Polyamide blend composition having excellent gas barrier performance
Abstract
A polyamide composition comprising a slow crystallization mixture comprising: (i) a first polyamide comprising a crystallizable polyamide homopolymer, a crystallizable polyamide copolymer, a crystallizable polyamide nanocomposite material or a mixture thereof; and (ii) a second semi-crystalline polyamide comprising a polyamide copolymer comprising 20% to 70% by weight of an m-xylylene diamine moiety, 1% to 30% by weight of an isophthalic acid moiety, 20% a 60% by weight of an aliphatic dicarboxylic acid and an optional clay.
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11 claims: 3 independent, 8 dependent
- 1ES 2 379 484 T3 REIVINDICACIONES 1. - Una composición de poliamidas que comprende una mezcla de lenta cristalización que comprende:(i) una primera poliamida que comprende un homopolímero de poliamida cristalizable, un copolímero de poliamida cristalizable, un material nanocompuesto de poliamida cristalizable o una mezcla de los mismos;y (ii) una segunda poliamida semi-cristalina que comprende un copolímero de poliamida que comprende 20% a 70% en peso de un resto m-xilileno-diamina, 1% a 30% en peso de un resto ácido isoftálico, 20% a 60% en peso de un ácido dicarboxílico alifático y una arcilla opcional.
- 2- La composición de la reivindicación 1, en donde dicha segunda poliamida comprende, además, una arcilla.
- 3- La composición de la reivindicación 1, en donde dicho ácido dicarboxílico alifático comprende ácido adípico.
- 4- La composición de la reivindicación 1, en donde dicha primera poliamida comprende un material nanocompuesto de poliamida.
- 5- La composición de la reivindicación 1, en donde dicha primera poliamida comprende nilón 6, nilón 66, nilón 6/66, nilón 66/6, nilón MXD6 o nilón 6I,6T o un material nanocompuesto de nilón 6, nilón 66, nilón 6/66, nilón 66/6, nilón MXD6 o nilón 6I,6T.
- 6- La composición de poliamidas de la reivindicación 1, en donde dicha mezcla de lenta cristalización comprende:(iii) al menos un polidieno oxidable, compatible con la poliamida;y (iv) al menos un catalizador de sal metálica que fomenta la oxidación.
- 7- La composición de poliamidas según una cualquiera de las reivindicaciones precedentes, que comprende, además, al menos un componente polímero adicional mezclado con dicha mezcla de lenta cristalización.
- 8- La composición de poliamidas según la reivindicación 7, en donde dicho al menos un componente polímero adicional es poli(tereftalato de etileno), copolímeros de PET, poliolefinas, copolímeros de etileno y alcohol vinílico, copolímeros de acrilonitrilo, polímeros acrílicos, polímeros de vinilo, policarbonato y poliestireno.
- 9- Un procedimiento para formar una composición de poliamidas, que comprende combinar:(i) una primera poliamida que comprende un homopolímero de poliamida cristalizable, un copolímero de poliamida cristalizable, un material nanocompuesto de poliamida cristalizable o una mezcla de los mismos;y (ii) una segunda poliamida semi-cristalina que comprende un copolímero de poliamida que comprende 20% a 70% en peso de un resto m-xilileno-diamina, 1% a 30% en peso de un resto ácido isoftálico y 20% a 60% en peso de un ácido dicarboxílico alifático y una arcilla opcional.
- 10- Uso de la composición de poliamidass según una cualquiera de las reivindicaciones 1 a 6, para producir una película, botella u otro artículo o recipiente de una sola capa o multicapas.
- 11- Uso según la reivindicación 10, en donde dicha composición de poliamidass forma una capa enteriza en una película, botella o recipiente multicapas que incluye una o más capas de otro polímero termoplástico.
Independent claims11
115 paragraphs in 24 sections, as filed
ES 2 379 484 T3
DESCRIPTION
Polyamide blend composition with excellent gas barrier behavior
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The invention relates to delamination resistant, high gas barrier polyamide compositions suitable for extended shelf life packaging applications. Polyamide products are particularly suitable for producing barrier packaging articles such as monolayer or multilayer films, foils, thermoformed containers, and molded bottles. Articles of this type are useful in a variety of applications for the packaging of oxygen sensitive foods, beverages, pharmaceuticals and health care products.
DESCRIPTION OF THE RELATED TECHNIQUE
Polyamide-based packaging of items such as films, bottles and containers that are useful for food packaging is well known in the art. In order to enhance keeping cool, it is well known to package food and beverage products within a packaging structure made up of multiple layers of two or more different plastics. For example, US Pat. 5,055,355 and 5,547,765 teach laminates of polyamides and copolymers of ethylene and vinyl alcohol that have good oxygen barrier properties. Packaging structures of this type generally include a barrier plastic layer that has low permeation to oxygen and / or carbon dioxide.
In order to enhance freshness, it is conventional practice to package food and other materials within a laminated packaging material that generally includes a barrier layer with low oxygen permeability. The material can be thin, allowing it to be wrapped around the material being packaged, or it can be thick enough to form a shaped container body. It is further known to include an oxygen scavenger in polymeric packaging materials. The oxygen scavenger reacts with oxygen that is trapped in the container or penetrates the container. This is described, for example, in US Patents 4,536,409 and 6,423,776.
