A high barrier amorphous polyamide-clay nanocomposite and a process for preparing same

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

Field of invention The present invention generally relates to a nanocomposite material comprising at least one highly blocking amorphous matrix polymer resin, preferably an amorphous polyamide, and a clay material uniformly dispersed therein. The present invention also relates to products made from nanocomposites and methods for making nanocomposites.

【0002】

Background of the invention Thermoplastic materials are increasingly used in the packaging of beverages and perishable foods. Plastics are often the material of choice for food and beverage packaging due to their transparency, flexibility, toughness, high gas barrier properties, light weight, workability and high luster.

【0003】

There are many highly blocking semi-crystalline polyamides, and one of them, a polyamide based on m-xylylenediamine and adipic acid, is commercially available as MXD6 from Mitsubishi Gas Chemical Company. These crystalline polymers have been found to have high barrier properties against oxygen and carbon dioxide. Polyamides, such as those based on m-xylylenediamine and adipic acid, may be useful for packaging oxygen-sensitive foodstuffs, especially as a central layer in a three-layer stretch blow molded container or a three-layer extruded film. It recognized.

【0004】

Amorphous polyamides are manufactured and advocated as polymers for food packaging and have whitening or fogging resistance when exposed to moisture as described in US Pat. Nos. 5,028,462 and 4,983,719. Improvements have been proposed, and improved physical properties have been proposed, as described in US Pat. No. 4,018,746. However, these patents do not disclose or suggest incorporating a clay material into such an amorphous polyamide to improve the barrier properties of the polyamide or the products produced from it. Moreover, these patents do not disclose, disclose or suggest that fogging is reduced in composite materials including clay materials and amorphous polyamides.

【0005】

The principle of using layered clay to disperse clay in a polymer matrix to enhance or improve the properties of the polymer matrix is well established. U.S. Pat. No. 4,739,007 discloses that a composite material consisting of a polyamide matrix and a well-dispersed silicate layer exhibits high mechanical strength and excellent high temperature properties. Other references describing polymer nanocomposites containing polyamide matrices and silicate dispersions include US Pat. No. 4,810,734, German Pat. No. 3,808,623, J. Inclusion Pheno. mena 5 (1987), pp. 473-485, Clay Minerals, 23 (1988), pp. 27; Polymer Preprints, 32 (April 1991), pp. 65-66; and Polymer Preprints, 28 (August 1987), pp. 447-448.

【0006】

Multilayer materials for packaging are known for films, bottles and other containers. For example, the multi-layer injection molded preforms disclosed in European Patent Application No. 0278403A2 and US Pat. No. 4,398,642 have an outer thermoplastic layer that gives the material excellent overall properties and a thermoplastic resin with excellent gas barrier properties. Including the inner layer of. Molded containers made from these multi-layer preforms have potential advantages in terms of handleability, safety and manufacturing cost. However, processing a multi-layer container generally requires additional steps and time-wasting steps.

【0007】

It is often desirable to disperse the clay in the inner or central layer of a multilayer product consisting of highly blocking polyamides such as m-xylylenediamine and adipic acid based polyamides. The use of these clays in the matrix polymer of the inner layer of the multilayer container reduces fogging of the multilayer structure and improves the appearance of the oriented film and the molded product (eg, bottle).

【0008】

However, clay particles in nylon-6 nanocomposites induce crystallization, for example as described in US Pat. No. 5,385,776. Although not bound by any particular theory, during processing, for example during film stretching or orientation, polymer / clay nanocomposites undergo very high levels of clouding from the crystallization of matrix polymers around dispersed particles. The polymer nanocomposites are unsuitable for food packaging. This crystallization phenomenon forms even voids and holes in the polymer film, destroying the usefulness of these compositions for barrier applications.

【0009】

Thus, there is still a need in the industry for amorphous polyamide nanocomposites with reduced fogging. There is also a need for oriented single-layer and / or multi-layer structures that include amorphous polyamide nanocomposites. In addition, there is a need for a process that can introduce a clay material with substantially separated discoid particles into an amorphous polyamide in order to yield a nanocomposite with improved barrier properties and good transparency. There is.

【0010】

Abstract of the invention The present invention relates generally to amorphous high-blocking polyamides, and more particularly to polyamide nanocomposites comprising high-blocking amorphous polyamides and clay materials. These amorphous polyamides exhibit unexpected resistance to fogging, crystallization and other defect formation in the presence of dispersed treatments or organically modified clays when subjected to orientation and other film processing steps.

【0011】

As embodied and broadly described herein, the present invention, in one embodiment of the invention, is (a) (i) a residue of a dicarboxylic acid component containing at least two diacids and (ii) a residue of a diamine component. The present invention relates to a polyamide-clay nanocomposite comprising an amorphous matrix polyamide containing the above and (b) a layered clay material, wherein the clay material is dispersed in the matrix polyamide.

【0012】

In another embodiment, the invention presents (a) (i) an amorphous matrix polyamide containing (i) a residue of a dicarboxylic acid component containing at least two diacids and (ii) a residue of a diamine component and (b) a layered clay. The present invention relates to a polyamide-clay nanocomposite comprising a material, wherein the layered clay material is dispersed in an amorphous matrix polyamide compatible oligomeric resin, and the clay-oligoform resin dispersion is incorporated into the matrix polyamide.

【0013】

In yet another embodiment, the present invention comprises (i) melt-mixing the clay material with a matrix polymer compatible oligomer resin to form an oligomeric resin-clay composite, and (ii) making the oligomeric resin-clay composite high. Regarding the process of producing an amorphous polyamide-clay nanocomposite comprising a step of mixing with a molecular weight amorphous matrix polyamide, the high molecular weight amorphous matrix polyamide is (i) a dicarboxylic acid component containing at least two diic acids. (Ii) Consisting of residues of the diamine component and increasing the molecular weight of the oligomer resin-clay composite material, the nanocomposite material is produced.

【0014】

In yet another aspect, the invention mixes a clay material with a mixture of (a) (i) a dicarboxylic acid component containing at least two diacids and (ii) a diamine component of an amorphous polyamide, and (b). ) The present invention relates to a method for producing an amorphous polyamide-clay nanocomposite material, which comprises performing polycondensation polymerization of components (i) and (ii) in the presence of the clay material.

【0015】

Other advantages of the present invention are described in part in a detailed description including the following drawings, but some are self-evident from the detailed description or will be apparent by practicing the present invention. The advantages of the present invention can be realized and achieved by the elements and combinations individually pointed out in the claims. It is understood that both the above general description and the following detailed description represent and explain preferred embodiments of the invention and do not limit the invention described in the claims. I want to.

【0016】

Detailed description of the invention The present invention will be made easier to understand by reference to the following detailed description of the invention and the examples described herein. It should be understood that the invention is not limited to any particular ingredient, product, method and / or condition, as the ingredients, products, methods and / or conditions described herein are of course variable. Also, it should be understood that the terminology used herein is merely to describe individual embodiments and has no limiting implications.

【0017】

Definition Furthermore, it should be noted that the singular expressions "a, an and the" used in the specification and claims include multiple referents unless it is clear from the context that they are not plural. I want to. For example, reference to a "product," "container," or "bottle" manufactured from the nanocomposites and methods of the invention shall include processing of multiple products, containers or bottles.

