols having 3 to 20 carbon atoms. Examples of such diols are: diethylene glycol, triethylene glycol,
1,4-cyclohexanedimethanol, propane-1,3-diol, butane-
1,4-diol, pentane-1,5-diol, hexane-1,6-thiol, 3-methylpentanediol- (2,4), 2-methylpentanediol- (
1,4), 2,2,4-trimethylpentanediol- (1,3), 2-ethylhexanediol- (1,3), 2,2-diethylpropanediol- (1,3)
), Hexanediol- (1,3), 1,4-di (2-hydroxyethyl) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3 -Tetramethylcyclobutane, 2,2-bis (3-hydroxyethoxyphenyl) propane, 2,2-bis (4-hydroxypropylphenyl) propane and the like. Polyesters may also be made from two or more of the above diols.

Small amounts of multifunctional polyols such as trimethylolpropane, pentaerythritol, glycerol and the like can also be used if desired. When 1,4-cyclohexanedimethanol is used, it can be cis, trans, or a cis / trans mixture. When phenylene dioxyacetic acid is used, it may be used as a 1,2; 1,3; 1,4; isomer or a mixture thereof.

The polymer may also contain small amounts of trifunctional or tetrafunctional comonomers to provide controlled branching to the polymer. Such comonomers include trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, trimellitic acid, trimellitic acid, pyromellitic acid, and other polyester-forming materials known in the art. Polyacids or polyols are included.
Suitable polyamides include partially aromatic polyamides, aliphatic polyamides, wholly aromatic polyamides and / or mixtures thereof. "Partially aromatic polyamide" means that the amide bond of the partially aromatic polyamide contains at least one aromatic ring and a non-aromatic species. Suitable polyamides have an article forming molecular weight and an I.P. V. have.

Preferred wholly aromatic polyamides include m-xylylenediamine or m-xylylenediamine in the molecular chain.
At least 70 mol% of structural units derived from a xylylenediamine mixture comprising xylylenediamine, and up to 30 mol% of p-xylylenediamine, and aliphatic dicarboxylic acids having 6 to 10 carbon atoms, Is further
No. 0-1156, Japanese Patent Publication No. 50-5751, Japanese Patent Publication No. 50-5735, Japanese Patent Publication No. 50-10196, and Japanese Patent Application Laid-Open No. 50-29697.

Isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, m- or p-xylenediamine, 1,3- or 1,4-cyclohexane (bis) methylamine,
Aliphatic diacids having 6 to 12 carbon atoms, aliphatic amino acids or lactams having 6 to 12 carbon atoms, aliphatic diamines having 4 to 12 carbon atoms and known polyamide-forming diacids and polyamides formed from diamines Can be used. Low molecular weight polyamides can also include small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride or other polyamide-forming polyacids and polyamines known in the art. .

Preferred partially aromatic polyamides include, but are not limited to, poly (m-xylylene adipamide), poly (m-xylylene adipamide-co-isophthalamide), poly ( Hexamethylene isophthalamide), poly (hexamethylene isophthalamide-co-terephthalamide), poly (hexamethylene adipamide-co-isophthalamide), poly (hexamethylene adipamide-co-terephthalamide), poly (hexa Methyleneisophthalamide-co-terephthalamide) and the like or mixtures thereof. More preferred partially aromatic polyamides include:
Without limitation, poly (m-xylylene adipamide), poly (hexamethylene isophthalamide-co-terphthalamide), poly (m-xylylene adipamide-co-isophthalamide) And / or mixtures thereof. The most preferred partially aromatic polyamide is poly (m-xylylene adipamide).

[0077] Preferred aliphatic polyamides include, but are not limited to, poly (
Hexamethylene adipamide) and poly (caprolactam). The most preferred aliphatic polyamide is poly (hexamethylene adipamide). Where good thermal properties are very important, partially aromatic polyamides are preferred over aliphatic polyamides.