For this purpose, various types of oxygen scavengers have been proposed. US Patent 4,536,409 recommends potassium sulfite as an oxygen scavenger. US Patent 5,211,875 describes the use of unsaturated hydrocarbons as oxygen scavengers in packaging films. It is also known in the art that ascorbic acid derivatives as well as sulfites, bisulfites and phenolic compounds can be oxidized by molecular oxygen and thus can serve as an oxygen scavenging material. US Patents 5,202,052 and 5,364,555 describe supports of polymeric material containing an oxygen scavenging material. These polymeric supports for oxygen scavenging material include polyolefin, PVC, polyurethanes, EVA, and PET.
The present invention in its various aspects is set forth in the accompanying claims.
Films and articles produced from the compositions of the present invention show excellent gas barrier properties, particularly oxygen and carbon dioxide barrier properties.
More particularly, polymeric compositions of the invention are slow crystallizing mixtures that include a first polyamide comprising a homopolymer, a crystallizable polyamide copolymer, or a polyamide nanocomposite, or a mixture thereof, and a second polyamide comprising an m- moiety. xylylenediamine, an isophthalic acid residue and at least one additional residue comprising a polyamide monomeric precursor. Direct blends of the above polyamide compositions with other polymeric materials, for example polyethylene terephthalate (PET), and articles formed therefrom are also provided. Each of the above compositions shows good melt processability, good mixability and low crystallization to give a barrier layer with high transparency and good adhesion to other polymeric layers in multilayer structures. The compositions also exhibit good recyclability. The composition can also be used for gas barrier film applications that require oxygen scavenging capabilities.
ES 2 379 484 T3
SUMMARY OF THE INVENTION
The invention provides a polyamide composition comprising a slow crystallizing mixture, comprising:
(i) a first polyamide comprising a crystallizable polyamide homopolymer, a crystallizable polyamide copolymer, a crystallizable polyamide nanocomposite, or a mixture thereof; and (ii) a second semi-crystalline polyamide comprising a polyamide copolymer comprising 20% to 70% by weight of a m-xylylene diamine residue, 1% to 30% by weight of an isophthalic acid residue, 20% a 60% by weight of an aliphatic dicarboxylic acid and an optional clay.
In one embodiment of the present invention, there is provided a polyamide composition comprising a slow crystallizing mixture, comprising:
(i) a first polyamide comprising a crystallizable polyamide homopolymer, a crystallizable polyamide copolymer, a crystallizable polyamide nanocomposite, or a mixture thereof;
(ii) a second semi-crystalline polyamide comprising a polyamide copolymer comprising 20% to 70% by weight of a m-xylylene diamine residue, 1% to 30% by weight of an isophthalic acid residue, 20% to 60% in weight of an aliphatic dicarboxylic acid and an optional clay;
(iii) at least one oxidizable polydiene, compatible with the polyamide; and (iv) at least one metal salt catalyst that promotes oxidation.
The invention further provides a process for forming a polyamide composition, comprising combining:
(i) a first polyamide comprising a crystallizable polyamide homopolymer, a crystallizable polyamide copolymer, a crystallizable polyamide nanocomposite, or a mixture thereof; <sup>Y</sup> (ii) a second semi-crystalline polyamide comprising a polyamide copolymer comprising 20% to 70% by weight of a m-xylylene diamine residue, 1% to 30% by weight of an isophthalic acid residue, 20% to 60 % by weight of an aliphatic dicarboxylic acid and an optional clay.
The invention still further provides a polymer composition, comprising:
(a) a component of the polyamide composition, comprising:
(i) a first polyamide comprising a crystallizable polyamide homopolymer, a crystallizable polyamide copolymer, a crystallizable polyamide nanocomposite, or a mixture thereof; <sup>Y</sup> (ii) a second semi-crystalline polyamide comprising a polyamide copolymer comprising 20% to 70% by weight of a m-xylylene diamine residue, 1% to 30% by weight of an isophthalic acid residue, 20% to 60 % by weight of an aliphatic dicarboxylic acid and an optional clay; and (b) at least one polymer component mixed with said component of the polyamide composition.
Films, bottles, and other articles and containers shaped from the polymer compositions of the invention are also provided.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the first embodiment of the present invention, an improved polyamide composition is prepared by combining at least two polyamides. The first polyamide is a crystallizable polyamide homopolymer, a crystallizable polyamide copolymer, a crystallizable polyamide nanocomposite, or a mixture thereof. The second polyamide is a polyamide copolymer comprising an m-xylelene diamine residue, an isophthalic acid residue, an aliphatic dicarboxylic acid, and an optional clay.