【0018】

The range can be expressed herein as from one particular value with "about" or "generally" and / or to another specific value with "about" or "roughly". When representing such a range, another embodiment includes from one particular value to and / or another particular value. Similarly, it should be understood that when a value is expressed as an approximation by using "about", the particular value forms another embodiment.

【0019】

As used herein, the following terms shall have the following meanings: A "layered clay material", "layered clay", "layered material" or "clay material" is any organic or inorganic material such as smectite clay mineral or a mixture thereof, which is in the form of multiple adjacent bond layers. It shall mean. Layered clays contain plaque particles and are generally swellable.

【0020】

"Plate", "platelet particles" or "particles" shall mean individual or aggregated unbonded layers of layered material. These layers can be in the form of individual plaque particles, regular or irregular small aggregates of plaque particles (tactoids), and / or small aggregates of tactoids.

【0021】

"Dispersed" or "dispersed" is a general term meaning various levels or degrees of separation of plate-like particles. Relatively high levels of dispersion include, but are not limited to, "intercalated" or "exfoliated".

【0022】

"Intercalated" or "intercalate" refers to layered clay materials, including treated or organically modified layered clay materials with increased intermediate layer gaps between adjacent discoid particles and / or tactoids. It shall mean.

【0023】

By "peeling" or "peeling" is meant a small plate dispersed in almost every single state throughout the carrier material, such as a matrix polymer. Typically "exfoliated" is used to indicate the highest degree of separation of discoid particles.

【0024】

"Peeling" shall mean a method of forming a strip from an inserted or less dispersed state of separation.

【0025】

By "nanocomposite" is meant a polymer or copolymer in which multiple individual discs obtained from a layered clay material are dispersed.

【0026】

By "matrix polyamide" or "matrix polymer" is meant a thermoplastic or thermosetting amorphous polyamide in which the clay material is dispersed to form a nanocomposite.

【0027】

Description of the invention The present invention generally relates to highly blocking amorphous matrix polyamides. These amorphous polyamides haze, crystallize and create other defects in the presence of dispersed and / or exfoliated organically modified clays when subjected to orientation and / or other processing steps. It was found to show unexpected resistance to.

【0028】

Prior art is based on the peak intensity and basal spacing value, or lack of main basal spacing, as measured by X-ray analysis of polymer-platelet particle composites. It defines the degree of separation. X-ray analysis alone can enable quantification of the level of dispersion achieved, even though it is often unclear whether or not the discoid particles are individually dispersed in the polymer. There are many. The basal spacing by X-ray diffraction indicates the separation distance of the slabs in the tactoid rather than the individual slabs. X-ray diffraction intensity (basic spacing peak height) can correlate with the barrier layer of products obtained from nanocomposites, including clay materials. For example, a low basal spacing peak height indicates that there is little tactoid, so the rest must be individual discs or irregular tactoids.

【0029】

Moreover, in polymer nanocomposites, X-ray analysis does not accurately predict the dispersion of discoid particles in the polymer or the resulting improvement in gas barrier properties. TEM images of polymer-platelet composites show that the platen particles incorporated into at least one polymer are in various forms, such as individual plates (peeled), irregular aggregates of plates. It exists in the form of ordered or stacked polymers of plaques (tactoids), swollen aggregates of stacked plaques (inserted tactoids) and aggregates of tactoids (but not limited to these). Shown.

【0030】

Although not bound by any particular theory, the improved degree of gas barrier (permeability) is the embodiment of the resulting particulate plates and aggregates, which are dispersed or evenly distributed. It will depend on the extent to which they are and the extent to which they are aligned perpendicular to the bundle of translucent material.

【0031】

In order to improve gas permeability in accordance with the present invention, the plaque particles representing the bulk of the composite material are stripped in the matrix polymer, preferably most of the plaque particles, preferably at least about. 75%, perhaps at least 90% or more, are dispersed in the form of individual discs and small aggregates with a minimum dimension thickness estimated from TEM-images of less than about 30 nm, preferably less than about 10 nm. As such, it is preferable that a large amount is peeled off. Polymer-plate nanocomposites containing more individual discs and fewer aggregates, regular or irregular, are most preferred.

【0032】

Larger incomplete dispersion levels (ie, in the presence of large aggregates and tactoids above about 30 nm) not only exponentially reduce the possible barrier improvement due to the platy particles, but also the strength, Other properties inherent in the polymeric resin, such as toughness, heat resistance and processability, can be adversely affected.

【0033】

Also, although not bound by any particular theory, delamination of platen particles during melt processing or mixing with polymers requires optimal mixing free energy, which is due to contributions from mixed enthalpy and mixed entropy. It is believed that there is. Melting clay with a polymer results in negative mixed entropy due to the reduced number of conformations accessible to the polymer chain when the polymer chain is present in the region between the two layers of clay. For example, mixed enthalpy is not sufficient to overcome negative mixed entropy, so it is believed that poor dispersion can be obtained with melt-workable polyesters. Polyamides, on the other hand, generally provide good dispersion due to their hydrogen bonding properties. However, the degree of this dispersion is often reduced due to negative mixed entropy.

【0034】

Furthermore, as mentioned above, clay particles in nylon-6 nanocomposites induce crystallization, for example. Although not bound by any particular theory, polymer / clay nanocomposites have very high levels of matrix polymer crystals around dispersed particles during processing, for example during film stretching and orientation. It causes haze and makes the polymer nanocomposite unsuitable for use in food packaging applications. This crystallization phenomenon causes voids and holes in the polymer film, which impairs the use of the composition of the present invention for blocking applications.

【0035】

Regarding the present invention, it has been found that by processing an amorphous polyamide with a layered clay material, the plate-like particles are sufficiently dispersed in the obtained polyamide nanocomposite material, and almost a single plate-like particle is produced. did. The resulting nanocomposite, when molded into a wall or product, has improved gas barrier properties compared to pure polyamide molded into the same or similar structure. In addition, these amorphous polyamides are unexpectedly resistant to fogging, crystallization and other defect formation in the presence of dispersed and / or exfoliated organically modified clays when subjected to orientation and / or other film processing steps. Found to show.

【0036】

In one embodiment, the invention is to insert (ie, organically modify) an amorphous polyamide and a swellable layered clay material of about 25% by weight or less, which is organic cations, preferably onium ions. Containing a mixture of polyamide-clay nanocomposites. This insert clay material mixture comprises platelet-like particles dispersed in a polyamide.

【0037】

polyamide The amorphous polyamide of the present invention can consist of a diamine component and a polycondensation polymerization reaction product (or residue) of at least one dicarboxylic acid component. A "residue", when used with respect to the components of the polyamides of the invention, refers to the product of the resulting species, or any subsequent formulation or chemical, in a special reaction scheme. It means whether or not the part is actually obtained from the species.

【0038】

The dicarboxylic acid component comprises a first diacid and preferably a second diacid. These diacids can be in any proportion of mol% of the total diacid moiety present in the polyamide. One of the diacids is preferably present in an amount of about 10-90 mol% of the total diacid portion present in the polyamide, more preferably in an amount of about 45-85 mol%, more preferably in an amount of about 50-80 mol%. preferable.

【0039】

The dicarboxylic acid of the present invention (but not limited to these) is a dicarboxylic acid having 3 to about 40 carbon atoms, more preferably an aromatic dicarboxylic acid having 8 to 14 carbon atoms, and preferably having 8 to 14 carbon atoms. It contains an aliphatic dicarboxylic acid of 4 to 12 and / or a dicarboxylic acid selected from an alicyclic dicarboxylic acid having 8 to 12 carbon atoms.

