A polymer clay nanocomposite comprising an amorphous oligomer.
Abstract
This invention is directed to a polymer clay nanocomposite, products produced from the nanocomposite, and a process for preparing a polymer clay nanocomposite. The polymer clay nanocomposite comprises (a) a matrix polymer, (b) an amorphous oligomer, and (c) a layered clay material.

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Expired 1 December 2020, 5.8 years ago.
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30 claims: 7 independent, 23 dependent
- 1REIVINDICACIONES 1. Un nanocompuesto de arcilla-polímero caracterizado porque comprende:(a) un polímero matriz;5 (b) un oligómero amorfo;y (c) un material de arcilla en capas, o residuo del mismo;en donde el compuesto de arcilla-polímero no comprende simultáneamente 10 (i) una poliamida matriz amorfa que comprende (a) un residuo de al menos un componente de ácido dicarboxílico y (b) un residuo de al menos un componente diamina;o poli(mxilenadipamida) y (ii) una resina oligomérica compatible con 15 poliamida matriz amorfa, o (m-xilenadipamida) oligomérica.
- 2El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el componente (a) comprende un poliéster, polieteréster, poliamida, poliésteramida, poliuretano, poliimida, polieterimida, 20 poliurea, poliamidoimida, polifenilenóxido, resina fenoxi, resina epoxi, poliolefina, poliacrilato, poliestireno, alcohol polietilen-co-vinílico, o una mezcla de los mismos.
- 3El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el componente (a) 25 comprende una poliamida cristalina o semi-cristalina.
- 4El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el componente (a) comprende poli(m-xililenadipamida).
- 5El nanocompuesto de conformidad con la 5 reivindicación 1, caracterizado porque el componente (b) comprende una poliamida oligomérica amorfa.
- 6El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el componente (a) y el componente (b) tienen la misma unidad monomérica. 10
- 7El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque comprende más de cero hasta aproximadamente 25 por ciento en peso del material de arcilla en· capas.
- 8El nanocompuesto de conformidad con la 15 reivindicación 1, caracterizado porque comprende de aproximadamente 0.5 hasta aproximadamente 15 por ciento en peso del material de arcilla en capas.
- 9El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el material de arcilla 20 en capas comprende montmorilonita, saponita, hectorita, mica, vermiculita, bentonita, nontronita, beidelita, volconscoita, magadita, ceniaita, o una mezcla de los mismos.
- 10El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el material de arcilla 25 en capas comprende montmorilonita sódica de tipo Wyoming o bentonita sódica de tipo Wyoming.
- 11El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el material de arcilla en capas se trata con un polímero soluble o insoluble en 5 agua,' un reactivo o monómero orgánico, un compuesto de silano, un metal, un organometálico, un catión orgánico para efectuar el intercambio catiónico, o una combinación de los mismos.
- 12El nanacompuesto de conformidad con la 10 reivindicación 11, caracterizado porque el material de arcilla en capas se trata con un catión orgánico representado por la fórmula:Γ R * Ί I Ro-M-R 3 I *4 en donde M es nitrógeno o fósforo, y Ri, R 2 , R 3 , y son 15 independientemente ligandos orgánicos y/u oligoméricos o hidrógeno.
- 13El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque es preparado por un proceso de mezclar los componentes (a), (b), y (c). 20
- 14El artículo preparado a partir del nanocompuesto de conformidad con la reivindicación 1.
- 15El artículo de conformidad con la reivindicación 14, caracterizado porque esta en la forma de película, hoja, tubería, fibra, preforma, perfil, un artículo extruido, un artículo moldeado o un recipiente moldeado. 5
- 16El artículo de conformidad con la reivindicación 14 en la forma de una botella.
- 17Un proceso para preparar un nanocompuesto de arcilla-polímero que comprende los pasos de:(a) mezclar por fusión un material de arcilla en 10 capas con una resina oligomérica amorfa, para formar un compuesto de arcilla-resina oligomérica;y (b) mezclar el compuesto de arcilla-resina oligomérica con un polímero matriz para producir el nanocompuesto de arcilla-polímero;15 caracterizado porque el nanocompuesto de arcillapolímero no comprende simultáneamente (I) una poliamida matriz amorfa que comprenden (i) un residuo de al menos un componente de ácido dicarboxílico y (ii) un residuo de al menos un componente diamina;o poli(m20 xilenadipamida) y (II) una resina oligomérica compatible con poliamida matriz amorfa, o (m-xilen adipamida) oligomérica.
- 18El proceso de conformidad con la reivindicación 17, caracterizado porque el paso (b) se conduce por una 25 mezcla por lote o un proceso de extrusión de composición por fusión.
- 19El proceso de conformidad con la reivindicación 17, caracterizado porque la resina oligomérica amorfa y el polímero matriz tienen la misma unidad monomérica.
- 20El proceso de conformidad con la reivindicación 17, caracterizado, porque la resina oligomérica amorfa es una poliamida oligomérica.
- 21El material nanocompuesto producido por el proceso de conformidad con la reivindicación 17.
- 22El artículo preparado a partir del material nanocompuesto de conformidad con la reivindicación 21.
- 23El. artículo de conformidad con la reivindicación 22, en la forma de película, hoja, fibra, preforma, perfil, un artículo extruido, un artículo moldeado o un recipiente moldeado.
- 24El artículo de conformidad con la reivindicación 22 en la forma de una botella.
- 25Un proceso para preparar nanocompuesto de arcilla-polímero caracterizado porque comprende mezclar por fusión un material de arcilla en capas, una resina oligomérica amorfa, y un polímero matriz, para producir el material nanocompuesto de arcilla-polímero, caracterizado porque el nanocompuesto de arcilla-polímero no comprende simultáneamente (a) una poliamida matriz amorfa que comprende (i) un residuo de al menos un componente de ácido dicarboxílico y (ii) un residuo de al menos un componente diamina o poli(fflxilenadipamida);y (b) una resina oligomérica compatible con poliamida 5 matriz amorfa, o (m-xilenadipamida) oligomérica.
- 26El nanocompuesto de arcilla-polímero producido por el proceso de conformidad con la reivindicación 25.
- 2727, Un nanocompuesto de arcilla-poliamida caracterizado porque comprende:10 (i) una poliamida matriz de alto peso molecular, e incorporado en eso (ii) un material de arcilla en capas, carácter!zado porque el · material de arcilla se dispersa en una resina oligomérica amorfa compatible con la poliamida matriz. 15
- 28El nanocompuesto de conformidad con la reivindicación 27, caracterizado porque el nanocompuesto de arcilla-polímero no comprende simultáneamente (a) una poliamida matriz amorfa que comprende (i) un residuo de al menos un componente de ácido dicarboxílico y 20 (ii) un residuo de al menos un componente diamina;o poli(mxilenadipamida);y (b) una resina oligomérica compatible con la poliamida matriz amorfa, o (m-xilenadipamida) oligomérica.
- 29El nanocompuesto de conformidad con la 25 reivindicación 28, caracterizado porque la resina oligomérica no es (m-xilenadipamida) oligomérica.
- 30El nanocompuesto de conformidad con la reivindicación 1, caracterizado porque el componente (a) comprende un poliéster, polieteréster, poliamida, 5 políésteramída, poliuretano, poliimida, polieterimida, poliurea, poliamidoimida, polifenilenóxido, resina fenoxi, resina epoxi, poliolefina, poliacrilato, poliestireno, alcohol polietilen-co-vinílico, o una mezcla de los mismos.
Independent claims30
341 paragraphs in 4 sections, as filed
(54) Title: A CLAY-POLYMER NANOCOMPOSITE THAT INCLUDES AN AMORPHIC OLIGOMER. (54) Tltle: A POLYMER CLAY NANOCOMPOSITE COMPRISING AN AMORPHOUS OLIGOMER.
(57) Summary
This invention is directed to a clay-polymer nanocomposite, the products produced from the nanocomposite, and a process for preparing a clay-polymer nanocomposite. The clay-polymer nanocomposite comprises (a) a matrix polymer, (b) an amorphous oligomer, and (c) a layered clay material.
(57) Abstract
Thls ¡nventlon ¡s directed to a polymer clay nanocomposlte, producís produced from the nanocomposlte, and a process for preparing a polymer clay nanocomposlte. The polymer clay nanocomposlte comprises (a) a matrlx polymer, (b) an amorphous ollgomer, and (c) a layered clay material.
<sup>r</sup> * (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY? (PCT)<sup>Wor</sup>"|||| IIIIMIIíWIIIHIIBilllBaWlimiBIBiBIHiil (43) International Publication Date (10) International Publication Number
June 2001 (07.06.2001) pct WO 01/40369 Al (51) International Patent Classification<sup>7</sup>: C08K 4/9,
3/34. 7/00 (21) International Application Number: PCT / USOO / 32829 (22) International FilingDate: 1 December2000 (01.12.2000) (25) Fiiing Language: English (26) Publication Language: English (30) Priority Data:
60 / 168,403 1 December 1999 (12/01/1999) US (71) Applicant: EASTMAN CHEMICAL COMPANY [US / US]; 100 North Eastman Road. Kingsport, TN 37660 (US).
(72) Inventors: BAGRODLA, Shriram; 2649 Suffolk Street, Kingsport, TN 37660-5803 (US). BERNARD, Linda, Gail: 309 Castaway Drive, Kingsport, TN 37663-3568 (US). CONNELL, Gary, Wayne; 212 Gilda Avenue, Churcb Hill, TN 37642-3101 (US). GELMER, John, Walker; 2624 Wildwood Drive, Kingsport, TN 37660-4754 (US). LAN, Tie; 760 Waterford Court, Lake Zurich, EL 60047 (US). MATAYABAS, James, Christopher, Jr .; 1380 West Saragosa Place, Chandler,
AZ 85224-7216 (US). OWENS, Jeffrey, Todd; 117 Wiliowbrook Drive, Kingsport, TN 37660-7581 (US). PSIHOGIOS, Vasiliki: Apartment 1,321 N. Smith Street, Palatine, IL 60067 (US). SHARP, Emerson, Eston, Jr .; 1208 Mouming Dove Drive, Kingsport, Tennessee 37663-2883 (US). TURNER, Sam, Richard; 1037 Sussex Drive, Kingsport, TN 37660-5836 (US).
(74) Agents: KATZ, Mitchell, A. et al .; Needle & Rosenberg, PC, Suite 1200, The Candler Buiiding. 127 Peachtree Street, NE, Atianta, GA 30303-1811 (US).
(81) Designated States (national): CA, CN, JP, MX.
(84) Designated States (regional): European patent (AT, BE, CH, CY, DE, DK, ES, Fl, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR) .
Published:
- With International search report.
- Before the expiration of the time limit for amending the claims and to be republished in the event of receipt of amendments.
For two-letter codes and other abbreviations, refer to the Gtiid · anee Notes on Codes and Abbreviations appearing at the begín · ning of each regular issue of the PCT Gazette.
(54) Title: A POLYMER-CLAY NANOCOMPOSITE COMPRISING AN AMORPHOUS OL1GOMER (57) Abstract: This invention is directed to a polymer-clay nanocomposite, products produced from the nanocomposite, and a process for preparing a polymer-clay nanocomposite. The polymer-clay nanocomposite comprises (a) a matrix polymer, (b) an amorphous oligomer, and (c) a layered clay material.