Preferred aliphatic polyamides include, but are not limited to, polycapramide (nylon 6), polyaminoheptanoic acid (nylon 7), polyaminonanonic acid (nylon 9), polyundecaneamide (nylon 11), Polylaurilactam (nylon 12), poly (ethylene adipamide) (nylon 2,6), poly (tetramethylene adipamide) (nylon 4,6), poly (hexamethylene adipamide) (nylon 6,6 ), Poly (hexamethylene sebacamide) (nylon 6,10), poly (hexamethylene dodecamide) (nylon 6,12), poly (
Octamethylene adipamide) (nylon 8,6), poly (decamethylene adipamide) (nylon 10,6), poly (dodecamethylene adipamide) (nylon 12
, 6) and poly (dodecamethylene sebacamide) (nylon 12, 8).

The most preferred polyamides include poly (m-xylene adipamide), polycapramide (nylon 6) and poly (hexamethylene adipamide) (nylon 6,6)
Is included. Poly (m-xylylene adipamide) is a preferred polyamide because of its availability, high barrier properties and processability.

[0080] Polyamides are usually manufactured by methods known in the art. Although not necessarily preferred, the polymers of the present invention may also include additives commonly used in polymers. Illustrative of such additives, as known in the art, include colorants, pigments, carbon black, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, There are reheating aids, crystallization agents, acetaldehyde reducing compounds, recycle strippers, oxygen scavengers, plasticizers, nucleating agents, mold release agents, compatibilizers, and the like, or combinations thereof.

[0081] All of these additives and many others, and their use, are well known in the art and do not require detailed discussion. Thus, it will be understood that any of these compounds may be used in any combination, as long as they do not interfere with the attainment of the objects of the present invention, although this will also involve limited numerical values. .

The present invention also includes, but is not limited to, films, sheets, pipes, tubes, profiles, moldings, preforms, stretch blown films and containers, injection blow molded containers, extrusion blow molded. It relates to articles made from the nanocomposites of the present invention, including films and containers, thermoformed articles and the like. The container is preferably a bottle.

The bottles and containers of the present invention provide improved shelf life for contents, including beverages and foodstuffs, which are sensitive to gas penetration. The articles, more preferably containers, of the present invention have a gas permeation rate or penetration rate (depending on clay concentration) that is at least 10% lower than that of similar containers made from clay-free polymers.
(Oxygen, carbon dioxide, water vapor) and the longer shelf life provided by the container is provided. Desirable values for the modulus and tensile strength of the sidewall can also be maintained.

[0084] The article may be multilayer. Preferably, the multilayer article has a nanocomposite disposed between other layers, but the nanocomposite can also be one layer of a two-layer article. In embodiments where the nanocomposite and its components are approved for food contact, the nanocomposite may form the food contact layer of the desired article. In other embodiments, the nanocomposite is preferably a layer other than the food contact layer.

The multilayer article can also include one or more layers of the nanocomposite composition of the present invention with one or more structural polymer layers. A wide variety of structural polymers can be used. Specific examples of structural polymers include polyester, polyetherester, polyamide, polyesteramide, polyurethane, polyimide, polyetherimide, polyurea, polyamideimide, polyphenylene oxide, phenoxy resin, epoxy resin, polyolefin, and polyacrylate. , Polystyrene, polyethylene-co-vinyl alcohol (EVOH), and the like, or combinations and blends thereof. Preferred structural polymers are polyesters such as polyethylene terephthalate and its copolymers.

In another embodiment of the present invention, the polymer / clay nanocomposite and molded article or extruded sheet may be formed simultaneously by co-injection molding or co-extrusion.

Another embodiment of the present invention is the use of a layer of silicate uniformly dispersed in a matrix of high barrier thermoplastic resin, combined with a multi-layer approach to packaging materials. By using layered clay to reduce the gas permeability of the high barrier layer, the amount of this material needed to generate an inherent barrier level in the end use is greatly reduced. Since high barrier materials are often the most expensive components in multilayer packaging, it would be indeed beneficial to reduce the amount of this material used. By using a layer of nanocomposite sandwiched between two outer polymer layers, the surface roughness is often much less than for a single layer of nanocomposite. Thus, the haze level is reduced by the multilayer approach.