【0040】

In one embodiment, the diacid is of formula (I) :. [0041]

[Chemical 1]

<img file="JP2002531663A_D0001.tif" />【0042】

Can be represented by. Appropriate R is as follows, but is not limited to these.

【0043】

[Chemical 2]

<img file="JP2002531663A_D0002.tif" />【0044】

In the embodiment defined by the formula (I), the dicarboxylic acid component is preferably iminodiacetic acid, oxydiacetic acid, thiodiacetic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, or the like. It is a mixture.

【0045】

Further suitable examples of dicarboxylic acids include, but are not limited to, phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanediacetic acid, and diphenyl. -4,4'-dicarboxylic acid, phenylenedi (oxyacetic acid), sebacic acid, succinic acid, adipic acid, glutaric acid, azelaic acid and the like can be mentioned.

【0046】

The diamine component contains an aliphatic diamine having about 2 to 12 carbon atoms. The aliphatic diamine can contain an aromatic group as long as an alkylene group (for example, a methylene group) is interposed between the amino group and the aromatic group. Aliphatic diamines also include alicyclic diamines such as piperazine. Examples of suitable aliphatic diamines are, but are not limited to, 1,2-ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, 1,12-dodecylenediamine, 1, 4-Cyclohexanebismethylamine, piperazine, p-xylylenediamine, m-xylylenediamine or a mixture thereof. The diamine component of the present invention preferably contains m-xylylenediamine.

【0047】

Other diamines or diamine mixtures can also be used with the preferred diamine (m-xylylenediamine) to form amorphous polyamides. The representative polyamides of the present invention are not limited to these, but are shown in Table I below.

【0048】

[table 1]

<img file="JP2002531663A_D0003.tif" />【0049】

Preferred amorphous highly blocking matrix polyamides of the present invention are adipic acid (A), 2,6-naphthalenedicarboxylic acid (NDA), isophthalic acid (IPA), terephthalic acid (TPA), 1,3-phenylenedioxy. Reaction containing a dicarboxylic acid component containing at least two of diacetic acid (PDA), 1,4-cyclohexanedicarboxylic acid (CHDA) and phenylindandidicarboxylic acid (PIDA) and a diamine component containing m-xylylene diamine (MX) Includes product or residue. The combination of at least two diic acids and diamines effectively interferes with the crystallization tendency of these macromolecules and retains a clear, transparent amorphous structure throughout the entire process. Amorphous polyamide can be formed by using more than one type of diamine with one type of diic acid. Amorphous polyamide can also be formed by using more than one type of diic acid and more than one type of diamine. MX is a preferred diamine due to its high barrier properties.

【0050】

In Table I, PDA (MX) is 100 mol% PDA and 100 mol% MX; PDA-10-TPA (MX) is 90 mol% PDA and 10 mol% TPA and 100 mol% MX; PDA-10-NDA (MX) 90 mol% PDA and 10 mol% NDA and 100 mol% MX; A-19-IPA (MX) 81 mol% A and 19 mol% IPA and 100 mol% MX; A-18-TPA (MX) 82 mol% A and 18 mol% TPA and 100 mol% MX; A-18-NDA (MX) 82 mol% A and 18 mol% NDA and 100 mol% MX; A-18-PIDA (MX) indicates 82 mol% A and 18 mol% PIDA and 100 mol% MX.

【0051】

As used in the present invention, "amorphous (or amorphous)" means that the polyamide does not show melting at the crystallization peak on the second DSC scan at a rate of 20 ° C / min. Amorphous polymers and / or polymer compositions are generally characterized by a high degree of transparency (clarity) and no sharp melting point. The polyamides shown in Table I do not show a clear melting point (Tm). After the formation of the nanocomposites of the invention, certain compositions exhibit a minor melting point with a ΔH of less than 0.5 cal / g due to the nucleation effect of clay, as shown in Example 4.

【0052】

Preferred polyamides are linear or almost linear polyamides, but if desired, polyamides having other structures including branched, stellate, crosslinked and dendritic structures can be used.

【0053】

The polyamide of the present invention exhibits an IV of about 0.25 to about 1.5 dL / g, preferably about 0.4 to about 1.2 dL / g, more preferably about 0.7 to about 0.9 dL / g. This IV is measured at a concentration of 0.5 g / 100 ml in a mixture of phenol / tetrachloroethane in a weight ratio of 60/40 at 25 ° C. Polyamides having an IV within the above range have a molecular weight high enough to be used in the formation of the products of the present invention.

【0054】

The amorphous polyamide of the present invention is synthesized by a method generally known in the industry for producing a polyamide. It is preferable that the diamine and diic acid components are reacted in a stoichiometric amount. Chlorides and esters of diic acid can be appropriately used. A solvent may be used in the production of the polyamide.

【0055】

Although not necessarily preferred, the polyamides of the invention can also contain suitable additives commonly used in polymers. Such additives can be used in regular doses and can be added directly to the reaction to form the polyamide or final polymer. Examples of such known additives are colorants, pigments, carbon blacks, fiberglass, fillers, impact resistant improvers, antioxidants, stabilizers, flame retardants, reheat aids, etc. Crystallization aids, acetaldehyde-lowering compounds, recycling release aids, oxygen sweeping agents, plasticizers, nucleating agents, mold release agents, compatibilizers, etc. or combinations thereof.

【0056】

All of these additives and many other additives and their use are known and do not require further explanation. Therefore, although only a limited number is mentioned, it should be understood that any of these compounds can be used in any combination as long as the invention does not prevent it from achieving its objectives.

【0057】

Clay material (platelet particles) The nanocomposite composition of the present invention is a layered clay of less than about 25% by weight, preferably about 0.5 to about 20% by weight, more preferably about 0.5 to about 15% by weight, most preferably about 0.5 to about 10% by weight. Including material. The clay material contains discoid particles. The amount of slab particles is determined by measuring the amount of silicate residues in the ash of the polymer / slab composition when treated according to ASTM D5630-94.

【0058】

Useful clay materials include natural, synthetic and modified phyllosilicates. Natural clays include smectite clays such as montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, byderite, volconscoite, magadite, keniyaite and the like. Examples of synthetic clay include synthetic mica, synthetic saponite, and synthetic hectorite. Examples of the modified clay include fluorinated montmorillonite and fluorinated mica. Suitable clays are available from a variety of companies, including Nanocor, Inc., Southern Clay Products, Kunimine Industries, Ltd. and Rheox.

【0059】

In general, a layered clay material useful in the present invention is, to the extent referred to as tactoid, an agglomeration of individual plate-like particles that are tightly stacked like curds. The individual plaque particles of clay preferably have a thickness of less than about 2 nm and a diameter in the range of about 10 to about 3000 nm.

【0060】

It is preferred that the clay be dispersed in the polyamide so that most of the clay material is present as individual plate-like particles, small tactoids and small aggregates of tactoids. Preferably, most of the tactoids and aggregates in the polyamide / clay nanocomposites of the present invention have a minimum dimensional thickness of less than about 20 nm. Polyamide / clay nanocomposite compositions containing relatively high concentrations of individual plate-like particles and relatively low in tactoids or aggregates are preferred.