A CLAY-POLYMER NANOCOMPOSITE THAT INCLUDES A
AMORPHIC OLIGOMER
DESCRIPTION OF THE INVENTION
This application claims priority to the application for 5 provisional patent Serial No. 60 / 168,403, filed on December 1, 1999, which is incorporated herein by reference in its entirety.
This invention relates to a nanocomposite composition comprising a matrix polymer, preferably a polyamide, at least one amorphous oligomeric resin, and a layering clay material uniformly dispersed therein. This invention also relates to articles produced from the nanocomposite and processes for producing the nanocomposite.
Polymer clay composites have received a lot of attention lately because of their potential to improve polymer properties, including gas barrier, heat deflection temperature, and modulus. Polymer clay compounds have been found to frequently exhibit rapid crystallization which has been attributed to nucleation of the polymer matrix by clay. This feature may be an advantage for opaque crystalline molded parts with improved heat resistance and modulus such as the nylon compounds described in US Patent Nos. 5,385,776 and 4,739,007 and
PET compounds discussed in Journal of Applied Polymer Science, Vol. 71 (1999), pg. 1139-1146. However, the rapid crystallization of polymer clay compounds precludes their use in applications where rapid crystallization is not desired, including, but not limited to, profile extrusion, extrusion blow molding, stretch, film extrusion, and blown film. The rapid crystallization of polymer clay compounds makes it difficult, if not impossible, to obtain transparent patches and greatly reduces the availability of the processing window.
US Patent No. 4,739,007 describes composite materials comprising a polyamide matrix polymer and a well dispersed layered silicate material that has been treated with monomeric components of the polyamide, then subjected to subsequent polymerization, which imparts high mechanical strength and excellent high temperature properties. US Patent No. 4,889,885 describes composite materials comprising mixing polyamide-free matrix polymers and a well-dispersed silicate material that has been treated with a monomer and / or oligomer of a resin other than polyamide resin, and a polymerization step to polymerize the monomer and / or oligomer in the mixture formed in the mixing step.
US Patent No. 5,285,776 describes
<img file="MXPA02005457A_D0001.tif" />
Composite materials comprising a Nylon-6 matrix and a minor amount of a layered silicate material that is incorporated during melt extrusion and imparts the rapid nucleation of the polyamide within the gamma glass structure thereby enhancing the modulus and resistance to plasticization by water.
US Patent No. 4,810,731 describes nylon compounds comprising a layered silicate material that has been treated with some organic ammonium compounds and incorporated by synthesis using a dispersion aid.
PCT application WO 93/04117 describes composites, which comprise a polyamide matrix and a layered silicate material that has been modified with some primary or secondary organic ammonium compounds incorporated during melt extrusion to impart an improved modulus to the compound polymeric.
Journal of Applied Polymer Science, Vol. 71 (1999), pg. 1139-1146, describes the rapid crystallization of composite materials comprising a polyethylene terephthalate matrix and an undescribed clay material.
PCT application WO 93/11190 describes nylon compounds comprising a layered silicate material which has been treated with some organic ammonium compounds then with some silane compounds incorporated by melt mixing.
MXD6 is a commercially available partially aromatic semi-crystalline nylon resin prepared from adipic acid and meta-xylylenediamine and is also available as a copolyamide having comonomers including isothalic acid. MXD6 and its co-polyamides are preferred barrier materials for use in multi-layer PET bottles because of their similar processing conditions and rheology with PET and because of their improved resistance to delamination from PET compared to EVOH. Although MXD6 crystallizes faster than PET, its crystallization rate is just slow enough to allow the manufacture of multi-layer bottles. However, because the MXD6 oxygen barrier is only 10-40 times the oxygen barrier of PET, further improvements in the gas barrier properties of MXD6 containing materials are desirable.
During this work it has been found that MXD6-clay compounds, for example, can significantly improve the oxygen barrier and thus provide improved barrier multi-layer bottles and / or allow the preparation of multi-layer bottles of high barrier comprising thin layers of the barrier material, which reduces the cost of raw material and improves
recyclability. However, it has also been found that many MXD6-clay compounds crystallize faster than clay-free MXD6, making bottle preparation more difficult and sometimes impossible. For many MXD6-clay compounds, it has been found that as clay loading increases and the resulting gas barrier properties increase, the crystallization rate of the polymer becomes faster. It is, therefore, desirable to significantly improve the gas barrier properties of the MXD6 using nanocomposite technology without increasing the crystallization rate compared to that of pure MXD6.
It is an objective of this invention to overcome the nucleating effect caused by the presence of the clay plate particles and to provide polymer clay compounds which have the benefits of the improved properties allowed by the incorporation of the clay plate particles, but which remain easily processable for a wide variety of applications.
Surprisingly, it has been found that when some amorphous oligomeric resins are used to treat clays, the increase in crystallization rate of the polymeric matrix material is decreased, and in some cases reversed. Additionally, the use of amorphous oligomeric resins has been found to provide •<sup>20</sup> Additional benefits, including improved orocesabiiioad in blow molding applications, memory adhesion, improved recyclability, improved color, improved barrier, improved clarity, and / or combinations thereof.
Therefore, as encompassed and broadly described herein, this invention, in one embodiment, relates to a clay-polymer nanocomposite comprising (i) a matrix polymer, (ii) an amorphous oligomer, and (iii ) a layered clay material.
In another embodiment, the invention relates to a clay-polyamide nanocomposite comprising:
(i) a high molecular weight matrix polyamide, and incorporated herein (ii) a layered clay material, wherein the clay material is dispersed in an amorphous oligomeric resin compatible with the matrix polyamide.
In another aspect, this invention relates to a process for preparing a clay-polymer nanocomposite comprising the steps of:
(a) melt mixing a layered clay material with a compostable amorphous oligomeric resin with the mazriz polymer to form a clay-oligomeric resin compound; and (b) mixing the clay-oxyphomeric resin compound with a high molecular weight matrix polymer to produce the clay-polymer nanocomposite material.
In yet another aspect, the invention relates to a process for preparing clay-polymer nanocomposite comprising melt mixing a layered clay material, an amorphous oligomeric resin, and a matrix polymer to produce the clay-polymer nanocomposite material. .
Additional advantages of the invention will be indicated in part in the detailed description that follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages of the invention will be realized and achieved by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory of the preferred embodiments of the invention, and are not restrictive of the invention, as claimed.
The present invention may be more readily understood by reference to the following detailed description of the invention and the examples provided herein. It should be understood that this invention is not limited to the specific components, articles, processes and / or conditions described, since these may, of course, vary. It should also be understood that the terminology_ used herein is for the purpose of describing particular modalities only and is not intended to be limiting.
Definitions
It should also be noted that, as used in the specification and the appended claims, the forms
<td>singular</td><td>one / one / one</td><td>and</td><td>they include</td><td>references</td>
<td>plurals a</td><td>less than</td><td>the</td><td colspan="2">context clearly dictate what</td>
<td>contrary.</td><td>For example,</td><td>the</td><td>reference to a</td><td>Article,</td>
container or bottle prepared from the nanocomposite and process of this invention attempts to include the processing of a plurality of articles, containers or bottles.
The ranges may be expressed herein as about or about a particular value and / or up to about or about another particular value.
When this range is expressed, another modality includes the particular value and / or the other particular value. Likewise, when values are expressed as approximations, by the use of the antecedent approximately, it will be understood that the particular value forms another modality. It will be further understood that the endpoints of each of the ranges are significant relative to the other endpoint, and independently of the other endpoint.
Whenever used in this specification and claims, the terms indicated shall have the following meanings:
<img file="MXPA02005457A_D0002.tif" />
Layered clay material, layered clay, layered material, or clay material shall mean any organic or inorganic material or samples thereof, such as smectite clay mineral, which is in the form of a plurality of adjacent bonded layers . Layered clay comprises platelet particles and is typically extensible.
Platelets, platelet particles, clay particles or particles will mean individual or aggregated unbound layers of the layered material. These layers may be in the form of individual platelet particles, small ordered or disordered aggregates of platelet particles (tactiodes), and / or small aggregates of tactile.
Dispersion or dispersion is a general term that refers to a variety of levels or degrees of separation of platelet particles. Higher levels of dispersion include, but are not limited to interleaving and peeling.
Interleaved or intercalated shall mean a layered clay material including treated or organically modified layered clay material that has an increase in interlayer spacing between adjacent platelet and / or tactile particles.
Exfoliate or exfoliate will mean platelets
*
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<td>mainly scattered</td><td>in</td><td>a this</td><td>•do</td><td>individual /</td><td>L through</td>
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<td>height of separation of the</td><td colspan="2">particle</td><td>s of</td><td>platelet</td><td></td>
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<img file="MXPA02005457A_D0005.tif" />
Exfoliation shall mean a process to form an exfoliate from an interleaf or otherwise a less dispersed state of separation.
Nanocomposite will mean a composition or residue comprising a polymer or copolymer having dispersed therein a plurality of individual platelets obtained from a layered clay material.
Matrix polymer or matrix polyamide will mean a thermoplastic or thermoset polymer or polyamide in which the clay material disperses to form a nanocomposite.
A residue of a chemical species, as used in the specification and conclusive claims, refers to the portion that is the product resulting from the chemical species in a particular reaction scheme or subsequent formulation or chemical, regardless of whether the portion It is currently obtained from the chemical species. Thus, an ethylene glycol residue in a polyester refers to one or more repeat units of -OCH3CH2O- in the polyester, regardless of whether ethylene glycol is used to prepare the polyester. Equally,
<img file="MXPA02005457A_D0006.tif" />
A cebasic acid residue in a polyester refers to one or more portions of -CO (CH2) SCO- in the polyester, regardless of whether the residue is obtained by reacting the cebasic acid or an ester thereof to obtain the polyester.
A residue of a chemical composition, as used in the specification and conclusive claims, refers to the final composition or product that is produced by a process to prepare the composition or product from identifiable composition starting materials, regardless of whether the residue contains, after formation, identifiable quantities of the starting materials unchanged. In other words, a residue in a chemical formulation or composition can refer to the product produced by the relevant process, even though the process starting materials can be dissociated, mixed, reacted, or otherwise changed during the process to prepare the residue. For example, the residue of a composition formed by a process of mixing an aqueous solution comprising HCI and an aqueous solution comprising NaOH would refer to the final composition formed (comprising water and salt (NaCl)), regardless of whether the composition Final contain HCI or NaOH. In a further example, the residue of a composition formed by a process of mixing a layered clay material comprising a Wyoming-type bentonite and an amorphous oligomer would refer to the formed composition, regardless of whether the final composition contains Wyoming-type bentonite .
identifiable or unchanged.
Description of Modalities
In one embodiment, this invention relates to a composite material comprising at least one amorphous oligomeric resin, and clay platelet particles uniformly dispersed therein and the products produced from the compound.
In other embodiments, this invention relates to a clay-polymer nanocomposite comprising:
(i) a matrix polymer;
(ii) an amorphous oligomer; and (iü) a layered clay material, or a residue thereof.
However, in some embodiments, the nanocomposites of the invention are not a clay-polyamide nanocomposite comprising:
(a) an amorphous matrix polyamide comprising (i) a residue of a dicarboxylic acid component comprising at least one diacid and (ii) a residue of at least one diamine component, and (b) a layered clay material , where the clay material is dispersed in the matrix polyamide.