Suitable nylons within the scope of the invention to form the first polyamide of this embodiment include, but are not limited to, homopolymers or copolymers selected from aliphatic polyamides and aliphatic / aromatic polyamides with a molecular weight of 10,000 to 100,000. General processes useful for the preparation of polyamides are well known in the art. These include the reaction products of diacids with diamines. Useful diacids for preparing polyamides include dicarboxylic acids which are represented by the general formula:
HOOC - Z - COOH
ES 2 379 484 T3 where Z is representative of a divalent aliphatic radical containing at least 2 carbon atoms such as adipic acid, sebacic acid, octadecanedioic acid, pimelic acid, suberic acid, azelaic acid, dedecanedioic acid and glutaric acid. The dicarboxylic acids can be aliphatic acids or aromatic acids such as isophthalic acid and terephthalic acid. Suitable diamines for preparing polyamides include those of the formula:
H<sub>2</sub>N (CH<sub>2</sub>)<sub>n</sub>NH<sub>2</sub> where n has an integer value of 1-16, and includes compounds such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, hexadecamethylenediamine, aromatic diamines such as p-phenylenediamine, 4,4'enediamine 4,4'-diaminodiphenyl-sulfone, 4,4'-diaminodiphenylmethane, alkylated diamines such as 2,2-dimethylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine and 2,4,4, -trimethylpentamethylenediamine, as well as cycloaliphatic diamines such as diaminodicyclohexylmethane and other compounds. Other useful diamines include heptamethylenediamine, nonamethylenediamine, and the like.
Useful polyamide homopolymers and copolymers include poly (4-aminobutyric acid) (nylon 4), poly (6-aminohexanoic acid) (nylon 6, also known as poly (caprolactam)), poly (7-aminoheptanoic acid) (nylon 7), poly (8-amino-octanoic acid) (nylon 8), poly (9-aminononanoic acid) (nylon 9), poly (10-aminodecanoic acid) (nylon 10), poly (11-aminoundecanoic acid) (nylon 11), poly (12-aminodedecanoic acid) (nylon 12), nylon 4,6, poly (hexamethylene-adipamide) (nylon 6,6), poly (hexamethylene-sebacamide) (nylon 6,10), poly (heptamethylene-pimelamide) (nylon 7,7), poly (octamethylene-suberamide) (nylon 8,8), poly (hexamethylene-azelamide) (nylon 6,9 ), poly (nonamethylene azelamide) (nylon 9.9), poly (decamethylene azelamide) (nylon 10.9), poly (tetramethylene diamine-co-oxalic acid) (nylon 4.2), the polyamide of n-dodecanedioic acid and hexamethylenediamine (nylon 6,12), dedecamethylenediamine polyamide and n-dodecanedioic acid (nylon 12,12) and the like. Useful aliphatic polyamide copolymers include caprolactam / hexamethylene-adipamide copolymer (nylon 6.6 / 6), hexamethylene-adipamide / caprolactam copolymer (nylon 6 / 6.6), trimethylene-adipamide / hexaimidene copolymer (nylon 6,6 / 6). trimethyl 6.2 / 6.2), hexamethylene adipamide-hexamethylene azelaimide copolymer and caprolactam (nylon 6.6 / 6.9 / 6) and the like. Also included are other nylons that are not particularly defined here.
Of these polyamides, preferred polyamides include nylon 6, nylon 6,6, nylon 6 / 6,6 as well as mixtures thereof. Of these, nylon 6 is the most preferred. Polyamides used in the practice of this invention can be obtained from commercial sources or can be prepared according to known preparation techniques. For example poly (caprolactam) can be obtained from Honeywell International Inc., Morristown, New Jersey under the trademark CAPRON®.
Exemplary aliphatic / aromatic polyamides include poly (tetramethylene diamine-co-isophthalic acid) (nylon 4, I), polyhexamethylene isophthalamide (nylon 6, I), hexamethylene adipamide / hexamethylene isophthalamide (nylon 6,6 / 6I), hexamidamide / hexamethylene terephthalamide (nylon 6,6 / 6T), poly (2,2,2-trimethyl-hexamethylene teraphthalimide), poly (m-xylylene adipamide) (MXD6), poly (p-xylylene adipamide), poly (hexamethylene -terephthalamide), poly (dodecamethylene-terephthalamide), polyamide 6I / 6T, polyamide 6T / 6I, polyamide 6 / MXDT / I, polyamide MXDI, and the like. Mixtures of two or more aliphatic / aromatic polyamides can also be used. Aliphatic / aromatic polyamides can be prepared by known preparation techniques or can be obtained from commercial sources. Other suitable polyamides are described in US Patents 4,826,955 and 5,541,267.
In preferred embodiments of the invention, the first polyamide preferably comprises polyamides nylon 6, nylon 66, nylon 6/66, nylon 66/6, nylon MXD6 or nylon 6I, 6T or a nanocomposite material of nylon 6, nylon 66, nylon 6 / 66, nylon 66/6, nylon MXD6 or nylon 6I, 6T. Of these, the most preferred are nylon 6, nylon 66, nylon 6/66 or 66/6 and mixtures thereof, as well as nanocomposites of nylon 6, nylon 6,6, nylon 6/66 or 66/6 and mixtures thereof. Of these nylon 6 or nylon 6 nanocomposite is most preferred for the former polyamide.
The first polyamide is combined with a second polyamide component which is a polyamide copolymer comprising a m-xylylene diamine residue, an isophthalic acid residue and an aliphatic dicarboxylic acid, and an optional clay. More particularly, the second polyamide comprises a semi-crystalline polyamide copolymer with an m-xylylene diamine residue (mXDA), an isophthalic acid residue (IPA) and an aliphatic dicarboxylic acid. In preferred embodiments of the invention, aliphatic dicarboxylic acid comprises adipic acid, sebacic acid, octadecanedioic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid and / or glutaric acid. Most preferably, the aliphatic dicarboxylic acid comprises adipic acid.