【0061】

In addition, layered clay materials generally have a cation exchange capacity of about 0.3 to about 3.0 mm equivalent / g (mineral) (meq / g), preferably about 0.90 to about 1.5 meq / g, more preferably about 0.95 to about 1.25. It is a meq / g easily fluid and swelling powder. Clays include, but are not limited to, various exchangeable cations in the gallery between them, such as alkali metals (Group IA), alkaline earth metals (Group IIA) and mixtures thereof. Can have. The most preferred cation is sodium, but any cation or combination of cations can be used as long as most of the cations are interchangeable with organic cations (onium ions). The exchange can occur by treating individual clays or mixtures of clays with organic cations.

【0062】

A preferred clay material is a 2: 1 type phyllosilicate with a cation exchange capacity of 0.5-2.0 meq / g. The most preferred clay materials are smectite clay minerals, more specifically bentonite or montmorillonite, more specifically wioming sodium montmorillonite or wioming sodium bentonite with a cation exchange capacity of about 0.95 to about 1.25 meq / g.

【0063】

Other non-clay materials having the ion exchange capacity and size, such as chalcogens, can also be used as a source of discoid particles under the present invention. Chalcogens are heavy metals and salts of Group VIA (O, S, Se and Te). These materials are known and do not need to be described in detail here.

【0064】

The improvement in gas barrier property is obtained by increasing the concentration of plate-like particles in the polymer. Blocking properties are improved with as little as 0.01% of the plate particles (especially if they are well dispersed and regular), but compositions containing at least about 0.5% by weight of the plate particles are gas permeable. It is preferable because it shows the desired modification of the sex.

【0065】

Prior to incorporation into the polyamide, the particle size of the clay material is reduced by known methods such as milling, milling, hammer mill milling, jet mill milling and combinations thereof (but not limited to these). The average particle size is preferably reduced to less than 100 μm (diameter), more preferably less than 50 μm (diameter), and most preferably less than 20 μm (diameter).

【0066】

The clay material of the present invention can include refined but unmodified clay, modified clay or a mixture of modified clay and unmodified clay. In general, it is desirable to treat the selected clay material in order to facilitate the separation of the agglomerates of the plate-like particles into individual plate-like particles and small tactoids. Also, the polymer / plate interface is improved by separating the plate-like particles before incorporating them into the polymer. Any process that achieves the above objectives can be used. Many clay treatments used to modify clay for the purpose of improving the dispersion of clay materials are known and can be used in the practice of the present invention. The clay treatment can be performed before, during or after mixing the clay material and the polyamide.

【0067】

Organic cations In embodiments of the present invention, the intercalated layered clay material is produced by reacting the swollen layered clay with organic cations, preferably ammonium compounds (performing partial or complete cation exchange). for). If desired, the clay can be treated with two or more organic cations. In addition, a mixture of organic cations can also be used to make the inserted layered clay material (the inserted layered clay material in the polyamide nanocomplex contains a mixture of inserted clay). The method for producing the organoclay (inserted clay) can be batch, semi-batch or continuous.

【0068】

The organic cations used for insertion into the clay material or clay material mixture of the nanocomposites of the present invention are obtained from organic cation salts, preferably onium salt compounds. Organic cation salts useful for the nanocomposites and methods of the present invention generally include the following formula (I): [0069]

[Chemical 3]

<img file="JP2002531663A_D0004.tif" />【0070】

(In the formula, M is nitrogen or phosphorus; X^- Are halides, hydroxides or acetate anions, preferably chloride and bromide anions; R₁ , R₂ , R₃ And R₄ Can be independently organic and / or oligomeric ligands or hydrogen) Can be represented by.

【0071】

Examples of useful organic ligands include, but are not limited to: linear or branched alkyl groups with 1-22 carbon atoms; direct benzyl and alkyl moieties of structure with 1-100 carbon atoms. Alkyl group which is a substituted benzyl moiety containing a fused ring moiety having a chain or a branched chain; an aryl group such as a substituted phenyl containing a phenyl and a fused ring aromatic substituent; β, γ unsaturated having 6 or less carbon atoms Group; as well as an alkylene oxide group having a repeating unit of 2 to 6 carbon atoms. Examples of useful oligomeric ligands include, but are not limited to, poly (alkylene oxide), polystyrene, polyacrylate, polycaprolactone and the like.

【0072】

Examples of useful organic cations include, but are not limited to: alkylammonium ions such as tetramethylammonium, hexylammonium, butylammonium, bis (2-hydroxyethyl) dimethylammonium, hexylbenzyldimethyl. Ammonium, benzyltrimethylammonium, butylbenzyldimethylammonium, tetrabutylammonium, di (2-hydroxyethyl) ammonium and the like, as well as alkylphosphonium ions such as tetrabutylphosphonium, trioctyloctadecylphosphonium, tetraoctylphosphonium, octadecyltriphenylphosphonium and the like. Or a mixture thereof.

【0073】

Other particularly useful organic cations of the present invention include alkylammonium ions such as dodecylammonium, octadecyltrimethylammonium, bis (2-hydroxyethyl) octadecylmethylammonium, octadecylbenzyldimethylammonium and the like or mixtures thereof. Is not limited to these.

【0074】

Specific examples of suitable polyalkoxyammonium compounds include hydrochlorides of polyalkoxylated amines, such as JEFFAMINE (manufactured by Huntsman Chemical), ie, JEFFAMINE-506 and JEFFAMINE 505, and trade name ETHOMEEN (manufactured by Akzo Chemie America). ETHOMEEN 18/25, which is an amine available as, ie, octadecylbis (polyoxyethylene [15]) amine (the numbers in parentheses represent the total number of ethylene oxide units). Another specific example of a suitable polyalkoxylated ammonium compound is octadecylmethylbis (polyoxyethylene [15]) ammonium chloride (the number in parentheses represents the total number of ethylene oxide units) ETHOQUAD 18/25 (Akzo Chemie America). (Made).

【0075】

Many means of modifying layered clay with organic cations are known and any of them can be used in the practice of the present invention. In one embodiment of the invention, a layered clay or clay mixture is dispersed in hot water, most preferably in hot water at 50-80 ° C, and organic cation salts are added separately with stirring or organic cations. Sufficient time for the organic cations to exchange most of the metal cations present in the gallery between the layers of the clay material after adding a mixture of salts (pure or dissolved in water or alcohol). By the blending method, the layered clay is organically modified with an organic cation salt. The organically modified layered clay material is then isolated by known methods including, but not limited to, filtration, centrifugation, spray drying and combinations thereof.

【0076】

It is desirable to use a sufficient amount of organic cation salts that can exchange most of the metal cations in the layered particle gallery for organic cations; therefore, use at least about 0.5 equivalents of total organic cation salts and about. 3 equivalents or less of organic cation salts can be used. It is preferable to use about 0.5 to 2 equivalents, more preferably about 1.0 to 1.5 equivalents of the organic cation salt. Most of the metal cation salts and most of the excess organic cation salts should be removed by washing and other known techniques, but not necessary.

【0077】

Other clay treatment Clays can be further treated to aid exfoliation in the composite and / or to improve the strength of the polyamide / clay interface. Any process that achieves the above objectives can be used. Examples of useful treatments include intercalation with water-soluble or water-insoluble polymers, organic reagents or monomers, silane compounds, metals or organometallics and / or combinations thereof. The treatment of the clay can be carried out prior to the addition of the polyamide to the clay material mixture, during the dispersion of the clay with the polyamide, or during the next melt blending or melt molding process.