Similarly, in some other embodiments, the clay-polymer nanocomposites do not comprise (i) an amorphous matrix polyamide comprising (i) a residue of at least one dicarboxylic acid component and (ii) a residue of at least one diamine component ; or poly (m-xylene adipamide) or (ii) an oligomeric resin compatible with the amorphous matrix polyamide, or oligomeric (m-xylene adipamide).
In some embodiments, the polymer clay nanocomposite does not simultaneously comprise (i) and (ii) as described immediately above.
In still other embodiments, the nanocomposites of this invention are not a clay-polyamide nanocomposite comprising (a) an amorphous matrix polyamide comprising (i) a residue of at least one dicarboxylic acid component and (ii) a residue of a diamine component and (b) a layered clay material, wherein the layered clay material is dispersed in an oligomeric resin compatible with the amorphous matrix polyamide and wherein the oligomer-clay resin dispersion is incorporated into the matrix polyamide.
In some embodiments, the invention relates to a process for preparing a clay-polymer nanocomposite comprising the steps of:
. ... tóriMtetu ,, teatte »- arAaA- ·., '· # rfitj» -éii'-TB .. »M ii« i' • 'i irfmÜiííSaiít i (a) melt mix a clay material in layers with an amorphous oligomeric resin, to form a clay-oligomeric resin compound; and (bi-oligomeric mixing the clay-resin compound with a matrix polymer to produce the clay-polymer nanocomposite;
In some embodiments, the invention relates to a process for preparing a clay-polymer nanocomposite comprising the steps of (a) melt mixing a layered clay material with an amorphous oligomeric resin to form a clay-oligomeric resin compound and. (b) mixing the clay-oligomeric resin compound with a high molecular weight matrix polymer and producing a nanocomposite material.
As with the compositions of the invention, some embodiments of the processes of this invention do not comprise (i) preparing a low molecular weight (oligomer) version of a high amorphous barrier polyamide with amino or diacid end groups unbalancing the stoichiometry of polymerization to growth polycondensation by melting phase steps, and (ii; melt mixing the oligomer with the clay material.
Furthermore, in some embodiments of the process of the invention, the clay-polymer nanocomposite does not comprise
<img file="MXPA02005457A_D0007.tif" />
simultaneously (i) an amorphous matrix polyamide comprising (i) a residue of at least one dicarboxylic acid component and (ii) a residue of at least one diamine component; or poly (m-xylene adipamide) and (ii) an oligomeric resin compatible with the amorphous matrix polyamide, or oligomeric (m-xylene adipamide).
Typically, the layered clay material (typically a silicate) is treated with various agents as described below to improve the dispersibility of the layered clay material to form dispersed platelet particles in the composite. The nanocomposite compositions produced in accordance with the present invention are especially useful for preparing clear and film bottles that have improved gas barrier properties.
By virtue of their reduced tendency to crystallize, the nanocomposite compositions produced in accordance with the present invention are unexpectedly more processable than conventional clay-polymer compositions. Additionally, products produced from nanocomposites can achieve lower fog (especially when oriented), superior gas barrier properties, and better adhesion on multilayer films than products produced from compounds of, clayA .. OR. tfcAi .1..1 j or
conventional polymer.
The prior art has defined the degree of separation of the clay (platelet particles) based on the intensity of the peak and the base space gap, or lack of predominant basal spacing, as determined by X-ray analysis of the platelet-polymer particle compounds. Even though X-ray analysis only frequently does not unambiguously predict whether the platelet particles are individually dispersed in the polymer, it can often allow quantification of the level of dispersion achieved. Basal X-ray diffraction spacing indicates the separation distance of a platelet on a tactile rather than individual platelets. X-ray diffraction intensity (peak height of basal spacing) can be correlated to the barrier in an article that results from a nanocomposite that includes a clay material. For example, a low peak height of basal spacing indicates few tactiles; therefore, the remainder must be individual platelets or tactile platelets that are disordered.
Furthermore, in polymeric nanocomposites, X-ray analysis alone does not accurately predict the dispersion of platelet particles in the polymer or the resulting gas barrier enhancement. TEM images of platelet-polymer compositions show that platelet particles that are incorporated into at least one polymer exist in a variety of ways, including, but not limited to, individual platelets (the exfoliated state), agglomerates platelet disorders, stacked or ordered platelet aggregates (tactile), stacked platelet dilated aggregates (interspersed tactile), and tactile aggregates.
Without being limited by any particular theory, it is believed that the degree of improved gas barrier (permeability) depends on the rate of incorporation of the resulting particle and aggregate platelets, the degree to which they are uniformly dispersed or distributed, and the degree to which they are arranged perpendicular to the flow of the permeant.
To obtain the improvements in gas permeability in accordance with the present invention, it is preferable that the platelet particles representative of the mass of the compound are exfoliated, and preferably highly exfoliated, in the matrix polymer such that the majority, preferably at less than about 75% and perhaps as much as at least about 90% or more of the platelet particles, they are scattered in the form of individual platelets and small aggregates having a thickness in the shortest dimension of less than about 30 nm and preferably less than about 10 nm, as estimated from TEM images. Platelet-polymer nanocomposites containing more individual platelets and less aggregates, ordered or disordered are more preferred.
Significant levels of incomplete scattering 5 (i.e. the presence of large agglomerates and tactiles larger than about 30 nm) not only lead to an exponential reduction in potential barrier improvements attributed to platelet particles, but can also lead to effects Harmful to other properties inherent in polymeric resins such as strength, toughness, heat resistance, visual transparency and processability.
Again, without being limited by a particular theory, it is believed that the delamination of platelet particles during fusion or mixing processing with a polymer requires favorable free mixing energy, which has contributions from the enthalpy of mixing and the entropy of the mixed. Processing clay by melting with the polymers results in negative mixing entropy due to the reduced number of conformations, which are accessible to a polymer chain when it resides in the region between two layers of clay. It is believed to have poor dispersion using melt processable polyesters, for example, because the enthalpy of the mix is not sufficient to overcome the negative entropy of the mix. In
In contrast, good dispersions are generally obtained with polyamides due to their hydrogen bonding character. However, the degree of this dispersion is frequently decreased due to the negative entropy of mixing.
Furthermore, as described above, many prior art polyamide nanocomposites comprising clay particles induce rapid crystallization. Without being limited by any particular theory, it is believed that processing of the prior art polymer / clay nanocomposites, such as stretching or orientation of the films, leads to very high levels of matrix polymer crystallization fog around the dispersed particles, which makes polymeric nanocomposites undesirable for food packaging application. This crystallization phenomenon can still lead to the formation of voids and holes in the polymeric films, which destroys the usefulness of these compositions in barrier applications.
With respect to the present invention, it has been found that processing a matrix polymer, preferably a polyamide, an amorphous oligomer, preferably an oligomeric amorphous polyamide, a layered clay material gives good dispersion of platelet particles into a resulting polymeric nanocomposite, creating scattered clay domains, containing mainly individual platelet particles. The resulting nanocomposite has an improved gas barrier when it is turbid within a wall or article compared to a pure polymer formed within the same or similar structure. Furthermore, it has been found that these nanocomposites having an amorphous oligomer show unexpected resistance to fog formation, crystallization, and other formation defects in the presence of dispersed and / or exfoliated organically modified clays when they undergo orientation and / or other steps of film processing.
Measurement of peak temperatures for crystallization during cooling (T<sub>DC</sub>) and crystallization during heating (T<sub>ch</sub>) by DSC is a useful tool to quickly determine, qualitatively, the relative crystallization rates by comparison of T<sub>DC</sub>-T<sub>c</sub>h. The larger the Tc value<sub>C</sub>-Tc<sub>h</sub>, the faster the material crystallizes. Conversely, the lower the value of T<sub>DC</sub>-T<sub>c</sub>h, the material crystallizes more slowly, and the absence of a T<sub>DC</sub> and / or T<sub>ch</sub> it is indicative of crystallization which is much slower than the DSC measurement time scale, which typically uses an examination rate of approximately 5-20 ° C / min. This method is subtle for comparing composite compositions comprising the same polymeric matrix material. Heating and cooling rates are 20 ° C / min for T values<sub>DC</sub> and T<sub>ch</sub> given in this document.
Matrix polymers
Any melt processable matrix polymer can be used in this invention. Illustrative of the melt processable polymers are polyesters, polyether esters, polyamides, polyesteramides, polyurethanes, polyimides, polyetherimides, polyureas, polyamideimides, polyphenylene oxide, phenoxy resins, epoxy resins, polyolefins, polyacrylates, polystyrene, polyvinyl alcohols, polyvinyl alcohols, polyvinyl alcohols, polyvinyl alcohols and the like or their mixtures and combinations. Although the preferred polymers are linear or quasi-linear, polymers with other architectures, including branched, star, crosslinked, and dendritic structures, can be used if desired. The matrix polymers can be crystalline, semi-crystalline, or amorphous.
Preferred matrix polymers include those materials that are suitable for use in forming multilayer structures with polyesters, and include polyesters, polyamides, polyethylene-covinyl alcohols (such as EVOH), and similar polymers and / or copolymers or related. The most preferred matrix polymer is a polyamide and / or its copolymers.
Any polyamide can be used as a matrix polymer in the processes of this invention. In some embodiments, the polyamides include partially polyamides
-Ul. I, i.Jdt aromatic, aliphatic polyamides, fully aromatic polyamides and / or mixtures thereof. Parcialmente'-ί partially aromatic polyamide, is meant that the amide repeating units of the partially aromatic polyamide 'have at least one aromatic ring and at least one non-aromatic species attached thereto.
Preferred matrix polymers have a molecular weight for forming articles, preferably an average molecular weight number of more than about 10,000 g / mol, and / or preferably an inherent viscosity (IV) of more than 0.5, up to about 1.5 dL / g The matrix polymers of the present invention preferably have an IV of from about 0.6 to about 1.2 dL / g, and more preferably from about 0.7 to about 0.9 dL / g. measured at 25 ° C in a 60/40 weight percent phenol / 1,1,2,2-tetrachloroethane mixture at a concentration of 0.5 grams per 100 ml. Polymers having an IV within the ranges specified above are of sufficiently high molecular weight to be used in the formation of the articles of the present invention.
Preferred fully aromatic polyamides comprise at least 70% mol of structural units in the matrix polymer chains derived from a mixture of m25 xylylenediamine or a mixture of xylylenediamine comprising p-xylylenediamine and up to 30% of p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 10 carbon atoms, which are further described in Japanese Patent Publication Nos. 1156/75, No., 5751/75, No.,
5735/75 and No. 10196/75 and Specification of the Request for
Japanese Patent Open to the Public No. 29697/75, which are incorporated herein by reference in their entirety.
Polyamides formed from isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, meta- or para-xylylenediamine, 1,3- or 1,4-cyclohexane (bis) methylamine, aliphatic diacids with 6 to 12 carbon atoms, aliphatic amino acids or lactams with 6 to 12 carbon atoms, aliphatic diamines with 4 to 12 carbon atoms, and other generally known diacid-forming polyamides and diamines can be used.
Polyamide matrix copolymers that can be used in the invention include the amorphous matrix polyamide copolymers described in WO 00/34372, entitled A High Barrier Amorphous Polyamide-Clay Nonocomposite and A
Process for Preparing Same, published June 15, 2000. The description of WO 00/34372 is incorporated herein by reference in its entirety, particularly for its description of some amorphous matrix polyamides and co-polyamides, their properties and methods for its preparation, and its use to form nanocomposite compositions. Amorphous polyamides can comprise the polycondensation polymerization reaction product (or residue) of a diamine component and at least one dicarboxylic acid component.