The second polyamide comprises a copolymer comprising from 20% to 70% by weight of said m-xylylenediamine residue, from about 1% to about 30% by weight of said isophthalic acid residue, and from about 20% to about 60% by weight of said aliphatic dicarboxylic acid. Preferably, the
ES 2 379 484 T3 second polyamide comprises a copolymer comprising from 40% to 60% by weight of said m-xylylenediamine residue, from 5% to 15% by weight of said isophthalic acid residue and from 30% to 50% by weight of said aliphatic dicarboxylic acid. Most preferably, the second polyamide comprises a copolymer comprising 45 to 55% by weight of said m-xylylene diamine residue, 7% to 10% by weight of said isophthalic acid residue, and 35% to 45% in weight of said aliphatic dicarboxylic acid. Each of said first and second polyamides can be formed using techniques that are well known in the art.
In the overall polyamide composition, the first polyamide is preferably present in an amount of 5% to 50% by weight of the overall polyamide composition, and the second polyamide is preferably present in an amount of 50% to 95% by weight of the overall composition of polyamide. More preferably, the first polyamide comprises 5 to 45 weight percent and the second polyamide comprises 55 to 95 weight percent of the overall polyamide composition. Most preferably, the first polyamide comprises from 10 to 30 percent by weight and the second polyamide comprises from about 70 to about 90 percent by weight of the overall polyamide composition.
In a second embodiment of the invention, the polyamide compositions described above further comprise at least one oxygen scavenger compatible with polyamides. The polyamide compatible oxygen scavenger preferably comprises an oxidizable, nylon reactive functional polydiene or an oxidizable polyether. These are small, low molecular weight particles that are compatible and can be uniformly dispersed throughout the polyamide. Preferably, the oxidizable, nylon-reactive polydiene or polyether comprises an epoxy or anhydride functionality, such that it reacts with the carboxyl or amino end groups of the polyamide. The functionality in the polydiene or polyether can also react with an amide group on the backbone of the polyamide. The functionality can hang from the main chain or at the ends of the polydiene or polyether chain. Preferred functional polydienes are functional polyalcadiene oligomers having the following general backbone structure:
—— [CHRj-CR<sub>2</sub>= CR3 — CHR4] ------ [CHRj — CHR<sub>2</sub>] ---- CHR3 = CHR4 where R<sub>4</sub>, R<sub>2</sub>, R<sub>3</sub> and R<sub>4</sub> they can be the same or different and can be selected from hydrogen (-H) or any of the lower alkyl groups (methyl, ethyl, propyl, butyl, etc.). R<sub>2</sub> and R<sub>3</sub> they can also be a chloro group (-Cl). Illustrative of the backbone structure are polybutadiene (1,4 or 1,2 or mixtures of both), polyisoprene (1,4 or 3,4), poly-2,3-dimethyl-butadiene, polychloroprene, poly-2 , 3-dichlorobutadiene, polyalene, poly-1,6-hexatriene, etc.
Specific non-limiting examples of functionalized and oxidizable polyamide compatible polydienes as suitable oxygen scavengers include epoxy functionalized polybutadiene (1,4 and / or 1,2), maleic anhydride grafted or copolymerized polybutadiene (1,4 and / or 1 , 2), epoxy functionalized polyisoprene and polyisoprene grafted or copolymerized with maleic anhydride.
A preferred oxygen scavenger includes an anhydride-functional polybutadiene oligomer. The molecular weight of the functional polydiene oligomer preferably ranges from 500 to 8,000, preferably from 1,000 to 6000, and most preferably from 1,500 to 5,500. When incorporated, it is preferably present in the overall composition in an amount of 0.1% to 10% by weight, more preferably 1% to 10%, and most preferably 2% to 6%. The functional oxidizable polydiene is preferably present as a large number of small particles, the mean particle diameter of which is in the range of 10 nm to 1000 nm and wherein the particles are essentially uniformly distributed throughout the polyamide composition. The polyamide composition may comprise a mixture of the polyamide components and the polyamide-compatible and oxidizable polydiene, or a reaction product of the polyamide components with the polyamide-compatible oxidizable polydiene.
The polyamide composition of the second embodiment further preferably comprises at least one oxidation promoting metal salt catalyst such as a low molecular weight oxidation promoting metal salt catalyst. Suitable oxidation promoting metal salt catalysts comprise a conjugate ion that is present in acetates, stearates, propionates, hexanoates, octanoates, benzoates, salicylates and cinnamates, and combinations thereof. Preferably, the oxidation promoting metal salt catalyst comprises a cobalt, copper or ruthenium acetate, stearate, propionate, hexanoate, octanoate, benzoate, salicylate or cinnamate, or a combination thereof.