【0078】

Examples of useful pretreatments with polymers and oligomers are those disclosed in US Pat. Nos. 5,552,469 and 5,578,672, which are incorporated herein by reference. Examples of polymers useful for treating clay materials include polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polytetrahydrofuran, polystyrene, polycaprolactone, certain water-dispersible polyesters, nylon-6 and the like.

【0079】

Examples of useful pretreatments with organic reagents and monomers are those disclosed in EP780,340 Al, which are incorporated herein by reference. Examples of organic reagents and monomers useful for intercalating swellable layered clay include dodecylpyrrolidone, caprolactone, caprolactam, ethylene carbonate, ethylene glycol, bishydroxyethyl terephthalate, dimethyl terephthalate and the like or mixtures thereof. ..

【0080】

An example of a useful pretreatment with a silane compound is the treatment disclosed in WO 93/11190, which is incorporated herein by reference. Examples of useful silane compounds include (3-glycidoxypropyl) trimethoxysilane, 2-methoxy (polyethyleneoxy) propylheptamethyltrisiloxane, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride and the like. ..

【0081】

If desired, a dispersion aid may be present during or prior to the formation of the composite by melt mixing to aid in the exfoliation of the treated or untreated swelling layered particles into the polyamide. Many of these dispersion aids are known and include a wide range of substances including water, alcohols, ketones, aldehydes, chlorinating solvents, hydrocarbon solvents, aromatic solvents and the like or combinations thereof.

【0082】

It should be understood that based on the total composition, the dispersion aid and / or the pretreated compound may account for a significant amount of the total composition, and in some cases no more than about 30%. The amount of dispersion aid / pretreatment compound used is preferably as small as possible, but the amount of dispersion aid and / or pretreatment compound can be about eight times the amount of the plate-like particles.

【0083】

Product The polyamide-clay nanocomposite of the present invention can be molded into a product by conventional plastic processing techniques. Molded articles can be produced from the polyamide by compression molding, blow molding or other such molding techniques, all of which are known. The single-layer and / or multi-layer products manufactured from the nanocomposite material of the present invention include films, sheets, pipes, tubes, profiles, molded products, preforms, stretch blow molded films and containers, injection blow molded containers, and extrusion blows. Examples include, but are not limited to, molded films and containers, thermoformed products, and the like. The container is preferably a bottle.

【0084】

The bottles and containers of the present invention increase the shelf life of contents, including beverages and foods, which are vulnerable to gas permeation. The products of the invention, more preferably containers, are often at least 10% lower (depending on clay concentration) gas permeability or air permeability (oxygen, carbon dioxide) than similar containers made from clay-free polymers. , Water vapor), resulting in a correspondingly longer product shelf life of the container. Desirable values of lateral modulus and tensile strength can also be retained. The product also exhibits unexpected resistance to the development of fogging, crystallization and other defects.

【0085】

The product can also be multi-layered. In a multilayer product, the nanocomposite is preferably arranged in the middle of the other layers, but the nanocomposite can also be one layer of a two-layer product. In embodiments where the nanocomposite and its components are allowed to come into contact with food, the nanocomposite can form a food contact layer for the desired product. In other embodiments, the nanocomposite is preferably present in a layer other than the food contact layer.

【0086】

Multilayer products can also include one or more layers of the composite composition of the invention and one or more structural polymer layers. Various structural polymers can be used. Examples of structural polymers are polyester, polyether ester, polyamide, polyesteramide, polyurethane, polyimide, polyetherimide, polyurea, polyamideimide, polyphenylene oxide, phenoxy resin, epoxy resin, polyolefin, polyacrylate, polystyrene, polyethylene-co. -Vinyl alcohol (EVOH) etc. or combinations thereof and friends. Preferred structural polymers are polyesters such as poly (ethylene terephthalate) and copolymers thereof.

【0087】

In another embodiment, the product can be formed by co-extruding one layer of the aforementioned polyamide-clay nanocomposite layer with some other suitable thermoplastic resin. Polyamide-clay nanocomposites and shaped articles and / or extrusion sheets can also be simultaneously formed by co-injection molding or co-extrusion.

【0088】

Another embodiment of the present invention is to use a silicate layer uniformly dispersed in a matrix of high barrier thermoplastics in combination with a multi-layer approach to packaging materials. By reducing the gas permeability of the high barrier layer with layered clay, the amount of this material required to produce a constant barrier level in the end application is significantly reduced.

【0089】

Since high barrier materials are often the most expensive component in multi-layer packages, reducing the amount of this material used can be very beneficial. When the polyamide-clay nanocomposite layer is sandwiched between two polymer outer layers, the surface roughness is often much less than that of a single layer nanocomposite. Therefore, in the case of the multi-layer approach, the degree of fogging can be further reduced.

【0090】

Method The amorphous polyamide of the present invention can be produced by various methods using a clay material. In one embodiment of the invention, appropriately treated or modified sodium montmorillonite or other clay is melt processed or blended into a high molecular weight product of a highly blocking amorphous polyamide to give a polyamide-clay nanocomposite. Melt processing includes melting and extrusion blending. The use of extrusion formulations for mixing clays and polymers has several advantages. First, the extruder can handle the high viscosities exhibited by nanocomposites. Further, in the melt mixing method for producing a nanocomposite for producing a nanocomposite, the use of a solvent can be avoided. Low molecular weight liquids can often be expensive to remove from nanocomposite resins.

【0091】

The nanocomposite can then be directly co-extruded as a central layer of the three-layer packaging, as an injection molded container preform, or as an extruded film. An additional process of stretch blow molding into a container or extrusion as a barrier can result in a clear, highly barriered final product.

【0092】

In another embodiment, the process of the present invention is: (i) a low molecular weight product (oligomer) of an amorphous highly blocking polyamide with an amino-terminated group or a diic acid-terminated group in a molten phase step-for growth polycondensation. It is prepared by unbalancing the polymerization stoichiometry and consists of (ii) melting and mixing the oligomer with the clay material. The clay material is preferably treated or modified as described above. Such low molecular weight oligomers have been found to be very effective in dispersing organoclays or other suitable modified clays, preferably smectic clays, as concentrates during melt mixing. The desired IV or molecular weight value of the oligomer depends on several factors, including the selected oligomer and clay, and is readily determined by one of ordinary skill in the art.

【0093】

Concentrates are then let-down with MXD6 or one of the amorphous polyamides mentioned above to form a nanocomposite blend, which is then preformed, for example as a central layer or barrier film. Coextruded into. An additional stretch blow molding process into the container results in a clear, highly barriered product.

【0094】

Any melt-mixing device can be used, but generally the melt-mixing step is carried out by batch mixing or melt-blended extrusion, during which treated or untreated layered particles are introduced into the oligomeric resin. Prior to melt mixing, the treated or untreated layered particles can be present in various forms including pellets, flakes, chips and powders. The treated or untreated layered particles are preferably pulverized by known methods, for example, hammer mill pulverization and jet mill pulverization to reduce the size. Prior to melt mixing, the oligomeric resin can be present in various forms, including pellets, ground chips, powders or melted states thereof.

【0095】

The melt-mixing step can also be performed by dry mixing the oligomeric resin with treated or untreated layered particles and then passing the mixture through a blending extruder under conditions sufficient to melt the oligomeric resin.