The dicarboxylic acid component of the amorphous polyamides can comprise a first diacid and preferably a second diacid. The diacids can be in any mole percent ratio of the total diacid moieties present in the amorphous polyamide.
Preferably one of the diacids is present in an amount of from about 10 to about 90 mole percent of the total diacid portions present in the polyamide, · more preferably from about 45 to about 85 and even more preferably about
fifty up to about 80 mole percent of the total diacid moieties present in the polyamide.
The dicarboxylic acids of the amorphous polyamides include, but are not limited to dicarboxylic acids having from 3 to about 40 carbon atoms, and more preferably the dicarboxylic acids selected from aromatic dicarboxylic acids having preferably from 8 to 14 atoms carbon, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, and / or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
In one embodiment of the amorphous polyamides, the diacid component can be defined by formula (I):
HO<sub>2</sub>CCH<sub>2</sub>X (RX)<sub>AND</sub>CH<sub>2</sub>CO<sub>2</sub>H (I) where X is —O—, —S-, O
YesOól, and R is an aromatic moiety comprising from 6 to about 13 carbon atoms.
Suitable R groups include, but are not limited
<img file="MXPA02005457A_D0008.tif" />
l <
»
6 defined by
Preferably, in the embodiment as formula I), the dicarboxylic acid component comprises iminodiacetic acid, <oxydiacetic acid, thiodiacetic acid, 1,4-phenylenedioxydiacetic acid, 1,3-5 phenylenedioxydiacetic acid, etc., or mixtures of the same.
Examples of additional suitable dicarboxylic acids include, but are not limited to italic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, phenylendi (oxyacetic) acid, sebacic acid, succinic acid, adipic acid, glutaric acid, azelaic acid, and the like.
The diamine component of the amorphous polyamides comprises an aliphatic diamine having from about 15 2 to about 12 carbon atoms. Aliphatic diamines can contain aromatic groups, as long as an alkylene group (eg, a methylene group) interposes between an amino group, and an aromatic ring. Aliphatic diamines also include cycloaliphatic diamines such as piperazine. Examples of suitable aliphatic diamines include, but are not limited to 1,2-ethylenediamine, 1,3-propylene diamine, 1,6-hexamethylenediamine, 1,12-dodecylenediamine, 1,4-cyclohexanbismethylamine, piperazine, or mixtures thereof. The diamine component of this invention also comprises partially aromatic diamines such as, n-xylylenediamine, and m-xylylenediamine, or mixtures thereof. More preferably, the partially aromatic diamines comprise m-xylylenediamine.
Other diamines or mixtures of diamines with the preferred diamine (m-xylylenediamine) can also be used to form the amorphous polyamide. Some representative polyamides of this invention include, but are not limited to those shown in Table 1.
<td>Example</td><td>Polyamide</td><td>IV.</td><td>T<sub>{</sub> (° C)</td><td>T<sub>m</sub> (° C)</td>
<td>to</td><td>PDA (MX)</td><td> 0.522</td><td> 96.7</td><td>None</td>
<td>b</td><td>PDA-IO-TPA (MX)</td><td> 0.403</td><td> 101.1</td><td>None</td>
<td>c</td><td>PDA-IO-NDA (MX)</td><td> 0.390</td><td> 101.1</td><td>None</td>
<td>d</td><td>A-19-IPA (MX)</td><td> 0.828</td><td> 104.1</td><td>None</td>
<td>c</td><td>A-18-TPA (MX)</td><td> 0.778</td><td> 103.8</td><td>None</td>
<td>F</td><td>A-18-NDA (MX)</td><td> 0.798</td><td> 106.3</td><td>None</td>
<td><sup>s</sup></td><td>A-i9-PÍDA (MX)</td><td> 0.498</td><td> 109.6</td><td>None</td>
The preferred amorphous high barrier matrix polyamides of this invention may comprise the reaction product or residue of a dicarboxylic acid component comprising at least two of adipic acid (Ai, 2,6naphthalen dicarboxylic acid (NDA), isophthalic acid (IPA) , terephthalic acid (TPA), 1,3-phenylenedioxydiacetic acid (PDA), 1,4-cyclohexanedicarboxylic acid (CHDA), and phenylindane dicarboxylic acid (PIDA), and a diamine component that
comprises m-xiiílendiamina (MX). The combination of at least two of the diacids with the diamine effectively disrupts the crystallization tendency of these macromolecules to allow clear transparent amorphous structures to be maintained throughout the processing steps. Using more than one diamine with a diacid can form an amorphous polyamide. Also, using more than one diacid and more than one diamine can form an amorphous polyamide. MX is the preferred diamine due to its high barrier properties.
Referring to Table 1, PDA (MX) means 100% mol of PDA with 100% mol of MX; PDA-10-TPA (MX) means 90% mol of PDA and 10% mol of TPA with 100% mol of MX; PDA-10NDA (MX) means 90% mol of PDA and 10% mol of NDA with 100% mol of MX; A-19-IPA (MX) means 81% mol of A and 19% mol of IPA with 100% mol of MX; A-18-TPA (MX) means 82% mol of A and 18% mol of TPA with 100% mol of MX; A-18-NDA (MX) means 82% mol of A and 18% mol of NDA with 100% mol of MX, A-18-PIDA (MX) means 821 mol of A and 18% mol of PIDA with 100% mol from MX.
The polyamides of the invention may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamides and polyamides that form polyamides known in the art.
Preferred partially aromatic polyamides include, but are not limited to poly (m-nililenadipamida, poly (m-xililen adipamida-co-isoftalamida), poly (hexamethylene isoftalamida), poly (hexamethylene isoftalamida-cotereftalamida ;, poly (hexamethylene-adipamide) -isophthalamide), poly (hexamethylene adipamide-co-terephthalamide), poly (hexamethylene isophthalamide-co-terephthalamide) and the like or mixtures thereof. The most preferred partially aromatic polyamides include, but are not limited to poly (m-xylylene adipamide), poly (hexamethylene isof talamide-co-teref talamide) -, poly (m-xylylene adipamide-co-isophthalamide), and / or mixtures from the same. The most preferred partially aromatic polyamide is poly (m-xylylene adipamide).
Preferred aliphatic polyamides include, but are not. limited to poly (hexamethylene adipamide) and polycaprolactam). The most preferred aliphatic polyamide is poly (hexamethylene adipamide). Partially aromatic polyamides are preferred over aliphatic polyamides when good thermal properties are crucial.
Preferred aliphatic polyamides include, but are not limited to polycapramide (nylon 6), poly20 aminoheptanoic acid (nylon 7), poly-aminonanoic acid (nylon 9), polyundecane-amide (nylon 11), polylaurylactam (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), noli ( hexamethien-dodecamide) (nylon 6,12), poly (octamethylene 30 adipamide) (nylon 8,6), poly (decamethylene-adipamide, (nylon 10.5), poly (dodecamethylene-adipamide) (niion 12, ···) and poly (dodecamecilen-sebacamide} ínii n 12.8).
The most preferred polyamides include poly (mxiiilen adipamide), polycapranide (nylon 6), and poly (hexamethylene adipamide) (nylon 6,6), poly (hexamethylene isophthalamide-co-terephthalamide), poly (m-xylylene adipamide-coisophthalamide) and the like or mixtures thereof. Poly (Mxililen Adipamide) is a preferred polyamide due to its availability, high barrier, and processability. Partially aromatic polyamides are preferred for use in bottles because of their high gas barrier properties.
Amorphous polyamides are generally prepared by processes that are well known in the art, including those described in WO 00/34372, which is incorporated herein by reference in its entirety.
Suitable polyesters include at least one dibasic acid and at least one glycol. The primary terephthalic, isophthalic dibasic acids are naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and various naphthalenedicarboxylic isomers or mixtures of isomers can be used, but 1,4-, 1,5-, 2,6- and isomers are preferred 2,<sup>7</sup>-. 1,4-Cyclohexanedicarboxylic acid can be in the form of cis, trans, or cis / trans mixtures. In addition to the similar forms.
For arid, lower alkyl esters or acid chlorides can also be used.
The matrix polyester can be prepared 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 optionally be modified with up to about 50 mole percent of one or more different dicarboxylic acids. Such additional dicarboxylic acids include dicarboxylic acids having from 3 to about 40 carbon atoms, and more preferably dicarboxylic acids selected from aromatic dicarboxylic acids having preferably from 8 to 14 carbon atoms, aliphatic dicarboxylic acids having preferably from 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms. Examples of suitable dicarboxylic acids include italic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, phenylenoxyacetic acid, succinic acid, glutaric acid, adipic acid, acid azelaic, sebasic acid, and the like. Polyesters can also be prepared from two or more of the above dicarboxylic acids.
Typical glycols used in the polyester include those containing from two to about ten carbon atoms. Preferred glycols include ethylene glycol, propanediol, 1,4-butanediol, i, u-hexandiol, 1,4-cyclohexanedimethanol, diethylene glycol, and the like. The glycol component can optionally be modified with up to about 50 mole percent, preferably up to about 25 mole percent, and more preferably up to about 15 mole percent of one or more different diols. Such additional diols include cycloaliphatic diols preferably having 3 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms. Examples of such diols include: diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane, 1,6-diol, 3-methylpentanediol- (2,4) , 2-merylpentanediol (1,4), 2,2,4-1rimethylpentane-diol- (1,3), 2-ethylhexanodiol (1,3), 2,2-diethylpropane-diol- (1,3), hexanediol - (1,3), 1,4-di (2-hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane , 2,2— bis- (3-hydroxyethoxyphenyl) -propane, 2,2-bis- (4hydroxypropoxyphenyl) -propane and the like. Polyesters can also be prepared from two or more of the above diols.
polyols
Such small amounts of trimethylolpropane, such as oentaerythritol, glycerol and the like can be used if multifunctional. When 1,4-cyclohexanedimethanol is used, it may be the cis, rans, or cis / trans mixtures. When phenylenedioxyacetic acid is used, it can be used as the 1,2 isomers; 1.3; 1,4, or mixtures thereof.
The polymer may also contain small amounts of trifunctional or tetrafunctional comonomers to provide controlled branching on the polymers. Such comonomers include trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, trimellitic acid, pyromellitic acid, and other polyester-forming polyacids or polyols generally known in the art.
Although not necessarily preferred, the polymers of the present invention may also include the additives normally used in the polymers. Illustrative of such additives known in the art are colorants, pigments, carbon black, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, reheat aids, crystallization aids, acetaldehyde reducing compounds, aids in recycle release, oxygen scavengers, plasticizers, nucleators, template release agents, compatibilizers and the like or combinations thereof.
All these additives and many others and their use are
3'·!
known in the art and do not require extensive discussion. Therefore, it will only refer to a limited number, it being understood that any of these compounds can be used in any combination as long as they do not hinder the present invention to achieve its objectives.
Amorphous Oligomers
Any amorphous oligomer (which may alternatively be referred to as an amorphous oligomeric resin) can be used in the nanocomposite or process of this invention, provided that the amorphous oligomer has sufficient compatibility with the matrix polymer to provide the desirable crystallization rate and improvement barrier in the final nanocomposite.