Preferred metal carboxylates include cobalt, ruthenium, and copper carboxylate. Of these, the most preferred are
ES 2 379 484 T3 cobalt or copper carboxylate and most preferred is cobalt carboxylate. When incorporated, the metal salt catalyst is preferably present in the overall composition in an amount of 0.001% to 1% by weight, preferably 0.002% to 0.5%, and most preferably 0.005% to 0.1%. %. The most preferred range is 0.01% to 0.05%.
Each of the polyamide compositions of the invention preferably further comprises a nano-scale dispersed clay, known in the art as a nanoclay. A polyamide combined with a nanoclay is also known in the art as a polyamide nanocomposite material. Suitable clays are described in US Patent 5,747,560. Preferred clays include, but are not limited to, a natural or synthetic phyllosilicate such as montmorillonite, hectorite, vermiculite, beidylite, saponite, nontronite, or synthetic fluoromic, which has been cation exchanged with a suitable organoammonium cation. A preferred clay comprises montmorillonite, hectorite, or synthetic fluoromic, more preferably montmorillonite or hectorite, and most preferably montmorillonite. A preferred organoammonium cation for treating clay comprises an N, N ', N ", N'" - bis (hydroxyethyl), methyl, octadecyl-ammonium cation or an [omega] -carboxy-alkylammonium cation, i.e. the ammonium cation derived such as from [omega] -aminoalkanoic acids such as 6-amino-caproic acid, 11-aminoundecanoic acid, 12-aminodedecanoic acid. Preferred fine dispersions of nano-scale silicate wafers can be obtained through in situ polymerization of a polyamide-forming monomer or monomers or through melt mixing of polyamide in the presence of the clay. Methods of this type are described in US Patent 5,747,560. The clay preferably has a mean plate thickness ranging from 1 nm to 100 nm and a mean length and a mean width, each of which ranges from 50 nm to 700 nm. It is preferably present in the overall polyamide composition in an amount of 0% to 10% by weight, more preferably 0.5% to 6%, and most preferably 0.8% to 4%.
The polyamide compositions of the invention may also optionally include one or more conventional additives, the uses of which are well known to those skilled in the art. The use of additives of this type may be desirable to enhance the processability of the compositions, as well as to improve the products or articles formed therefrom. Examples of such additives include oxidative and thermal stabilizers, lubricants, mold release agents, flame retardants, oxidation inhibitors, dyes, pigments and other coloring agents, ultraviolet light stabilizers, organic or inorganic fillers including particulate and fibrous fillers, reinforcing agents, nucleating agents, plasticizers as well as other conventional additives known in the art. Additives of this type can be used in amounts of up to 10% by weight of the overall polyamide compositions.
Representative UV stabilizers include various substituted resorcinols, salicylates, benzotriazole, benzophenones, and the like. Suitable lubricants and mold release agents include stearic acid, stearyl alcohol, and stearamides. Exemplary fire retardants include organic halogenated compounds, including decabromodiphenyl ether and the like, as well as inorganic compounds. Suitable coloring agents, including dyes and pigments, include cadmium sulfide, cadmium selenide, titanium dioxide, phthalocyanines, ultramarine blue, nigrosine, carbon black, and the like. Representative oxidative and thermal stabilizers include the Group I metal halides of the Periodic Table of the Elements such as sodium halides, potassium halides, lithium halides; as well as cuprous halides; and, in addition, chlorides, bromides, iodides. Also hindered phenols, hydroquinones, aromatic amines as well as substituted members of the above groups and combinations thereof. Exemplary plasticizers include lactams such as caprolactam and lauryl lactam, sulfonamides such as o, p-toluenesulfonamide and N-ethyl, N-butyl-benzenesulfonamide, and combinations of any of the foregoing, as well as other plasticizers known in the art. .
Suitable fillers include inorganic fillers, including those of a fibrous and granular nature, as well as mixtures thereof. Fibrous fillers include glass, silica glass, ceramics, asbestos, alumina, silicon carbide, gypsum, metal (including stainless steel), as well as other inorganic and carbon fibers. Granular fillers include wollastonite, sericite, asbestos, talc, mica, clay, kaolin, bentonite, and silicates, including alumina silicate. Other granular fillers include metal oxides such as alumina, silica, magnesium oxide, zirconium oxide, titanium oxide. Additional granular fillers include carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates include calcium sulfate and barium sulfate, boron nitride, glass beads, silicon carbide as well as other materials not specifically indicated herein. The fillers can be hollow, for example glass microspheres, silane globes, carbon globes, and hollow glass fibers. Preferred inorganic fillers include glass fibers, carbon fibers, metal fibers, potassium titanate monocrystals, glass beads, glass flakes, wollastonite, mica, talc, clay, titanium oxide, aluminum oxide, calcium carbonate, and barium sulfate. Particularly most preferred are glass fibers. Inorganic fillers should preferably be treated with silane, titanate, or other conventional coupling agent, and glass fibers should preferably be treated with an epoxy resin, vinyl acetate resin, or other conventional converging agent.