【0096】

Further, the melt-mixing step can also be performed by separately supplying the oligomer resin and the treated or untreated layered particles to the compound extruder. When the treated layered particles are used in this method, it is preferable to add the oligomeric resin first to minimize the decomposition of the treated layered particles.

【0097】

In yet another embodiment involving melt mixing of the oligomers, the high concentration layered particles are melt mixed with the oligomeric resin by mixing in a reactor. The resulting composite is then chain extended and polymerized to a high molecular weight or charged into a high molecular weight polyamide in an extruder to give the final nanocomposite.

【0098】

In another embodiment of the melt mixing step, the molten oligomeric resin can be fed directly to the compounding extruder along with the treated or untreated layered particles to obtain an oligomeric resin-clay nanocomposite.

【0099】

The oligomer resin and the high molecular weight amorphous polyamide may have the same or different repeating unit structures, that is, the same or different monomer units. The oligomer resin preferably has the same monomer unit in order to enhance compatibility or miscibility with the high molecular weight amorphous polyamide.

【0100】

If desired, a dispersion aid may be present during or before the formation of the composite by melt mixing to aid in the exfoliation of the treated or untreated swelling layered particles into the polymer. .. Many of these dispersion aids are known and include a wide range of materials including water, alcohols, ketones, aldehydes, chlorinating solvents, hydrocarbon solvents, aromatic solvents and the like or combinations thereof.

【0101】

A third aspect of the process of the present invention comprises (i) adding modified clay to a mixture of diic acid and diamine of the desired polyamide and (ii) performing polycondensation polymerization in the presence of clay. The molecular weight of a polymeric material can be determined by any of many known techniques, or a combination thereof, for example, chain extension, reactive extrusion, let-down, solid phase polymerization or annealing, annealing under inert gas flow. , Vacuum annealing, charging in a melting reactor (let down), or any combination thereof.

【0102】

The resulting nanocomposite can then be processed into the desired barrier film or container according to the manufacturing method described in the aforementioned aspects of the process of the invention.

【0103】

Polymer nanocomposites produced according to the present invention exhibit at least 10% lower gas permeability than unmodified polymers.

【0104】

Example The following examples and experimental results are described in order to sufficiently disclose and explain specific methods for carrying out and evaluating the present invention to those having ordinary knowledge in the art, and are merely representatives of the present invention. It is intended as an example and is not intended to limit the scope of what the inventors consider to be their own explanations. Efforts have been made to ensure accuracy with respect to numerical values (eg, quantity, temperature, etc.), but some errors and deviations may have occurred. Unless otherwise noted, parts are parts by weight, temperature is ° C or ambient temperature, and pressure is at or near atmospheric pressure.

【0105】

Example 1 This example illustrates the preparation of an amorphous polyamide containing 1,3-phenylenedioxydiacetic acid (PDA) and m-xylylenediamine (MX). 67.8 g (0.3 mol) resorcinol bis (carboxymethyl) ether [(1,3-phenylenedioxy) diacetic acid], 40.8 g in a 500 ml round bottom flask with a short distillation column, stirrer and nitrogen inlet. (0.3 mol) of m-xylylenediamine and 75.0 g (4.17 mol) of water were added. The flask was depressurized to 100 mm, any oxygen was purged and nitrogen was injected 3 times. The flask was placed in a Belmont metal bath at 130 ° C and stirred at 100 RPM. After 18 minutes, the condensing receiver trapped 20 ml of water and the reaction mixture became a white solid. The stirrer was stopped and the temperature was raised to 220 ° C. After 8 minutes, the temperature setting was raised to 275 ° C. After 19 minutes, the temperature reached 265 ° C and the reaction mixture began to melt, so stirring was started at 25 RPM. 50 ml of water was captured in the condensing receiver. After 17 minutes, the temperature reached 275 ° C, 2/3 of the reaction mixture had melted and 60 ml of water was trapped in the condensing receiver. After 8 minutes, most of the white solid melted, the stirrer was raised to 100 RPM and the temperature setting was raised to 280 ° C. 62 ml of water was captured by the condensing receiver. After 5 minutes, all white solids had melted and were at a temperature of 280 ° C. These conditions were maintained for 28 minutes. Stirring was reduced to 25 RPM and maintained for 2 minutes. The heat was removed, the polyamide was cooled, removed from the flask and ground to pass through a 3 mm screen. Analysis result: IV = 0.52dL / g, Tg = 96.7 ° C, color = L^*= 83.45, a^*= 0.72, b^*= 28.67, NMR confirmed that the composition was a PDA (MX). Oxygen permeability to compression molded film is 0.19cc-ml / 100in²It was -day-atm.

【0106】

Example 2 Example 2 illustrates the preparation of a polyamide containing 90 mol% 1,3-phenylenedioxydiacetic acid (PDA) and 20 mol% terephthalic acid (TPA) and m-xylylenediamine (MX). 61.02 g (0.27 mol) of 1,3-phenylenedioxydiacetic acid, 4.98 g (0.03 mol) of terephthalic acid, 40.8 g in a 500 ml round bottom flask with a short distillation column, stirrer, and nitrogen inlet. (0.3 mol) of m-xylylenediamine and 75.0 (4.17 mol) of water were added. The flask was placed in a Belmont metal bath at 170 ° C and stirred at 100 RPM. After 8 minutes, the condensing receiver trapped 35 ml of water and the reaction mixture became a white solid. The stirrer was stopped and the temperature was raised to 220 ° C. After 12 minutes, the temperature setting was raised to 275 ° C and 52 ml of water was trapped in the condensing reservoir. After 7 minutes, the temperature reached 263 ° C and the reaction mixture began to melt, so stirring was started at 25 RPM. 60 ml of water was captured in the condensing receiver. After 9 minutes, the temperature reached 275 ° C, 1/3 of the reaction mixture had melted and the stirrer was raised by 50 RPM. 70 ml of water was captured by the condensing receiver. After 9 minutes, most of the white solid melted, the stirrer was raised to 100 RPM and 72 ml of water was captured by the condensing receiver. After 5 minutes, all white solids had melted and the agitation was reduced to 50 RPM. These conditions were maintained for 30 minutes.

【0107】

The heat was removed, the polyamide was cooled, removed from the flask and ground to pass through a 3 mm screen. The analysis results are as follows: IV = 0.40dL / g, Tg = 101.1 ° C, color = L^*= 92.90, a^*= 3.22, b^*= 36.48. It was confirmed by NMR that the composition was PDA-10-TPA (MX).

【0108】

Example 3 This example prepares an amorphous polyamide containing 90 mol% 1,3-phenylenedioxydiacetic acid (PDA) and 10 mol% naphthalenedicarboxylic acid (NDA) and m-xylylenediamine (MX). Is illustrated. 61.02 g (0.27 mol) of resorcinolbis (carboxymethyl) ether [(1,3-phenylenedioxy) diacetic acid], 6.48 in a 500 ml round bottom flask with a short distillation column, stirrer, and nitrogen inlet. g (0.03 mol) of 2,6-naphthalenedicarboxylic acid, 40.8 g (0.3 mol) of m-xylylenediamine, and 75.0 g (4.17 mol) of water were added. The flask was placed in a Belmont metal bath at 170 ° C and stirred at 100 RPM. After 10 minutes, the reaction mixture turned into a white solid and the stirrer was shut down. 22 ml of water was trapped in the condensing reservoir and the temperature setting was raised to 220 ° C. After 10 minutes, the temperature setting was raised to 275 ° C and 40 ml of water was trapped in the condensing reservoir. After 7 minutes, the temperature reached 263 ° C and the reaction mixture began to melt, so stirring was started at 25 RPM. 50 ml of water was captured in the condensing receiver. After 9 minutes, the temperature reached 275 ° C and 1/3 of the reaction mixture melted. The stirrer was raised to 50 RPM and 60 ml of water was captured by the condensing receiver. After 9 minutes, most of the white solid melted, the stirrer was raised to 100 RPM and 62 ml of water was captured by the condensing receiver. After 5 minutes, all white solids had melted and the agitation was reduced to 50 RPM. These conditions were maintained for 30 minutes. The heat was removed, the polyamide was cooled, removed from the flask and ground to pass through a 3 mm screen. Analysis result: IV = 0.39dL / g, Tg = 101.1 ° C, color = L^*= 82.41, a^*= 2.23, b^*= 36.62. Confirmation by NMR = PDA-10-NDA (MX).