Amorphous, as used by this invention, means that the oligomer (or matrix polymer) does not show a meltdown at the crystallization peak on a second DSC examination at a
<td>speed</td><td colspan="2">20 ° C / min. Typically,</td><td colspan="2">a composition</td>
<td colspan="2">amorphous oligomeric se</td><td>characterized by</td><td>a</td><td>high degree of</td>
<td>clarity (</td><td>transparency)</td><td>) and a lack of</td><td>a</td><td>melting point</td>
<td>clearly</td><td>definite.</td><td>Polymers</td><td>of</td><td>amorphous matrix</td>
<td>preferred</td><td>or oligomers</td><td colspan="2">amorphous are those</td><td>with melting ΔΗ</td>
less than about 5 cal / g, preferably less than 3 cal / g, and more preferably less than about 1 cal / g, · as measured in the second cycle at an examination rate of about 20 ° C / min. Some have been found
<img file="MXPA02005457A_D0009.tif" />
Amorphous matrix oligomeric polymers provide additional benefits, including improved adhesion, improved recyclability, improved color, improved barrier, improved transparency, and combinations thereof.
Oligomers or oligomeric resins are typically low molecular weight versions of a high molecular weight matrix polymer. It should be understood that "oligomers" or oligomeric resins typically do not include any substantial concentration of purely monomeric or dimeric polymeric precursors that are generated during the initial stages of preparation of the high molecular weight matrix polymer. For example, a polyethylene terephthalate oligomer includes at most minor amounts of terephthalic acid, dimethyl terephthalate, ethylene glycol, ethylene glycol diacetate, the di- (ethylene glycol) ester of terephthalic acid, or similar monomeric or dimeric precursors of polyethylene terephthalate. . Likewise, a poly (m-xylylene adipamide) oligomer contains at most minor amounts of adipic acid, m-xylenediamine, or diamide comprising two m-xylenediamine residues attached to the carboxylic acid groups of adipic acid or monomeric or dimeric precursors. poly (m-xylylene adipamide). Preferably, the amorphous oligomeric resins of the present invention contain a total of less than about 5 weight percent precursors.
Π ζ polymeric, monomeric or dimeric. More preferably, the oligomeric resins contain a toral of less than about 3, 2, 1, or 0.5 weight percent polymeric, monomeric, or dimeric precursors.
In some embodiments, especially those of condensation polymers where at least two different difunctional monomers are required (at least monomers A "and monomers B), an oligomer or an oligomeric resin preferably has an average degree of polymerization of at least four repeating units monomeric. The generic use of oligomers derived from crystalline or semi-crystalline polyamides or polyester for the preparation of nanocomposites is described in WO 00/34377, published June 15, 2000, which is incorporated herein by reference in its entirety, for its description regarding to the preparation and utility of those classes of oligomeric resins in the formation of nanocomposites.
The preferred values for the IV or the molecular weight of the oligomers depend on various factors including the composition of the oligomer, the matrix polymer, and the clay selected and is easily determined by those skilled in the art without undue experimentation. Typically, the amorphous oligomers of the invention have an average molecular weight number of from about 200 to about 10,000 g / mol and can be a homo- or co-Λ.
oliqomer. Preferably, the amorphous oligomers have an average molecular weight number of from about 1000 to about 8000 g / mol. The amorphous oligomers are preferably co-oligomers. The IV of the oligomers prior to melt mixing is preferably approximately 0.1 and 0.5 dL / g, and more preferably 0.3 dL / g to 0.5 dL / g as measured in a mixture of 60 weight percent phenol and 40 percent 1,1,2,2-tetrachloroethane by weight at a concentration of 0.5 g / lOOml (solvent) at 25 ° C.
Such amorphous oligomers have been found to be very effective in dispersing an organo-layered clay material or another suitable to form a residue comprising an exfoliated nanocomposite. High dispersion of layered clay material can be induced if the layered clay material is mixed by fusion with the oligomers to form a concentrate, which is then dropped into an extruder or other similar device with a high matrix polymer molecular weight. Alternatively, the high dispersion of the layered clay material can also be obtained if the layered clay material, the oligomers and the high molecular weight matrix polymer are essentially melt blended simultaneously in a single pass mixing process.
While not wishing to be bound by theory, it is believed that the relatively low molecular weight and / or relatively low melting point of the amorphous oligomers of the invention aids in the rate of their diffusion and / or insertion into the clay material in layers, when compared to high molecular weight matrix polymers. The resulting increased penetration of the oligomers into the layered clay materials can therefore selectively improve the separation of the layered clay material to produce platelet particles, even when present at relatively low concentrations. This benefit effect is believed to be independent of any subsequent polymerization and / or increase in molecular weight of the oligomers, which is not believed to occur at a significant rate, or to significantly affect the properties of the nanocomposites of this invention.
The amount of amorphous polymer or oiigomer sufficient to overcome the nucleating effect of the clay inducing undesirably rapid crystallization of the matrix polymer will vary depending on variables including selection of the matrix polymer and selection and amounts of clays, clay treatments, and dispersion aids and is readily determined by those skilled in the art. Typically less than about 25 percent by weight of amorphous polymer or oligomer is required, preferably less than about 20 percent is used
is by weight of amorphous polymer or oligomer. Additionally, for compatibility with the matrix polymer, it is preferred that the amorphous polymeric or oligomeric resin and the high molecular weight matrix polymer have the same monomer unit.
The amorphous oligomers of the present invention are preferably polyamides and / or oligomeric polyesters. The oligomeric polyamide, for example, comprises the polycondensation polymerization reaction product (or residue) of at least one diamine component and at least one dicarboxylic acid component. In some preferred embodiments, the amorphous oligomeric polyamides of the present invention comprise at least two dicarboxylic acid components, and / or at least two diamine components. While not wishing to be bound by theory, it is believed that the increase in polymer chain disorder induced by the presence of more than one component of dicarboxylic acid or more than one component of two diamines tends to induce amorphous physical properties in the resulting oligomers.
Although preferred amorphous oligomers are linear or quasi-linear, polymers and oligomers can be used if desired with other architectures, including branched, star, crosslinked, and dendritic structures.
The amorphous oligomers of the present invention are synthesized by methods generally known in the art to produce polymer. For example, condensation polymer oligomers that typically have at least two different monomer units in a 1: 1 molar stoichiometry can easily be produced by unbalancing the 1: 1 polymerization stoichiometry of the amino and diacid end groups of the monomer units employed during the step of polycondensation of the synthesis of a matrix polymer.
The amorphous oligomeric polyamides employed in this invention can be prepared in analogy to the methods described in US Patent No. 5,340,884 which is incorporated herein by reference in its entirety. For example, the melt phase polymerization from a diacid-diamine complex can be employed, which can be prepared in situ or in a separate step. In any method, diacids and diamines are used as starting materials. Alternatively, an ester form of the diacid, preferably the dimethyl ester, can be used. If the ester is used, the reaction should be carried out at a relatively low temperature, generally 80 degrees to 120 degrees C, until the ester is converted to an amide. The mixture is then heated to the polymerization temperature. When the diacid-diamine complex is used, the mixture is heated to melt and stirred to equilibrium.
<td></td><td>The</td><td>weight</td><td>molecular</td><td>of the oligomers</td><td>amorphous</td><td>I know</td>
<td>controls</td><td>by</td><td>the</td><td>proportion</td><td>diacid-diamine. A</td><td>excess</td><td>of</td>
<td>monomers</td><td>of</td><td colspan="2">diamine produces</td><td>a concentration</td><td>higher</td><td>of</td>
terminal amino groups. An excess of diacid monomers produces a higher concentration of terminal acid groups.
Diacid chlorides, esters, etc., can be suitably used. A solvent can be used in the preparation of the oligomers.
The amorphous oligomeric resins of the current invention do not comprise oligomeric (m-xylylene adipamide) (i.e. oligomeric MXD6), which is a non-amorphous, semi-crystalline material.
Materials, of clay (Platelet Particles)
The nanocomposite composition of the present invention comprises less than about 25 weight percent, preferably from about 0.5 to about 20 weight percent, more preferably from about 0.5 to about 15 weight percent, and more preferably from about 0.5 up to about 10 weight percent of a layered clay material. The layered clay material comprises or can be treated or dispersed to produce platelet particles. The amount of platelet particles is determined by measuring the amount of silicate residue in the ashes of the polymer / platelet composition when treated in accordance with ASTM D563.0-94.
Clay materials<sup>-</sup> Useful include synthetic and modified phyllosilicates. Natural clays include smectite clays, such as montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, beidelite, volconscoite, magadite, ceniaite, and the like. Synthetic clays include synthetic mica, synthetic saponite, synthetic hectorite, and the like. Modified clays include fluoronated montmorillonite, fluorinated mica, and the like. Suitable clays are available from various companies including Nanocor, Inc., Southern Clay Products, Kunimine Industries, Ltd., and Elementis-Rheox.
Generally, the layered clay materials useful in this invention are an agglomeration of individual platelet particles that are tightly stacked like cards in a deck in dominoes called tactiles. The individual platelet particles of the clays preferably have a thickness of less than about 2 nm and a diameter in the range of about 10 to about 3000 nm.
Preferably, the clays are dispersed in the polyamide so that most of the clay material exists as individual platelet particles, small tactiles, and small aggregates of tactiles.
they have a capacity of approximately 0.3 milliequivalents per
Preferably, a majority of the tactiles and aggregates in the residues comprising the polyamide / clay nanocomposites of the present invention will have thickness in their smallest dimension of less than about 20 nm. Polyamide / clay nanocomposite compositions with the highest concentration of individual platelet particles and least tactile or aggregates are preferred.
In addition, layered clay materials are typically extensible free-flowing powders that have a cation exchange capacity of up to about 3.0 gram of mineral (meq / g), preferably of about 0.90 to about 1.5 meq / g, and more preferably of about 0.95 15 to about 1.40 meq / g. Clay can have a wide variety of interchangeable cations present in the galleries between the layers of the clay, including, but not limited to cations, comprising the alkali metals (group IA), the alkaline earth metals (group 20 HA), and its mixtures. The most preferred cation is sodium; however, any cation or combination of cations can be used provided that most of the cations can be exchanged for organic cations (onium ions). The exchange can occur by treating an individual clay or a mixture of clays with organic cations.
<td>The</td><td>materials</td><td>clay</td><td>preferred</td><td>are</td>
<td>phyllosilicates</td><td>2: 1 type</td><td>what's wrong with it</td><td>a capacity</td><td>of</td>
<td>exchange</td><td>cationic</td><td>0.5 to 2.0</td><td colspan="2">meq / g. In many</td>
<td>modalities,</td><td>the materials</td><td>clay</td><td>they are minerals</td><td>of</td>
<td colspan="3">smectite clay, particularly</td><td>bentonite</td><td> 0</td>
montmorillonite, more particularly Wyoming type sodium montmorinolite or Wyoming type sodium bentonite having a cation exchange capacity of about 0.95 to about 1.25 meq / g. Such clays are readily available in the United States and other parts of the world including Kunipia clays available from Kunimine Industries, Inc.
Other non-clay materials that have the ion exchange capacity described above and size, such as chalcogens, can also be used as a source of platelet particles under the present invention. Calcogens are salts of a heavy metal and the VIA group (O, S, Se, and Te). These materials are known in the art and need not be described in detail here.