[0088] The following examples, the resin compositions claimed herein are submitted a more complete disclosure and description of how the rating is fabricated in how to provide those of ordinary skill in the art. They are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (eg, amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in ° C. or is at room temperature, and pressure is at or near atmospheric.

Examples 1 to 3 and Comparative Example 1 Southern Clay Pr having a cation exchange capacity of about 0.95 meq / g
purified Wyoming type sodium montmorillonite 30 obtained from Oducts
g is added to 1.0 liter of hot distilled water (about 85 ° C.) and then stirred at about 85 ° C.
Henschel high-speed multi-blade mixer with heater attached to hold
Stirred for minutes. An aqueous solution of 28.5 meq of hydrochloric acid and JEFFA listed in Table I
28.5 meq of amine from a mixture of MINE-506 (EOA) and JEFFAMINE-505 (POA) (shown as Examples 1-3) was added to the Henschel mixer and blended for about 2 minutes.

Comparative Example 1 was also listed in Table I, but as an intercalating agent JEFFAMINE-5
The same procedure was used above or below, except that only 06 (EOA) was used.

[0091] Almost immediately after the ammonium salt was added to the clay slurry, a white precipitate formed. The white precipitate was separated by use of a Beckman J-6B centrifuge and the volume ratio of distilled water to isopropanol 50:50 while stirring with a Henschel mixer.
And filtered, then dried at 60 ° C. for at least 24 hours. The particle size of the dried clay is about 10 to 15 μm using a hammer mill and then a jet mill.
Reduced. As listed in Table I, the clay product WAXS basal spacing and silicate content (ash) were measured.

[0092]

[Table 1]

4.3 g of the ammonium-inserted clay was weighed with PET 9921 (Eastman Che).
395.7 g dry-mixed.
T9921 contains about 3.5 mol% of 1,4-cyclohexanedimethanol,
. V. Polyethylene terephthalate having about 0.72 dL / g. The dry mixture was dried in a vacuum oven at 120 ° C. overnight and then extruded at a temperature of about 275 ° C. on a Leistritz Micro 18 mm twin screw extruder using a universal screw at 200 rpm. The extrudate was cooled on an air belt and then pelletized as it exited the die.

Using a Pasadena hydraulic press, a pressure of about 3000 lbs, a temperature of 280 ° C.,
A film was produced by compression molding with a molding time of about 1.15 minutes. Teflon coated aluminum foil was used to prevent the material from sticking to the hotplate. A 10 mil thick shim was used to achieve the target thickness. The formed film was immediately cooled with ice water to obtain an amorphous sample, thereby eliminating the effect of crystallization on the measured gas permeability. The permeability results of the films are shown in Table II along with a control (PET 9921 alone, obtained from Eastman Chemical Company) and a comparative example using no mixture of organic cations.

[0095]

[Table 2]

Table 2 shows that clay treated with a mixture of ammonium ions was converted to unmodified PET (
(PET 9921 control). Unmodified PET does not contain any platelet-like particles. In addition, unmodified PET
Do not contain platelet-shaped particles treated with a mixture of onium ions according to the invention.

[0097] Additionally, and even more particularly surprising, the results in Table II show that clay (used in polymer nanocomposites) treated with a mixture of different types of ammonium ions (EOA / POA) One type of ammonium ion (EOA
) Shows an improvement in oxygen permeability as compared to clay treated alone.

For example, Examples 1 and 3 show that the clay treated with a mixture of ammonium ions (EOA / POA) in a ratio of 50/50 has an oxygen transmission rate of 6.6 cc · mil / (100
in ² days · atmospheric pressure, while one kind of ammonium ion (EOA / PO
A treated with only 100/0 (A) has an oxygen transmission rate of 8.0 cc · mil / (10
0 in ² days / atm). The result is particularly surprising that while both clays have been treated with ammonium ions; clays treated with a mixture of ammonium ions provide unexpected improvement.