【0109】

Example 4 Example 4 illustrates the preparation of an amorphous polyamide containing 82 mol% adipic acid (A) and 18 mol% isophthalic acid (IPA) and m-xylylenediamine (MX). 46.72 g (0.32 mol) of adipic acid, 13.28 g (0.08 mol) of isophthalic acid, 55.5 g (0.408 mol) of m- in a 500 ml round bottom flask with a short distillation column, stirrer, and nitrogen inlet. Xylylene diamine and 75.0 (4.17 mol) of water were added. The flask was placed in a Belmont metal bath at 115 ° C and stirred at 100 RPM. After 8 minutes, a clear melt with some white non-melt was obtained. The agitation was raised to 200 RPM. These conditions were maintained for 18 minutes. The temperature setting was raised to 275 ° C. After 17 minutes, the metal bath temperature was 168 ° C. and when 40 ml of water was trapped in the condensing reservoir, the reaction mixture became a white solid. The stirrer was stopped. After 9 minutes, the temperature reached 216 ° C and the reaction mixture began to melt, so stirring was started at 25 RPM. After 8 minutes, the stirrer setting was raised to 100 RPM. After 11 minutes, the whole solid had melted and 70 ml of water was trapped in the condensing receiver. The stirrer setting was raised to 200 RPM and the bath temperature was 275 ° C. Decompression was started from 300 mmHg, and the pressure was gradually reduced by 0.3 mmHg for 5 minutes. The agitation setting was reduced to 100 RPM. The viscosity of the melt increased and stirring was gradually reduced to 25 RPM over 15 minutes. After a total decompression time of 20 minutes, the decompression was raised to atmospheric pressure to remove heat. The polyamide was cooled, removed from the flask and ground to pass through a 3 mm screen. The analysis results are as follows: IV = 0.83dL / g, Tg = 104.1 ° C, Tm = none, color = L^*= 82.15, a^*=-1.38, b^*= 24.15. It was confirmed by NMR that the composition was A-19-IPA (MX).

【0110】

Example 5 Example 5 illustrates the preparation of a polyamide containing 82 mol% adipic acid (A) and 18 mol% terephthalic acid (TPA) and m-xylylenediamine (MX). 46.72 g (0.32 mol) of adipic acid, 13.28 g (0.08 mol) of terephthalic acid, 55.5 g (0.408 mol) of m- in a 500 ml round bottom flask with a short distillation column, stirrer, and nitrogen inlet. Xylylene diamine and 75.0 (4.17 mol) of water were added. The flask was placed in a Belmont metal bath at 115 ° C and stirred at 100 RPM. After 12 minutes, it became an opaque liquid and the agitation was raised to 200 RPM. These conditions were maintained for 18 minutes. The temperature setting was raised to 275 ° C. After 13 minutes, the metal bath temperature was 168 ° C. and when 30 ml of water was trapped in the condensing reservoir, the reaction mixture became a white solid. The stirrer was stopped. After 10 minutes, the temperature reached 275 ° C and the reaction mixture began to melt, so stirring was started at 25 RPM. After 16 minutes, some began to melt, so the agitation setting was raised to 100 RPM. After 7 minutes, the stirrer setting was raised to 200 RPM. After 26 minutes, the whole solid had melted and 65 ml of water was trapped in the condensing receiver. Decompression was started from 300 mmHg, and the pressure was gradually reduced by 0.3 mmHg for 5 minutes. As the viscosity of the melt increased, stirring was gradually reduced to 25 RPM over 13 minutes. After a total decompression time of 20 minutes, the decompression was raised to atmospheric pressure to remove heat. The polyamide was cooled, removed from the flask and ground to pass through a 3 mm screen. The analysis results are as follows: IV = 0.80dL / g, Tg = 106.3 ° C, Tm = none, color = L^*= 83.49, a^*= -2.49, b^*= 22.98. NMR composition = A-18-TPA (MX). Oxygen permeability to compression molded film is 0.17cc-ml / 100in²It was -day-atm.

【0111】

Example 6 This example illustrates the preparation of an amorphous polyamide containing 82 mol% adipic acid (A) and 18 mol% naphthalenedicarboxylic acid (NDA) and m-xylylenediamine (MX). 46.72 g (0.32 mol) of adipic acid, 17.28 g (0.08 mol) of 2,6-naphthalenedicarboxylic acid, 55.5 g (0.408 mol) in a 500 ml round bottom flask with a short distillation column, stirrer and nitrogen inlet. ) M-Xylylene diamine and 75.0 (4.17 mol) of water were added. The flask was placed in a Belmont metal bath at 115 ° C and stirred at 100 RPM. After 12 minutes, it became a white opaque liquid and the agitation was raised to 200 RPM. These conditions were maintained for 18 minutes. The temperature setting was raised to 275 ° C. After 13 minutes, the metal bath temperature was 164 ° C, and when 30 ml of water was trapped in the condensing reservoir, the reaction mixture became a white solid. The stirrer was stopped. After 10 minutes, the temperature reached 275 ° C and the reaction mixture began to melt, so stirring was started at 25 RPM. After 16 minutes, some began to melt, so the agitation setting was raised to 100 RPM. After 7 minutes, the stirrer setting was raised to 200 RPM. After 26 minutes, the whole solid had melted and 65 ml of water was trapped in the condensing receiver. Decompression was started from 300 mmHg, and the pressure was gradually reduced by 0.3 mmHg for 5 minutes. As the viscosity of the melt increased, stirring was gradually reduced to 25 RPM over 13 minutes. After a total decompression time of 20 minutes, the decompression was raised to atmospheric pressure to remove heat. The polyamide was cooled, removed from the flask and ground to pass through a 3 mm screen. The analysis results are as follows: IV = 0.80dL / g, Tg = 106.3 ° C, Tm = none, color = L^*= 83.49, a^*= -2.49, b^*= 22.98. NMR = A-18-NDA (MX). Oxygen permeability to compression molded film is 0.17cc-ml / 100in²It was -day-atm.