Improvements in the gas barrier result from increases in the concentration of platelet particles in the polymer. While amounts of platelet particles as low as 0.01 percent provide improved barrier (especially when well dispersed and ordered), compositions having at least about 0.5 weight percent of platelet particles are preferred because they show the desired improvements in gas permeability.
Prior to incorporation into the polyamide, the particle size of the clay material is reduced in size by methods known in the art, including, but not limited to, grinding, spraying, hammer mill, jet mill, and their combinations. It is preferred that the average particle size be reduced to less than 100
<td>10 micron</td><td>of</td><td>diameter,</td><td>more preferably less</td><td>of</td><td> 50</td>
<td>microns</td><td>of</td><td>diameter,</td><td>and more preferably less</td><td>of</td><td> 20</td>
<td>microns</td><td>of</td><td>diameter.</td><td></td><td></td><td></td>
<td></td><td>The</td><td>material</td><td>clay of this invention</td><td colspan="2">can</td>
comprise refined but unmodified clays, modified clays, or mixtures of modified and unmodified clays. Generally, it is desirable to treat the selected clay material to facilitate separation of the agglomerates of platelet particles into individual platelet particles and small tactiles. Separating the platelet particles prior to incorporation into the polymer also improves the polymer / platelet interface. Any treatment that achieves the above goals 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 this invention. Clay treatments can be conducted before, during, or after mixing the clay material with the polymer.
Organic Cations
In one embodiment of this invention, a layered clay material interspersed by the reaction and / or treatment of an expandable layered clay material with a composition compound comprising or capable of generating organic cations, preferably a compound of ammonium (to carry out partial or complete cation exchange). If desired, two or more organic cations can be used to treat a clay. Furthermore, mixtures of the organic cations can also be used to prepare an interlayer layered clay material, wherein the interlayer layered clay material in a polyamide nanocomposite comprises a mixture of intercalated clays, The process for preparing organoclays (clays interspersed) can be conducted in a batch, semi-batch or continuous form.
The organic cations used to intercalate a clay material or a mixture of clay materials of a nanocomposite of this invention can be derived from organic cationic salts, preferably onium salt compounds. Organic cationic salts useful for the nanocomposite and process of this invention can generally be represented by the following formula
XR4 (I) where M is nitrogen or phosphorus, X 'is a halide, hydroxide, or acetate anion, preferably chloride and bromide; and
Ri, R<sub>2</sub>, R<sub>3</sub>, and R<sub>4</sub> they are independently organic and / or oligomeric ligands or can be hydrogen.
Examples of useful organic ligands include, but are not limited to, linear or branched alkyl groups having 1 to 22 carbon atoms, aralkyl groups that are benzyl, and substituted benzyl portions that include fused ring portions that have linear chains or branches from 1 to 100 carbon atoms in the alkyl portion of the structure, aryl groups such as phenyl and substituted phenyl including fused ring aromatic substituents, beta groups, gamma, unsaturated having six or fewer carbon atoms, and alkyleneoxide groups having repeating units comprising 2 to 6 carbon atoms. Examples of useful oligomeric ligands include, but are not limited to alkylene polyoxide, polystyrene, polyacrylate, polycaprolactone, and the like.
Quaternary ammonium compounds are a preferred class of organic cations, especially quaternary ammonium cations containing one or two long-chain alkyl groups having at least about 12 carbon atoms, such as octadecyl or tallow groups, one or more groups lower alkyl such as a methyl group, and one or two alkylene oxide groups having monomeric or repeating units comprising from 2 to 6 carbon atoms.
Examples of useful organic cations include, but are not limited to, alkylammonium ions, such as tetramethylammonium, hexylammonium, butylammonium, bis (2hydroxyethyl) dimethylammonium, hexyl benzyl dimethyl ammonium, benzyl trimethyl ammonium, butyl benzyl dimethyl ammonium, tetrabutyl ammonium, di ( 2-hydroxyethyl) ammonium, and the like, and alkyl phosphonium ions such as tetrabutyl phosphonium, trioctyl octadecyl phosphonium, tetraoctyl phosphonium, octadecyl triphenyl phosphonium, and the like or mixtures thereof.
Other organic cations particularly useful for this invention include, but are not limited to alkyl ammonium ions such as dodecyl ammonium, octadecyl trimethyl ammonium, bis (2-hydroxyethyl) octadecyl methyl ammonium, octadecyl benzyl dimethyl ammonium, and the like or mixtures thereof.
Illustrative examples of suitable polyalkoxylated ammonium compounds include the hydrochloride salts of polyalkoxylated amines such as JEFFAMINE (ex Huntsman
Chemical), especially, JEFFAMINE-506 and JEFFAMINE 505, and an amine available under the trade name ETHOMEEN (from Akzo Chemie America), especially, ETHOMEEN 18/25 which is octadecyl bis (polyoxyethylene [15]) amine, where the numbers in square brackets they refer to the average number of ethylene oxide units. A further illustrative example of a suitable polyalkoxylated ammonium compound is ETHOQUAD 18/25 (ex Akzo Chemie America) which is octadecyl methyl bis (polyoxyethylene [15]) ammonium chloride.
Numerous methods are known for modifying clays in layers with organic cations, and any of these can be used in the practice of this invention. One embodiment of this invention is the organic modification of a layered clay with an organic cationic salt by the process of dispersing a layered clay or clay mixture in hot water, more preferably 50 to 80 ° C, adding an ammonium salt organic (pure or dissolved in water or alcohol) or an organic amine and a Bronsted acid (thereby forming the organic ammonium salt in situ) or their combinations and mixtures with stirring, then combining for a period of time sufficient for the organic cations to exchange most of the metal cations present in the galleries between the layers of the clay materials. The organically modified layered clay materials are then isolated by known methods in
the technique, including, but not limited to, filtration, centrifugation, spray drying, and combinations thereof.
It is desirable to use a sufficient amount of the organic cationic salts to allow the exchange of most of the metal cations in the galleries of the layered particles for the organic cations; therefore, at least about 0.5 equivalent of total organic cation salts are used and up to about 3 equivalents of organic cation salts can be used. It is preferred that approximately 0.5 to 2 equivalents of organic cationic salts are used, more preferably
<td>about 1.0 to 1.5</td><td>equivalents.</td><td>. Is</td><td>desirable but not</td>
<td>it is required to remove the</td><td>majority of</td><td>the</td><td>cationic salts</td>
<td>metallic and most</td><td>of excess</td><td>of</td><td>cationic salts</td>
<td>15 organic washing and others</td><td colspan="2">known techniques</td><td>in the technique.</td>
Other Clay Treatments
The clay can be further treated for the purposes of aiding peeling in the compound and / or improving the strength of the polyamide / clay interface.
Any treatment that achieves these goals can be used. Examples of useful treatments include intercalation with water-soluble or water-insoluble polymers, organic reagents or monomers, silane, metal or organometallic compounds, and / or combinations thereof. The treatment of the clay may be accomplished prior to the addition of a polyamide to the clay material mixture, during dispersion of the clay with the polyamide, or during a subsequent melt combination or melt fabrication step.
Examples of useful pretreatment with polymers and 5 oligomers include those described in US Patents 5,552,469 and 5,578,672, incorporated herein by reference. Examples of polymers useful for treating the clay material include polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, polytetrahydrofuran, polystyrene, polycaprolactone, some water dispersible polyesters, Nylon-6, and the like.
Examples of useful pretreatment with organic reagents and organic monomers include those described in EP 780,340 Al, incorporated herein by reference. Examples of useful organic monomers and reagents for intercalating expanded layered clay include dodecyl pyrrolidone, caprolactone, caprolactam, ethylene carbonate, ethylene glycol, bishidroxyethyl terephthalate, dimethyl terephthalate, and the like or mixtures thereof.
Examples of useful pretreatment with silane compounds include those treatments described in WO 93/11190, incorporated herein by reference. Examples of useful silane compounds include (3-glycidoxypropyl) trimethoxysilane, 2-methoxy (polyethylenexy) propyl heptamethyl trisiloxane, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium, and the like.
If desired, a dispersion aid may be present during or prior to compounding by melt mixing for purposes of assisting the exfoliation of the treated or untreated expandable layer particles within the polyamide. Many such dispersing aids are known, covering a wide range of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents, and the like or combinations thereof.
It should be appreciated that on a total composition basis, dispersion aids and / or pretreatment compounds can account for a significant amount of the total composition, in some cases up to about 30 weight percent. While it is preferred to use as little dispersion / pretreatment aid compound as possible, the amounts of the dispersion aids and / or pretreatment compounds can be as much as about 8 times the amount of the platelet particles.
Articles
The clay-polyamide nanocomposites of this invention can be formed into articles by conventional plastic processing techniques. Molded articles can be made from the described polyamides
formerly by compression molding, blow molding or other such molding techniques, all of which are known in the art. Monolayer and / or multilayer articles prepared from the nanocomposite material of this invention include, but are not limited to film, sheet, pipes, tubes, profiles, molded articles, preforms, films, and stretch blow molded containers, containers injection blow molded, extrusion blow molded films and containers, thermoformed articles and the like. The containers are preferably bottles.
The bottles and containers of this invention provide increased shelf life for contents, including beverages and foods that are sensitive to gas permeation. The articles, most preferably containers, of the present invention frequently show a gas transmission or permeability rate (oxygen, carbon dioxide, water vapor) of at least 10% less (depending on the clay concentration) than that of containers. Similar made from clay free polymers, resulting in a corresponding longer shelf life of the product provided by the container. Desirable values for side wall modulus and tensile strength can also be maintained. Articles also show unexpected resistance to
> ·. -T »~> ^» 3.
Fog formation, crystallization, and other formation defects.
Items can also be multi-layered. Preferably, the multi-layer articles have a nanocomposite material disposed in-between the other layers, although the nanocomposite may also be a single-layer or two-layer article. In embodiments where the nanocomposite and its components are approved for food contact, the nanocomposite can form the food contact layer of the desired articles. In other embodiments, it is preferred that the nanocomposite be in a different layer than the food contact layer.
Multilayer articles may also contain one or more layers of the nanocomposite composition of this invention and one or more layers of a structural polymer. A wide variety of structural polymers can be used. Illustrative of structural polymers are polyesters, polyether esters, polyamides, polyesteramides, polyurethanes, polyimides, polyetherimides, polyureas, polyamidaimides, polyphenylenoxides, phenoxy resins, epoxy resins, polyolefins, polyacrylates, polystyrene alcohols, polyethylene alcohols. , and the like or their mixtures and combinations. Preferred structural polymers are polyesters, such as polyethylene terephthalate and its copolymers.
<img file="MXPA02005457A_D0010.tif" />
In another embodiment, co-extruding a layer of the clay-polyamide nanocomposite specified above with some other suitable thermoplastic resin can form articles. The clay-polyamide nanocomposite and the molded article and / or extruded sheet can also be formed at the same time by co-injection or co-extrusion molding.
Another embodiment of this invention is the combined use of uniformly dispersed silicate layers in the matrix of a high barrier thermoplastic along with the proposal of multiple layers for packaging materials. By using a layered clay to decrease gas permeability in the high barrier layer, the amount of this material that is needed to generate a specific barrier level in the final application is greatly reduced.
Since high barrier material is frequently the most expensive component in multilayer packaging, a reduction in the amount of this material used can be quite beneficial. With the clay-polyamide nanocomposite layer being sandwiched between two other outer polymeric layers, the surface roughness is often considerably less than for a monolayer nanocomposite material. Thus, with a multi-layer proposal, the fog level can be further reduced.