Examples 1 and 2 (75% EOA / 25% POA) and Examples 1 and 4 (25% EOA
OA / 75% POA) also shows that films made from nanocomposites treated with a mixture of organic cations outperform films made from nanocomposites treated with only one organic cation. This shows that the blocking characteristics are improved.

The following examples further illustrate the generation of mixed onium ion treated clays.

ETHOQUAD 18 / 25-ODA clay system: Nanocor, Inc. with a cation exchange capacity of 1.4 meq / g. 100 g of purified sodium montmorillonite (Na-CWC) obtained from Co., Ltd. was added to 4.0 liters of hot distilled water (about 85 ° C.) to form a clay slurry, and the slurry was dispersed with a paddle-type stirrer to disperse the clay solid. Was stirred until it did. ETHOQUAD
A mixed onium ion solution was prepared by mixing the 18/25 aqueous solution and ODA in a 1: 1 molar ratio in an HCl solution. This mixed onium ion solution was added to the clay slurry. Immediately upon stirring, a clay precipitate formed. The entire mixture was mixed and kept at 85 ° C. for about 2 hours. Water was removed by filtration. The resulting precipitate was washed twice before drying in an oven at 120 ° C. The dried clay is pulverized with a mechanical pulverizer, and further pulverized with a jet mill or an air classifier mill to about 10 to 15 μm.
Particle diameter. Finally, the ground sample was analyzed by powder X-ray diffraction. Tables II and III below summarize the composition and basal spacing of clays treated with mixed ETHOQUAD 18 / 25-ODA with different molar ratios of ETHOQUAD 18/25 and ODA.

[0102]

[Table 3]

Q182-Q142 system: Q182 and Q142 are quaternary ammonium surfactants available from Tomah Products, Inc. Q182 has a _C18 straight chain, while Q182
142 has an ether bond with a C ₃ which is attached to a linear and a nitrogen atom of C _11. When the matrix polymer is polymerized or further polymerized while in contact with an intercalated and / or delaminated intercalant containing a plurality of ion-exchanged onium ions of different polarities, different chain lengths and polar surfactants The combination of agents
This produces a large number of onium ion-intercalated clays that have good compatibility with the matrix polymer. Combinations of onium ions of different chain lengths and polarities have areas of good compatibility with many matrix polymers, but rearrangement and destruction of delaminated clay platelets (resulting in better dispersibility) Prevent the insertion of clay resulting.
Basal spacing data for single onium ion exchange, clay with only Q142 or Q182 onium ion and mixed onium ion exchange, Q142 / Q182 clay are shown in Table III below as Examples 10, 11 and 12.

[0104]

[Table 4]

Throughout this specification, various publications are referenced. The disclosures of these publications are incorporated herein by reference in their entirety to more fully describe the state of the art to which this invention pertains.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), AU, BR, CA, CN, JP, MX (72) Inventors Matayabas, James Christopher Jr. United States, Tennessee 37664-4048, Kingsport, Wesley Road 3429 (72) Inventor Barbie, Robert Boyd United States of America, Tennessee 37663-2131, Kingsport, Rambling Road 500 (72) Inventor Run, Thier United States of America, Illinois 60047, Lake Zurik, Waterford Coat 760 F-term (reference) 4G073 BB48 BB63 BB69 BB71 BD16 CM07 CM14 CM15 CM16 CM19 CM20 CM21 CM22 CM25 CN03 CN04 FB29 UB40 4J002 AA001 BB001 BC021 BE031 BG001 CC161 CD001 CF001 CF11 CH011 CL081 CL031 CL081 CM041 DJ036 FB086 FD206

Claims (71)