【0112】

Example 7 This example illustrates the preparation of an amorphous polyamide containing 81 mol% adipic acid (A) and 19 mol% phenylindandicarboxylic acid (PIDA) and m-xylylenediamine (MX). 46.72 g (0.32 mol) of adipic acid, 25.76 g (0.08 mol) of 2,6-phenylindanicarboxylic acid, 55.5 g (55.5 g) in a 500 ml round bottom flask with a short distillation column, stirrer, and nitrogen inlet. 0.408 mol) of m-xylylene diamine and 75.0 (4.17 mol) of water were added. The flask was placed in a Belmont metal bath at 115 ° C and stirred at 25 RPM. After 14 minutes, bubbles were generated and the agitation was raised to 300 RPM. The condition was maintained for 14 minutes. The temperature setting was raised to 140 ° C. After 9 minutes, the temperature setting was raised to 150 ° C. and 10 ml of water was captured by the condensing receiver. After 3 minutes, the metal bath temperature was 160 ° C. and 12 ml of water was captured by the condensing receiver. After 3 minutes, the metal bath temperature was 275 ° C and 15 ml of water was captured by the condensing receiver. After 6 minutes, the metal bath temperature was 198 ° C and 21 ml of water was captured by the condensing receiver. There were some bubbles left. After 10 minutes, the bath temperature reached 244 ° C and 35 ml of water was trapped in the condensing reservoir. The reaction mixture was a thick white paste with agitation reduced to 25 RPM. After 16 minutes, the metal bath temperature was 275 ° C and 1/2 of the reaction mixture had melted. After 3 minutes, 3/4 of the reaction mixture had melted and 66 ml of water was trapped in the condensing reservoir. After 5 minutes, the entire paste was thawed, and the pressure was reduced from 500 mmHg, and the pressure was gradually reduced by 0.3 mmHg for 8 minutes. As the viscosity of the melt increased, stirring was gradually reduced to 25 RPM over 12 minutes. After a total decompression time of 20 minutes, the decompression was raised to atmospheric pressure to remove heat. The polyamide was cooled, removed from the flask and ground to pass through a 3 mm screen. The analysis results are as follows: IV = 0.50dL / g, Tg = 109.6 ° C, Tm = none, color = L^*= 78.08, a^*=-1.33, b^*= 19.26. NMR composition = A-19-PIDA (MX).

【0113】

Example 8 Example 8 illustrates the preparation of one embodiment of the polyamide-clay nanocomposites of the present invention. Amorphous copolyamide (1,000 g A-20-IPA (MX) with IV of about 0.91 dL / g) and Nanocor, Inc. onium ion-inserted clay (29.0 g) prepared as described in Example 5. CWC-ODA) was dry-mixed and dried in a vacuum dryer infused with a small amount of nitrogen at 75 ° C for about 16 hours. Extrusion speed of 3.8 kg / hour by Leistritz Micro 18 simultaneous rotation 2-screw extruder with barrel and die temperature set at 250 ° C and a common compound screw of about 300 RPM including vacuum ventilation with the mixture in an AccuRate feeder. Extruded with. The extruded product was quenched in water and diced to give 807 g of copolyamide nanocomposite containing about 0/90 dL / g IV and about 1.9 wt% ash. DSC analysis showed a slight endothermic melting of 0.4 cal / g at about 200 ° C in the first scan, whereas the second scan after cooling at a rate of about 200 ° C / min showed no endothermic melting. I was not able to admit.

【0114】

Example 9 Example 9 illustrates one of the embodiments of the polyamide-clay nanocomposite of the present invention and the simultaneous extrusion of poly (ethylene terephthalate) (PET). The copolyamide nanocomposite (about 700 g) obtained in Example 8 was dried for about 16 hours in a vacuum dryer infused with a little nitrogen at 75 ° C. Eastman Chemical Company's PET9921 was dried separately in a hopper dryer at approximately 120 ° C. The copolyamide nanocomposite and PET 9921 are then extruded simultaneously to form a copolyamide nanocomposite with an intermediate layer of approximately 7.0 mils in thickness and two outer layers of PET 9921 with a total film thickness of approximately 21 mils. A layer film was formed. Several 2-inch square 3-layer film pieces were stretched biaxially with a 4x4 elongation ratio using a TMLong device.

【0115】

Stretched film has excellent color and about 0.6% cloudiness, L^*= Approximately 94.6, a^*= About -0.9, and b^*= Showed transparency of about 0.1. Optical microscopic analysis of the stretched film revealed very few giant particles and few voids. The oxygen permeability of the film using Mocon Oxatran 2120 is 0.48cc-mil / 100in.²-Day-atm, which is much better than the control sample in Comparative Example 1 and better than the polyamide nanocomposite in Comparative Example 2.

【0116】

Comparative example 1 The method of Example 9 was repeated except for the clay-free MXD6 6007 marketed by Mitsubishi Gas and Chemical Company, which was used in place of the copolyamide nanocomposite to make an extruded product with an overall thickness of 20.5 mils. A three-layer film with a central clay-free barrier layer about 6.0 mils thick was obtained.

【0117】

The stretched film has a good color, but with increased fogging, about 2.45% fogging, L^*= Approximately 94.7, a^*= About -0.09, and b^*= Showed transparency of about -0.1. The oxygen permeability of the film using Mocon Oxatran 2/20 is 0.83cc-mil / 100in.²-day-atm, which is much higher than the film containing the intermediate layer of nanocomposite in Example 5 (0.35cc-mil / 100in).²-day-atm).

【0118】

Comparative example 2 The method of Example 8 was repeated, except that MXD6 6007 of Mitsubishi Gas and Chemical Company was used in place of the copolyamide prepared as described in Example 4. The method of Example 2 was repeated except that (1) MXD6 nanocomposite was used instead of copolyamide nanocomposite and (2) Eastman Chemical Company's PET 20261 was used instead of PET 9921. The total thickness of the three-layer film was about 21 mils and the thickness of the intermediate MXD6 nanocomposite layer was about 1.4 mils.

【0119】

The stretched film became cloudy, and it was about 2.5% cloudy. Optical microscopic analysis of the stretched film revealed a large number of giant particles and a large number of voids. The oxygen permeability of the film using Mocon Oxatran 2/20 is 2.81cc-mil / 100in.²It was -day-atm.

【0120】

Example 10 As described in Example 4, amine-terminated copolyamides were prepared with a low molecular weight, except that an excess of m-xylylenediamine was used, to obtain a substance with an IV of about 0.3 dL / g. This material was then used in place of the high IV copolyamide in the method of Example 8. After the extrusion was completed, 100 g of extruded pellets were dry mixed with 300 g of MXD6 6007 polyamide pellets from Mitsubishi Gas and Chemical Company. The molecular weight of MXD6 polyamide was as follows: M_n= 10,000g / mol, M_w= 25,000g / mol, and M_z= 40,000 g / mol. The mixture was then extruded with a Leistritz extruder under the same conditions as the clay polymer mixture except for an extrusion rate of 2.0-2.5 kg / hour. It is found that the resulting copolyamide nanocomposite provides a three-layer film with excellent appearance and oxygen barrier.

【0121】

Example 11 The method of Example 4 was repeated except that Nanocor, Inc. onium ion-inserted clay (29.0 g of CWC-ODA) was added to the flask prior to the addition of m-xylylenediamine. It has been found that the resulting copolyamide nanocomposite provides a three-layer film with excellent appearance and oxygen barrier.

【0122】

Various publications are cited throughout this specification. The entire disclosure of these publications is incorporated herein by reference in order to more fully explain the status of the art belonging to the present invention. It will be appreciated by those skilled in the art that various modifications and modifications can be made without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art by considering the details and implementation of the invention disclosed herein. Details and examples are considered for illustration purposes only, and the true scope and spirit of the invention is intended to be set forth in the claims below.