ES 2 379 484 T3
Preferably, the polyamide compositions of the invention are produced by melt extrusion mixing of the first and second polyamides, as well as any other components of the composition, including oxygen scavenging compositions and metal salt catalysts. The composition can be formed by dry mixing solid particles or pellets of each of the polyamide components and then melt mixing the mixture of any other components in suitable mixing means such as an extruder, a roller mixer or the like. Typical melting temperatures range between 230 ° C and 300 ° C, more preferably between 235 ° C and 280 ° C, and most preferably between 240 ° C and 260 ° C for polyamide compositions. Mixing is preferably carried out for a suitable period of time to achieve essentially uniform mixing. This period can easily be determined by those skilled in the art. If desired, the composition can be cooled and pelleted for further processing, can be extruded into a fiber, filament, or shaped element or can be formed into films and optionally stretched or oriented uniaxially or biaxially by either means. known in the art.
The polyamide compositions of this invention can be used to produce various single-layer or multi-layer films, articles, bottles, containers and the like, using conventional processing techniques, including extrusion, lamination, extrusion lamination, co-injection, stretch blow molding, co-extrusion blow molding and blown film techniques. The preferred method of producing monolayer or multilayer films is by co-extrusion. The preferred method of producing bottles includes extrusion blow molding, co-extrusion blow molding, injection blow molding, co-injection-blow molding, injection-stretch-blow molding or co-injection molding. stretch-blown, and the containers are preferably produced through thermoforming techniques. Processing techniques for producing mixtures as well as for producing films, sheets, containers, and bottles are well known in the art. For example, the first and second polyamide components (i) and (ii) of the polyamide composition can be pre-mixed and then the final mix can be fed into a feed hopper of an extruder, or each of the components It can be fed into feed hoppers from an extruder and then mixed in the extruder. A molten and plasticized stream from the extruder is fed into a single manifold die and extruded to form a layer. It then emerges from the row in the form of a single layer film of material. After exiting the die, the film is cast onto a first temperature controlled casting roll, runs around the first roll, and then onto a second temperature controlled roll, which is typically cooler than the first roll. Temperature controlled rollers control the rate of cooling of the film after it leaves the die. Once cooled and hardened, the resulting film is preferably essentially transparent.
When forming a multilayer structure, the material for the individual layers is fed into feed hoppers of the extruders of equal numbers, with each extruder handling the material for one or more of the layers. The molten and plasticized streams from the individual extruders are fed into a single collector co-extrusion die. While in the spinneret, the layers are juxtaposed and combined, then emerge from the spinneret as a single multi-layer film of polymeric material. After exiting the die, the film is cast onto a first temperature controlled casting roll, runs around the first roll, and then onto a second temperature controlled roll that is typically cooler than the first roll. Temperature controlled rollers largely control the rate of film cooling after it leaves the die.
In another method, a film-forming apparatus may be one referred to in the art as a blown film apparatus, and includes a multi-manifold circular die head for a bubble blown film through which the composition of laminated film is forced through and transforms into a film bubble that can ultimately be folded into a film. Coextrusion processes for forming film and laminate laminates are generally known. See, for example, "Modern Plastics Encyclopedia," Vol. 56, No. 10A, pp. 131-132, McGraw Hill, October 1979. Alternatively, individual layers may first be laminated to sheets and then laminated together under heat and pressure with or without intermediate adhesive layers.
As mentioned above, the composition can also be used to form a shaped article through any well-known process, including extrusion blow molding and injection stretch blow molding. An injection molding process softens the mixture of thermoplastic components in a heated cylinder, injecting it while in a molten state under high pressure into a closed mold, cooling the mold to induce solidification, and expelling molded pre-formed products from the mold. . Molding compositions are well suited for the production of pre-shaped products and subsequent reheat stretch-blow molding of these pre-shaped products into final bottle shapes that have the desired properties. The pre-shaped, injection molded product is heated to
ES 2 379 484 T3 at a suitable orientation temperature, often in the range of 80 ° C to 150 ° C, and then stretch blow molded. The latter process consists of first stretching the hot pre-formed product in the axial direction by mechanical means such as by pushing with a central rod attachment, followed by high pressure air blowing (up to 35 kg / cm<sup>2</sup>) to stretch it in the direction of the hoop. In this way, a biaxially oriented, blown bottle is produced. Typical blow ratios are often between 5: 1 and 15: 1.
The polyamide compositions of this invention can be formed as an integral layer in a multilayer film, bottle or container that includes one or more layers of another thermoplastic polymer such as polyesters, particularly polyethylene terephthalate (PET) and PET copolymers , polyolefins, ethylene vinyl alcohol copolymers, acrylonitrile copolymers, acrylic polymers, vinyl polymers, polycarbonates, polystyrenes, polyamides, fluoropolymers and the like. The polyamide compositions of this invention are particularly suitable as barrier layers in the construction and manufacture of multilayer bottles and thermoformed containers in which layers of PET or polyolefin act as structural layers. Multilayer PET / polyamide bottles of this type can be produced by co-injection stretch blow molding processes, similar to the injection stretch blow molding process as described above. Similarly, multilayer bottles of this type can be produced by blow molding and co-extrusion. The latter process typically employs optional co-extrusion adhesive layers suitable for adhesion.