[Claims] 1. A clay / organic cation intercalating material comprising: (i) a melt-processable matrix polymer, and incorporated therein, (ii) a layered clay material into which a mixture of at least two organic cations has been inserted. A polymer / clay nanocomposite with improved gas barrier properties, comprising: 2. The melt-processable matrix polymer is polyester, polyetherester, polyamide, polyesteramide, polyurethane, polyimide,
Polyetherimide, polyurea, polyamideimide, polyphenylene oxide,
The nanocomposite of claim 1, comprising a phenoxy resin, an epoxy resin, a polyolefin, a polyacrylate, a polystyrene, a polyethylene-co-vinyl alcohol or a copolymer thereof or a mixture thereof. 3. The nanocomposite of claim 1, wherein the melt-processable matrix polymer comprises a polyester, a polyamide, a polyethylene-co-vinyl alcohol or a copolymer thereof or a mixture thereof. 4. The nanocomposite of claim 1, wherein the melt-processable matrix polymer comprises poly (m-xylylene adipamide), EVOH or a copolymer thereof or a mixture thereof. 5. The nanocomposite of claim 1, wherein the melt-processable matrix polymer comprises poly (ethylene terephthalate) or a copolymer thereof. 6. The nanocomposite of claim 1, comprising the layered clay material in an amount greater than 0 and up to about 25% by weight. 7. The nanocomposite of claim 1, comprising from about 0.5 to about 15% by weight of the layered clay material. 8. The nanocomposite of claim 1, comprising about 0.5 to about 10% by weight of the layered clay material. 9. The nanocomposite according to claim 1, wherein the layered clay material is a natural, synthetic or modified phyllosilicate. 10. The nanometer according to claim 1, wherein the layered clay material comprises montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, beidellite, vorconscoite, saponite, magadiite, keniyaite, or a mixture thereof. Composite materials. 11. The nanocomposite of claim 1, wherein the clay material comprises Wyoming-type montmorillonite or Wyoming-type bentonite. 12. The clay material has a cation exchange capacity of about 0.9 to about 1.5 meq / g.
The nanocomposite according to claim 1, which is a free-flowing powder having: 13. The method of claim 1, wherein at least 50% of the layered clay material is dispersed in the matrix polymer in the form of single platelet-shaped particles and tactoids having a thickness less than or equal to 30 nm. Nanocomposites. 14. The nanocomposite of claim 13, wherein the tactoid has a thickness of less than about 20 nm. 15. The organic cation is derived from an onium salt compound.
A nanocomposite according to claim 1. 16. The nanocomposite according to claim 15, wherein the onium salt compound comprises an ammonium salt compound or a phosphonium salt compound. 17. The nanocomposite of claim 1, wherein the mixture of organic cations comprises an alkyl ammonium ion, an alkyl phosphonium ion or a polyalkoxylated ammonium ion. 18. The nanocomposite of claim 17, wherein the alkyl ammonium ion comprises dodecyl ammonium, octadecyl ammonium, bis (2-hydroxyethyl) octadecylmethyl ammonium, octadecylbenzyldimethyl ammonium or tetramethyl ammonium. 19. The nanocomposite of claim 17, wherein the alkyl phosphonium ion comprises tetrabutyl phosphonium, trioctyl octadecyl phosphonium, tetraoctyl phosphonium or octadecyl triphenyl phosphonium. 20. An organic cation comprising a mixture of polyalkoxylated ammonium ions, wherein the polyalkoxylated ammonium ions are oligooxyethylene amine hydrochloride, oligooxypropylene amine hydrochloride, octadecylmethyl bis (polyoxyethylene [ 15) The nanocomposite of claim 17, wherein the nanocomposite is derived from ammonium chloride or octadecylbis (polyoxyethylene [15]) amine, wherein the number in parentheses is the total number of ethylene oxide units. 21. The oligooxyethyleneamine hydrochloride having a number average molecular weight of about 1