To form stretch blow molded bottles
of one or several layers, it is often customary to initially form a preform of the desired cup by means of an injection molding process. The crystallization rate of the materials comprising the preform must be slow enough to allow the formation of an essentially non-crystalline article. Unless the preform is essentially non-crystalline, it is excessively difficult to stretch blow mold into the desired shape to form a bottle. In a key embodiment of this invention, the layered silicate materials and treatment compounds are selected to promote the dispersion of the individual platelets within the polymer, preferably polyamide, to allow for increased maximum barrier, minimal mist formation and formation of injection molding preforms that are essentially non-crystalline in character.
Processes
Many processes are known for preparing platelet-polymer particle compositions, and any of these processes can be used to prepare the compounds of this invention. Although any melt mixing device can be used, typically, the melt mixing step is conducted by a batch mixing process or by a melt composition extrusion process during which the treated layered particles or
untreated are introduced into a polyamide. The use of the composition by extrusion is preferred to mix the clay and the oligomers and / or the matrix polymer due to the ease of preparation and the potential to achieve high clay loads. Before fusion mixing, the treated or untreated layered particles can exist in various forms including pellets, flakes, chips, and powder. It is preferred that the treated or untreated layered particles are reduced in size by methods known in the art, such as hammer milling and jet milling.
This invention generally relates to a process comprising the steps of (1) preparing a polymeric and / or oligomeric platelet particle-resin compound by melt mixing platelet particles and an amorphous polymeric and / or oligomeric resin and (2) preparing a high molecular weight platelet-polymer nanoparticle (clay) material.
In a first embodiment, this invention relates to a process for preparing a polymer clay nanocomposite comprising the steps of: (i) melt mixing a layered clay material with a matrix polymer compatible amorphous oligomeric resin to form a compound of clay-resin, and (ii) mixing the platelet-resin particle compound with a high-matrix polymer
molecular weight, producing a polymeric nanocomposite material. The amorphous oligomeric resins of this invention are not believed to further appreciably polymerize or their molecular weights to increase significantly during these melt mixing steps.
Although any melt mixing device can be used, typically, the melt mix step is
<td>leads in</td><td>a</td><td>mixing process</td><td>in batch or by</td><td>a process of</td>
<td>extrusion</td><td>of</td><td colspan="2">composition by fusion during</td><td>which the</td>
<td>10 particles</td><td>in</td><td>layers treated or</td><td>untreated</td><td>are introduced</td>
<td>within</td><td>a</td><td>oligomeric resin</td><td>or polymeric</td><td>amorphous. Before</td>
From the melt mix, the oligomeric or polymeric resin can exist in a wide variety of forms including pellets, ground chips, powder, or its molten state.
Referring to the first embodiment of this invention, in one embodiment, the melt mixing step can be accomplished by dry mixing the oligomeric or polymeric resin with the treated or untreated layered particles then passing the mixture through a low composition extruder. Sufficient conditions to melt the oligomeric or polymeric resin.
In another embodiment of the first embodiment, the melt mixing step is conducted by feeding the amorphous oligomeric or polymeric resin and treated or untreated layered clay particles separately into a
composition extruder. When the treated layered particles are used in this process, it is preferred that the resin is added first to minimize degradation of the treated layered particles.
Using the composition by extrusion to mix the clay and the resin has two advantages. Mainly, the extruder is capable of handling the high viscosity presented by the nanocomposite material. Furthermore, in a proposal for fusion mixing to produce nanocomposite materials, the use of solvents can be avoided. Low molecular weight liquids can often be from the nanocomposite resin.
The amorphous oligomeric or polymeric resin and the high molecular weight matrix polymer can have the same or different repeat unit structure, that is, they can be comprised of the same or different monomer units. Preferably, the resin has the same monomer unit to improve compatibility or miscibility with the high molecular weight matrix polymer.
In another embodiment of this invention, the molten amorphous polymeric or oligomeric resin can be fed directly to a composition extruder along with the treated or untreated layered particles to produce the platelet-resin particle compound.
If desired, a dispersing aid may be
niÉiiaa.ÉtiiijlIfi 'present during or before the formation of the compound by fusion mixing for the purposes of assisting the exfoliation of the particles in expandable treated or untreated layers within the polymer. Many such dispersion aids are known that cover a wide range of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents and the like or combinations thereof.
The formation of platelet-polymer particle (clay) nanocomposites can be accomplished by several different methods. For polyesters, these include, but are not limited to, melt processable polyester melt composition.
For polyamides, the formation of a nanocompound includes, but is not limited to, the melt composition of an oligomeric polyamide compound with a high molecular weight melt processable polyamide. The monomeric unit of the melt processable polyamide may be the same or different from the amorphous oligomeric polyamide.
In one embodiment of this invention, the melt mixing step is accomplished by dry mixing the polyamide matrix, the amorphous polymer or oligomer, and the treated layered particles then passing the mixture through a composition extruder under conditions sufficient to melt the polyamide.
In another embodiment of this invention, the melt mixing step is conducted by feeding a matrix of amorphous polyamide, polymer or oligomer, and separately treated layered particles into a composition extruder. In one embodiment of this invention, an oligomeric polyamide or amorphous eopolymer is melt blended with the treated clay to form a concentrate that is then melt blended with a matrix polyamide. This process can be conducted in two separate steps in which the concentrate is isolated as a solid, or in a two-step series in which the concentrate is used as a melt mix, or in a single step in which the components are added simultaneously or sequentially.
If desired, the compounds may be treated before, during, or after the preparation of the compounds of this invention for the purposes that other fillers, additives, and reagents incorporate. Useful additives and reagents include, but are not limited to adhesive modifiers, oxygen scavenging catalysts, oxygen scavengers, toners, dyes, coloring agents, UV absorbers, mold release agents, impact modifiers, and combinations thereof. . Useful fillers include, but are not limited to, glass fibers, glass beads, carbon black, carbon fiber, titanium dioxide, and the like or combinations thereof.
Examples
The following examples and experimental results are included to provide those of common skill in the art with a full description and representation of the particular forms, in which the present invention may be practiced and evaluated, and are intended to be exemplary of the invention only and not they try to limit the scope of what the inventors consider to be their invention.
Efforts have been made to ensure precision with respect to numbers (eg, quantities, temperature, etc.); however, some errors and deviations may have occurred. Unless otherwise noted, parts are parts by weight, temperature is in ° C or at room temperature, and pressure is at or near atmospheric.
Comparative Example 1
A low molecular weight semi-crystalline poly (m-xylylene adipamide) was prepared and determined to possess an average molecular weight number of approximately 3,000 (per amine and carboxylate end group titration) and to have an IV of approximately 0.415 dL / g . 1625 grams (81% by weight) of this oligomeric poly {mxililenadipamide) were dry mixed with 376 grams (19% by weight) of
1.28MC, an organoclay available from Nanocor,
Inc., then dried at 80 ° C overnight in a vacuum oven. The mixture was then extruded into a Leistritz Micro 18 co-rotating twin screw extruder equipped with a general composition screw. The pellet feeder
AccuRate was set at 10 rpm, a speed of approximately 4 kg / hr, with a nitrogen atmosphere on the feeder and hopper. Barrel and die temperatures were set at 235 ° C for zone 1, 240 ° C for zones 2 through 6, 245 ° C for zone 7, and 250 ° C for zone 8. Screw turn was approximately 250 rpm. The material was air-cooled on a casting strip, then pelletized as it exited the extruder. After extrusion was complete, 155.6 grams (16% by weight) of the pellets were dry mixed with 845.0 grams (84% by weight) of polyamide MXD6 6007, of
Mitsubishi Gas Company. The mixture was then extruded into the Leistritz extruder under the same conditions used with the polymer clay mixture except that the temperature in zone I was 240 ° C, the temperature in zones 2 through 8 was 260 ° C, and the AccuRate feeder it was set at 4.0 rpm, at a feed rate of approximately 2 kg / hour.
The material obtained was determined to comprise
2.0% by weight of ash due to clay. The material obtained was characterized by light microscopy (OM), electron transmission microscopy (TEM), and wide-angle X-ray diffraction (WAXD) to determine the degree of dispersion of the organoclay within the polymer matrix and to assess the morphology of the composite material. The composite material was found to have a high degree of transparency, the clay is well distributed within the polymer matrix, and most of the clay is exfoliated into individual layers and small tactiles. The crystallization characteristics of this material were analyzed using differential scanning calorimetry. The t<sub>m</sub>
<td>is 237 ° C</td><td>with ΔΗ = 13 cal / g, and</td><td>the T<sub>DC</sub>-T<sub>ch</sub></td><td>is</td><td> 41.</td><td></td><td></td>
<td> 10</td><td>A</td><td>movie</td><td>of</td><td>three</td><td>layers</td><td>than</td>
<td>understands</td><td>an inner layer</td><td>22%</td><td>in</td><td colspan="2">volume of</td><td>this</td>
Composed with two external layers of PET-9921, available from. Eastman Chemical Company. The oxygen permeability of the film was then determined on a Mocon
Oxatran 2/20 which is 1.3 cc-mil / 100 in<sup>2</sup>-day-atm. A 4-square-inch section of the three-layer film was stretched on an instrument Τ. M. Long (4x4 orientation at approximately 110 ° C). The percent fog of the oriented film was determined to be 6.8% and the oxygen permeability was determined to be 0.63 cc-mil / 100 in-day-atm.
Comparative Example 2
The procedure of Comparative Example 1 was repeated except that of the heavy materials was adjusted to 233 grams (23% by weight) of the extrusion pellets and 767 grams (77% by weight) of the MXD6 6007 to give a compound comprising 3.0%
by weight of ash. The results are shown in Table 2 below.
Comparative Example 3
The procedure of Comparative Example 5 1 was repeated except that the amount of the heavy materials was adjusted to 78 grams (8% by weight) of the extruded pellets and 923 grams (92% by weight) of MXD6 6007 to give a compound comprising 1.0% by weight of ash. The results are shown in Table 2 below.
Example 1
The procedure of Comparative Example 1 was repeated using a 50/50 low molecular weight amorphous poly (m-xylylene adipamide-co-mxilylenysophthalamide) copolymer with IV of approximately 0.48 dL / g in place of the low weight poly (m15 xylynadipamide) molecular. The amorphous poly (mxililenadipamide-co-m-xylylene isophthalamide) can be prepared in analogy with the method described in Example 12 of US Patent No. 5,340,884. 724 grams (83% by weight) of this oligomeric poly (m20 xylylene adipamide-co-m-xylylene isophthalamide) were dry mixed with
153 grams (17% by weight) of 1.28MC, available from Nanocor, Inc., then dried at 75 ° C for a weekend in a vacuum oven. The blend was then extruded into the Leistritz co-gyrated twin screw extruder:
Micro 18 equipped with a general composition screw. The AccuRate pellet feeder was set at 4 rpm, a feed rate of approximately 2.0 kg / hr, with a nitrogen atmosphere above the feeder and hopper. Barrel and die temperatures were set at 235 ° C for zone 1, 250 ° C for zones 2 through 6, and 260 ° C for zones 7 and 8, and the screw turn was approximately 300 rpm. After the extrusion was complete, 803 grams (17% by weight) of the extruded pellets were dry mixed with 4009 grams (83% by weight) of polyamide MXD6 6007, available from Mitsubishi Gas Company. The mix was then extruded into the Leistritz extruder under the same conditions used with the polymer clay mix except that the temperature in zone 1 through 6 was 250 ° C, zones 7 and 8 was 260 ° C, and the AccuRate feeder was set at 3.5 rpm, a slightly slower feed rate of about 2kg / hour. The results are shown in the
Table 2.