Polyesters useful for the co-injection stretch blow molding process include polyethylene terephthalate and its copolymers, in an intrinsic viscosity (VI) range of 0.5 to 1.2 dl / g, more preferably in the IV range of 0.6 to 1.0 dl / g and most preferably in the IV range of 0.7 to 0.9 dl / g. Polyolefins used in coextrusion blow molding preferably comprise polymers of alphaolefin monomers having 2 to 6 carbon atoms, and include homopolymers, copolymers (including graft copolymers) and terpolymers of alpha-olefins and the like. Examples thereof include, but are not limited to, ultra-low density polyethylene (ULDPE); low-density polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Linear Metallocene Low Density Polyethylene (mLLDPE), Medium Density Polyethylene (MDPE); high-density polyethylene (HDPE); Polypropylene; polybutylene; polybutene-1; poly-3-methylbutene-1; poly-pentene-1; poly-4-methylpentene-1; poly-isobutylene; polyhexene and the like. Polyolefins of this type may have a weight average molecular weight of 1,000 to 1,000,000, and preferably 10,000 to 500,000. Preferred polyolefins include polyethylene, polypropylene, polybutylene, and copolymers and mixtures thereof. The most preferred polyolefins include polyethylene and polypropylene.
Preferred fluoropolymers include, but are not limited to, chlorotrifluoroethylene homopolymers and copolymers, ethylene-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene-propylene copolymer, perfluoroalkoxyethylene, polychlorotrifluoroethylene (fluoroethylene) (polychlorotrifluoroethylene) vinylidene) and copolymers and blends thereof. As used herein, copolymers include polymers that have two or more monomeric components. The most preferred fluoropolymers include homopolymers and copolymers of poly (chlorotrifluoroethylene) (PCTFE). Particularly preferred are PCTFE materials sold under the trademark ACLON (TM) and which are commercially available from Honeywell International Inc. of Morristown, New Jersey.
Suitable copolymers of ethylene and vinyl alcohol suitable for use in the present invention can be prepared by the methods described in US Patents 3,510,464; 3,560,461; 3,847,845; and 3,585,177. Acrylonitrile copolymers, acrylic polymers, vinyl polymers, polycarbonates, polystyrenes, and fluoropolymers suitable for use in the present invention can be prepared by methods that are well known in the art. Suitable polyamides can be prepared using methods previously described herein. Additional layers can also include coextrusion adhesives to co-extrude various layers together. Non-limiting examples of other optional polymeric layers and coextrusion adhesive layers that can be used in films of the present invention are described, for example, in US Pat. 5,055,355; 3,510,464; 3,560,461; 3,847,845; 5,032,656; 3,585,177; 3,595,740; 4,284,674; 4,058,647; and 4,254,169.
The polyamide compositions of the invention may comprise direct blends of the first and second polyamides with an additional polymer component. This additional polymer component may comprise any of the aforementioned polymers, including particularly polyethylene terephthalate and PET copolymers, polyolefins, ethylene vinyl alcohol copolymers, acrylonitrium copolymers, acrylic polymers, vinyl polymers, polycarbonate, polystyrene. and the like. The additional polymer component preferably comprises at least 50% by weight of the overall direct mix composition, more preferably at least 80% and most preferably at least 90% by weight of the overall direct mix composition. As with each of the other compositions described herein, these direct mix compositions can be made into single or multi-layer films, as well as other items such as bottles and
ES 2 379 484 T3 containers. However, these direct blends are particularly intended to be transformed into single-layer structures. Direct blends may also additionally comprise at least one polyamide compatible oxygen scavenger and optionally at least one oxidation promoting metal salt catalyst, as described above.
The single or multilayer films of the invention include at least one polyamide composition layer, which polyamide composition layer has first and second surfaces. In a preferred multilayer film structure a two-layer film is formed comprising at least one thermoplastic polymer layer attached to at least one of said first and second surfaces of said polyamide composition. In another preferred multilayer film construction, a three-layer film is formed comprising at least one thermoplastic polymer layer attached to each of said first and second surfaces of the polyamide composition layer. For example, a three-layer film may comprise a PET / polyamide / PET composition layer structure. Other preferred film structures include, but are not limited to, PET / co-extrusion adhesive / EVOH / polyamide composition / EVOH / co-extrusion adhesive / PE; PE / co-extrusion adhesive / EVOH / polyamide composition / co-extrusion adhesive / PE; and PE / coextrusion adhesive / polyamide composition / co-extrusion adhesive / PE, wherein the PE layer may comprise LDPE, HDPE, LLDPE or any other polyethylene layer as described above. Adhesive materials can also be mixed into PE or EVOH layers rather than used as a discrete layer.
Optionally, adhesive layers, also known as "co-extrusion adhesives" can be formed or disposed between each of the layers of the film. Suitable adhesive layers include adhesive polymers such as modified polyolefin compositions with at least one functional moiety selected from the group consisting of unsaturated polycarboxylic acids and anhydrides thereof. Said unsaturated carboxylic acid and anhydrides include maleic acid and anhydride, fumaric acid and anhydride, crotonic acid and anhydride, citraconic acid and anhydride, itaconic acid and anhydride, and the like. Of these, the most preferred is maleic anhydride. Modified polyolefins suitable for use in this invention include compositions described in US Patents 3,481,910; 3,480,580; 4,612,155 and 4,751,270. Other adhesive layers include, but are not limited to, copolymers of olefin alkyl esters and [alpha], [beta] -ethylenically unsaturated acid alkyl esters such as those disclosed in US Patent 5,139,878. Preferred modified polyolefins comprise from 0.001 to 10 percent by weight of the functional moiety, based on the total weight of the modified polyolefin. More preferably, the functional moiety comprises 0.005 to 5 percent by weight, and most preferably 0.01 to 2 percent by weight. The modified polyolefin composition can also contain up to 40 weight percent thermoplastic elastomers and alkyl esters as described in US Patent 5,139,878. Alternatively, one or more adhesive polymers can be directly blended or co-extruded to form other layers of the film, thus providing adhesion, while minimizing the number of layers in the film.