21. The nanocomposite of claim 20, having 100 g / mol and the hydrochloride salt of oligooxypropylene amine having a number average molecular weight of about 640 g / mol. 22. The melt-processable matrix polymer comprises poly (ethylene terephthalate) or a copolymer thereof, the layered clay material comprises Wyoming-type montmorillonite or Wyoming-type bentonite, and the mixture of at least two organic cations has a number average molecular weight. The nanocomposite of claim 1, comprising about 1100 g / mol of an oligooxyethylene amine hydrochloride and a number average molecular weight of about 640 g / mol of an oligooxypropylene amine hydrochloride. 23. A mixture of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane at a concentration of 0.5 g / 100 ml (solvent), measured at 25 ° C., at least 0.5 dL / g. I. V. The nanocomposite of claim 1, comprising: 24. An article made from the nanocomposite of claim 1. 25. The article of claim 24 in the form of a film, sheet, pipe, extrudate, molded article or molded container. 26. The article of claim 24 in the form of a bottle. 27. The article of claim 24, wherein the gas permeability is at least 10% lower than an article formed from a clay-free polymer. 28. An article having a plurality of layers wherein at least one layer is formed from the nanocomposite of claim 1. 29. The nanocomposite is disposed between two other layers.
An article according to claim 8. 30. A method according to claim 2, comprising one or more layers of structural polymer.
An article according to claim 8. 31. Producing an intercalated layered clay material by reacting (i) an intumescent layered clay material with a mixture of at least two organic cations; and (ii) intercalated with a matrix polymer. Incorporating the intercalated layered clay material into the matrix polymer by melt processing with the clay. A method of making a polymer / clay nanocomposite with improved gas barrier properties comprising: 32. The method according to claim 31, wherein step (ii) is performed by a batch mixing method or a melt compounding extrusion method. 33. A polymer / clay nanocomposite made by the method of claim 31. 34. An article made from the nanocomposite of claim 33. 35. The article of claim 34 in the form of a film, sheet, pipe, extrudate, molded article or molded container. 36. The article of claim 34 in the form of a bottle. 37. Producing an intercalated layered clay material by: (i) reacting an expandable layered clay material with a mixture of at least two organic cations; and (ii) converting the clay material to a polymer-forming material. And (iii) condensation polymerizing the components in the presence of the clay material. A process for producing a polymer / clay nanocomposite with improved gas barrier properties comprising the steps of: 38. A polymer / clay nanocomposite made by the method of claim 37. 39. An article made from the nanocomposite of claim 38. 40. The article of claim 39 in the form of a film, sheet, pipe, extrudate, molded article or molded container. 41. The article of claim 39 in the form of a bottle. 42. An insertion material comprising a layered clay material into which a mixture of at least two organic cations has been inserted and a melt-processable polymer. 43. The melt-processable polymer is polyester, polyetherester, polyamide, polyesteramide, polyurethane, polyimide, polyetherimide, polyurea, polyamideimide, polyphenylene oxide, phenoxy resin, epoxy resin, polyolefin, polyacrylate, polystyrene. 43. The insert of claim 42, comprising polyethylene, co-vinyl alcohol or a copolymer thereof or a mixture thereof. 44. The insert of claim 42, wherein the melt-processable polymer comprises a polyester, a polyamide, a polyethylene-co-vinyl alcohol or a copolymer thereof or a mixture thereof. 45. The melt-processable polymer is poly (m-xylene adipamide),
43. The intercalator of claim 42 comprising EVOH or a copolymer thereof or a mixture thereof. 46. The intercalant of claim 42, wherein the melt processable polymer comprises poly (ethylene terephthalate) or a copolymer thereof. 47. The insertion material of claim 42, comprising from about 5 to about 85% by weight of the melt-processable polymer interposed between adjacent layers of the layered material, based on the total weight of the insertion material. 48. The interposer of claim 42, comprising from about 15 to about 70% by weight of polymer intercalated between adjacent layers of the layered material, based on the total weight of the intercalator. 49. The method according to claim 49, wherein the polymer intercalated between adjacent layers of the layered material is about 30%.
43. The insertion material of claim 42, comprising from about 50% to about 50% by weight. 50. The insert of claim 42, wherein the layered clay material is a natural, synthetic or modified phyllosilicate. 51. The insert of claim 42, wherein the layered clay material comprises montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, beidellite, vorconscoite, saponite, magadite, kenyaite, or a mixture thereof. material. 52. The insertion material of claim 42, wherein the clay material comprises a smectite clay. 53. The clay material has a cation exchange capacity of about 0.9 to about 1.5 meq / g.