The material obtained was determined to comprise 2.1% by weight of ash due to clay. The material obtained was then characterized by light microscopy (OM), electron transmission microscopy (TEM), and wide angle X-ray diffraction (WAXD) to determine the degree of dispersion of the organoclay within the polymer matrix and to assess the morphology of the composite material. The composite material was determined to have a ·· 'ti
High degree of transparency, the clay is well distributed within the polymer matrix, and most of the clay is exfoliated into individual layers and small tactiles. The crystallization characteristics of this material were analyzed using differential scanning calorimetry. The t<sub>m </sub>is 234 ° C with ΔΗ = 11 cal / g, and the T.<sub>::;</sub>-T<sub>ch</sub> is 9, demonstrating a significant reduction in crystallization rate with few and some reduction in melting point and percent crystallinity.
A three layer film comprising a 21 volume% inner layer of this compound was extruded with two outer layers of PET-9921, available from Eastman Chemical Company. The oxygen permeability of the film in a 2/20 Mocon Oxatran was later determined to be 0.17 cc15 mil / 100 in-day-atm, demonstrating a significant improvement in the barrier. A 4-inch square section of the three-layer film was stretched using a TM instrument (4x4 orientation at approximately 110 ° C). The percent of oriented film fog was determined to be 2.9% and the oxygen permeability was determined to be 0.56 cc-mil / 100 in.<sup>2</sup>-day-atm.
Example 2
The procedure of Comparative Example 1 was repeated using an amorphous low molecular weight poly (m-xylylenediglylamide) with IV of 0.30 dL / g. 165 dry blended
grams (83¾wt) of this oligomeric poly (m-xylylene glycollamida) with 35 grams (17wt%) of 1.28MC, available from Nanocor, Inc. After extrusion was completed, they were mixed into Dry 185 grams (19- ·· by weight) of the extruded pellets with 792 grams (81% by weight) of polyamide MXD6 6007, available from Mitsubishi Gas Company. The mixture was then extruded in the Leistritz extruder under the same conditions used as in Example 1. The results are shown in Table 1. The material obtained was determined to comprise 2.0% by weight of ash due to clay. The material obtained was then characterized by light microscopy (OM), electron transmission microscopy (TEM), and wide angle X-ray diffraction (WAXD) to determine the degree of dispersion of the organoclay within the polymer matrix and to assess the morphology of the composite material. The composite material was found to have a high degree of transparency, the clay is well distributed within the polymer matrix, and most of the clay is exfoliated into individual layers and small tactiles. The crystallization characteristics of this material were analyzed using differential scanning calorimetry. The t<sub>m </sub>is 235 ° C with ΔΗ = 12 cal / g, and the T<sub>DC</sub>-T<sub>ch</sub> is 25, demonstrating a significant reduction in crystallization rate with few and some reduction in melting point and percent crystallinity.
A three layer film comprising a 21 volume% inner layer of this compound was extruded with two outer layers of PET-9921, available from Eastman Chemical Company. The oxygen permeability of the film was determined to be 0.62 ccmil / 100 in.<sup>2</sup>-day-atm, demonstrating a significant improvement in the barrier. A 4 square inch section of the three layer film was stretched using a TM Long instrument (4x4 orientation at approximately 110 ° C). The percent of oriented film fog was determined to be 2.9% and the
Λ oxygen permeability is 0.62 cc-mil / 100 in -day-atm.
The benefits of using an eopolymer or oligomer are demonstrated in Table 2 below. Table 1 shows the observed values of T<sub>DC</sub>-T<sub>c</sub>h and oxygen and fog permeabilities for three-layer films (with PET-9921 outer layers from Eastman Chemical Company) comprising clay-MXD6 and pure MXD6 compounds comprising crystallizable polyamide oligomers, see Comparative Examples 1-3 . The results show that using crystallizable oligomers provides a significant barrier improvement, as indicated by the reduced oxygen permeability, but also increases the crystallization rate, as indicated by an increase in the value of T<sub>DC</sub>~ T<sub>C</sub>h and fog greatly increased, especially after orientation. Table 1 also shows the observed values of T, -<sub>c</sub>-T<sub>ch</sub> and the oxygen permeabilities of the three layer film (with PET-9921 outer layers) for clay-MXD6 compounds comprising amorphous polyamide oligomers and amorphous polyesters, see Examples 1 and 2. The results show that using oligomers or polymers amorphous reduce the crystallization rate, as indicated by a decrease in the value of T<sub>DC</sub>-T<sub>ch</sub>, without significantly reducing the melting point or percent crystallinity of the matrix, as indicated by T<sub>m</sub>, and ΔΗ, while achieving superior barrier, as indicated by reduced oxygen permeability and maintaining an acceptably low amount of mist. Thus, it is surprising that the use of an amorphous oiigomer with a layered clay material provides compounds that have the desired crystallinity with reasonable crystallization rates, improved barrier, and reduced fog.
TABLE 2
<td></td><td colspan="2">Variables of composition</td><td colspan="3">Thermal Properties</td><td colspan="3">Three Layer Film Properties</td>
<td>Example</td><td>Copolymer or Oiigomer</td><td>wt% clay</td><td>Tcc-Tch</td><td>Tm (° C)</td><td>ΔΗ (cal / g)</td><td>Barrier layer Vol%</td><td>Oxygen permeability disoriented / or disoriented (ce- rní 1/10 0inch<sup>:</sup>day-atm)</td><td>'έ of Fog</td>
<td>MXD6 Control</td><td>None</td><td>None</td><td> 34</td><td> 236</td><td> 13</td><td> 22</td><td> 1.5/0.94</td><td> 1.5</td>
<td>Example Comparative one</td><td>Oiigomer of polyamide crystallizable</td><td> 2.0</td><td> 41</td><td> 237</td><td> 13</td><td> 22</td><td> 1.3/0.63</td><td> 6.8</td>
<td>Example Comparative</td><td>Polyamide oiigomer</td><td> 3.0</td><td> 45</td><td> 237</td><td> 13</td><td> 29</td><td> 0.72/0.58</td><td> 7.3</td>
<img file="MXPA02005457A_D0011.tif" />
<td></td><td>Ά Γ i 3 taiiz</td><td>uble</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>E i emolo '' omparat ivo</td><td>Oli-d omero poi shaggy</td><td>ae able</td><td> 1.1</td><td> 34</td><td> 2 37</td><td></td><td> 23</td><td> . 1/0.63</td><td> 1.9</td>
<td>Example 1</td><td>poly ami oliomer: to love</td><td>of</td><td> 2.1</td><td>d</td><td> 2 3 4</td><td>: L</td><td> 21</td><td>a.17 / 0.56</td><td> 2.9</td>
<td>Example 2</td><td>Olictomer cop amorphous</td><td>of</td><td> 2.0</td><td> 25</td><td> 235</td><td> - -</td><td> 21</td><td> 0,62/0.62</td><td> 2.9</td>
Example 3
Example 3 illustrates a one-step process for the preparation of the nanocomposites of the invention. In this example all three ingredients, a pretreated organoclay, an amorphous oligomeric resin, and the matrix polymer are fed into the extruder feed end in a one step process.
A matrix polymer, MXD6 6007, poly (mxililenadipamide) with an IV of approximately 1.1 dL / g, can be purchased from Mitsubishi Chemocal Co.
An organomontmorillonite clay starting material, (such as Nanomer, 134.MN) can be provided by Nanocor Inc. of Arlington Heights, IL, or prepared by a process similar to the following. An initial montmorillonite layered clay material can be purified by the process described in the Patent
North American No. 6,050,509. The organomontmorillonite clay is then prepared by exchanging the purified Na-montmorillonite with bis (220 hydroxyethyl) octadecyl methyl ammonium chloride for onium ions. The finished organoclay product is washed with an alcohol / water mixture to remove excess surfactant, then dried and ground. The organic cation exchanged with that for most of the clay's original sodium cations is bis (2-hydroxyethyl) octadecyl methyl ammonium.
An amorphous oligomeric poly (m-xylylene adipamide · co-m-xylenylenisophthalamide) copolyamide is prepared in analogy to the procedure described in WO 00/34372, in combination with the imbalance of polymerization stoichiometry of
<td></td><td>the components</td><td>monomeric 1: 1, such as</td><td>I know</td><td>described in</td><td>the</td>
<td> 10</td><td>Present. East</td><td>material is analyzed by</td><td colspan="2">qualification of</td><td>the</td>
<td></td><td>amine groups and</td><td>late carboxylate, and it</td><td colspan="3">determine who owns</td>
<td></td><td>preferably</td><td>an appropriate number</td><td>of</td><td colspan="2">molecular weight</td>
<td></td><td>average of</td><td>approximately 3,000,</td><td>and</td><td>an IV</td><td>of</td>
<td></td><td>approximately</td><td>0.4 dL / g.</td><td></td><td></td><td></td>
<td> 15</td><td colspan="2">Initial materials for</td><td>the</td><td>process of</td><td>a</td>
step, i.e. about 20.4% by weight of the oligomeric resin, 4.6% of the organo-montmorillonite clay from Nanocor, Inc. and 75% by weight of Μλδ6-6007 from Mitsubishi Chemical Co. are then extruded in a screw extruder 57mm cufflinks (Werner Pfleiderer) equipped with a general composition screw. Barrel and die temperatures are set at approximately 270 ° C.
The resulting nanocomposite material can be used as the middle layer of the injected co25 three layer preform. The inner and outer layers of the three layer preform can be made from Eastman Chemical Company PET9921W, which are approximately 0.80 dL / g IV. The nominal thickness of the middle layer is approximately 10% of the total thickness. Preforms can be stretch blow molded on a Sidel SBO 2/3 machine in a 16 oz bottle.
Through this application, various publications are referenced. The descriptions of these publications in their entirety are hereby incorporated for reference within this application 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 or 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. The specification and examples are intended to be considered as examples only, the true scope and spirit of the invention being indicated by the following claims.
Contents4
11 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11
7 members in 6 offices
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 16840399 | United States of America | P | |
| 0032829 | United States of America | W |
Members7
| Document | Office | Kind | |
|---|---|---|---|
| CA2393015A1 | Canada | A1 | |
| WO0140369A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2002119266A1 | United States of America | A1 | |
| EP1235876A1 | European Patent Office (EPO) | A1 | |
| MXPA02005457AThis record | Mexico | A | |
| US6552113B2 | United States of America | B2 | |
| JP2003515648A | Japan | A |
Numbers
- Application
- 2005457
Titles2
- English
- A POLYMER CLAY NANOCOMPOSITE COMPRISING AN AMORPHOUS OLIGOMER.
- Spanish
- UN NANOCOMPUESTO DE ARCILLA-POLIMERO QUE COMPRENDE UN OLIGOMERO AMORFO.
Classification
- CPC, 5
- B82Y30/00
- C08J5/005
- C08K7/00
- C08K9/04
- Y10T428/1352
- IPC, 7
- C08J3 20
- C08J5 00
- C08K3 04
- C08K7 00
- C08K9 04
- C08L77 06
- C08L101 00