43. The intercalating material of claim 42, which is a free flowing powder having the formula: and which is selected from the group consisting of sodium montmorillonite, sodium bentonite, calcium montmorillonite, calcium bentonite or mixtures thereof. 54. The method according to claim 42, wherein at least 50% of the layered clay material is intercalated and dispersed in the form of discrete platelet-shaped particles and tactoids having a thickness of less than or equal to 60 nm. Insertion material. 55. The insertion material of claim 54, wherein the thickness of the tactoid is less than about 30 nm. 56. The organic cation is derived from an onium salt compound.
3. Insertion material according to 2. 57. The insertion material according to claim 56, wherein the onium salt compound comprises an ammonium salt compound or a phosphonium salt compound. 58. The intercalating material of claim 42, wherein the mixture of organic cations comprises an alkyl ammonium ion, an alkyl phosphonium ion or a polyalkoxylated ammonium ion. 59. The insertion material of claim 58, wherein the alkyl ammonium ion comprises dodecyl ammonium, octadecyl ammonium, bis (2-hydroxyethyl) octadecyl methyl ammonium, octadecyl benzyl dimethyl ammonium or tetramethyl ammonium. 60. The insertion material of claim 58, wherein the alkyl phosphonium ion comprises tetrabutyl phosphonium, trioctyl octadecyl phosphonium, tetraoctyl phosphonium or octadecyl triphenyl phosphonium. 61. The organic cation comprises a mixture of polyalkoxylated ammonium ions, wherein the polyalkoxylated ammonium ions are oligooxyethylene amine hydrochloride, oligooxypropylene amine or bis (polyoxyethylene [15]) amine. 58. The hydrochloride salt of octadecylmethylbis (polyoxyethylene [15]) ammonium chloride or octadecyl, wherein the number in parentheses is the total number of ethylene oxide units.
Insertion material according to. 62. The hydrochloride of oligooxyethyleneamine has a number average molecular weight of about 1
62. The insert of claim 61 having 100 g / mol and the hydrochloride salt of oligooxypropylene amine having a number average molecular weight of about 640 g / mol. 63. The melt processable polymer comprises poly (ethylene terephthalate) or a copolymer thereof, the layered clay material comprises a clay selected from montmorillonite and bentonite, and the mixture of at least two organic cations has a number average molecular weight of about 43. The intercalating material of claim 42 comprising an oligooxyethylene amine hydrochloride in the range of 200-5000 g / mol and an oligooxypropylene amine hydrochloride having a number average molecular weight of about 640 g / mol. 64. A release material formed by shearing the insert material of claim 42 to form a plurality of exfoliated clay layers and clay tactoids. 65. (i) producing an intercalated layered clay material by reacting the expandable layered clay material with a mixture of at least two organic cations;
And (ii) melt-treating the matrix polymer with the inserted clay material to insert the matrix polymer between adjacent layers of the inserted clay material. Of a polymer / clay intercalant capable of forming a nanocomposite with improved gas barrier properties. 66. The method according to claim 65, wherein step (ii) is performed by a batch mixing method or a melt compounding extrusion method. 67. A polymer / clay insert prepared by the method of claim 65. 68. A polymer / clay exfoliating material made by shearing an intercalating material made by the method of claim 65. 69. Producing an intercalated layered clay material by intercalating the expandable layered clay material with at least two organic cations; and (ii) polymerizing the clay material with a polymer-forming polymerizable material. By melt processing the matrix polymer with the inserted clay.
Inserting the matrix polymer between adjacent layers of the inserted clay material;
And (iii) subjecting the polymer component to condensation polymerization in the presence of the clay material to insert the polymer between adjacent layers of the layered clay material; A method of making a polymer / clay intercalant capable of forming a nanocomposite with improved gas barrier properties. 70. A polymer / clay insert prepared by the method of claim 69. 71. A polymer / clay exfoliating material made by shearing an intercalating material made by the method of claim 69.