Films produced in accordance with the present invention can be oriented by stretching or tensioning the films at stretch ratios of 1.1: 1 to 10: 1, and preferably at a stretch ratio of 2: 1 to 5: 1. The term "stretch ratio" as used herein indicates the increase in dimension in the direction of stretch. Therefore, a film that has a 2: 1 stretch ratio has its length doubled during the stretching process. Generally, the film is stretched by passing it over a series of preheating and heating rollers. The heated film travels through a set of downstream back draw rollers at a faster speed than film penetrating the back draw rollers at an upstream location. The change in speed is compensated for by stretching on the film.
Films can be stretched or oriented in any desired direction using methods well known to those of skill in the art. The film can be stretched uniaxially, either in the longitudinal direction coincident with the direction of motion of the film being removed from the film forming apparatus, referred to in the art as "machine direction", or in a direction that is perpendicular to the machine direction and referred to in the art as the "transverse direction", or biaxially, both in the longitudinal direction and in the transverse direction. The films can be additionally annealed or heat treated to further enhance their barrier properties. In the annealing or heat treatment processes, heated fluids or IR radiation heaters can be used. These types of techniques are well known in the art.
Films of the invention preferably have a thickness of 5 µm to 400 µm, more preferably 10 µm to 200 µm, and most preferably 1 µm to 100 µm. While thicknesses of this type are preferred as they provide an easily flexible film, it is to be understood that other film thicknesses can also be produced to meet a particular need and still fall within the scope of the present invention. Thicknesses of this type that are contemplated include plates, thick films and sheets that are not easily
ES 2 379 484 T3 flexible at room temperature (approx. 20 ° C).
A noteworthy characteristic of films and articles produced from the composition of this invention is that they exhibit excellent gas barrier properties, particularly oxygen and CO2 barrier properties. Resistance to oxygen permeation or barrier can be measured using ASTM D-3985 processes. In general, the films of this invention have an Oxygen Transmission Rate (OTR) of 1 cc / 100 in.<sup>2</sup> (645.16 cm<sup>2</sup>) / day, at a relative humidity (RH) of 80% in air at atmospheric pressure. For purifying compositions, the OTR (in cc.mil/100 in<sup>2</sup> (645.16 cm<sup>2</sup>) / day, preferably ranges from 0.001 to 2, more preferably from 0.001 to 0.5, and most preferably from 0.001 to 0.1 cc mil/100 in.<sup>2 </sup>(645.16 cm<sup>2</sup>) / day, at 80% RH in air at atmospheric pressure. The OTR for non-oxygen scrubbing compositions, measured at 65% RH, at 23 ° C in pure oxygen, is preferably less than 1.5 cc.mil/100 in.<sup>2 </sup>(645.16 cm<sup>2</sup>) / day, more preferably less than 1.2 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>) / day and, most preferably less than 1.0 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>) / day, at atmospheric pressure. In general, the films of this invention preferably have a carbon dioxide transmission rate, measured in accordance with ASTM F2476 (performed at 80% RH, 23 ° C), less than 2 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>) / day, more preferably less than 1.6 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>) / day, less than 1.0 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>) / day at atmospheric pressure.
The glass transition temperature (Tg) of the polyamide compositions of this invention, as determined by differential scanning calorimetry techniques, are preferably much less than 120 ° C, which is generally the upper temperature limit for moldability. stretch-blow molding by reheating pure PETs in distortion-free bottles. Furthermore, in co-injection stretch blow molding processes to produce single or multi-layer bottles, extensive voiding could occur with potential barrier loss if the Tg of the polyamide composition exceeds 110 ° C. Therefore, the polyamide composition preferably has a Tg of 20 ° C to 110 ° C, more preferably 40 ° C to 100 ° C, and most preferably 60 ° C to 90 ° C.
The polyamide compositions of this invention preferably exhibit low crystallization behavior similar to PET, characterized by no onset or slow onset of crystallization, as determined by differential scanning calorimetry peak crystallization exotherm (Tcc). (DSC) that appears after cooling the melt from 280 ° C at a programmed cooling rate of 20 ° C / min. For PET, the Tcc is approximately 190 ° C, which is approximately 70 ° C lower than its crystalline melting point (Tm) of 260 ° C. Thus, the polyamide composition of this invention preferably exhibits a low Tcc or crystallization temperature of about 160 ° C or less, upon cooling from the melt at a cooling rate of 10 ° C / min in a DSC apparatus. . At faster cooling rates (80 ° C / min), the polyamides of this invention exhibit a lower Tcc.
The following non-limiting examples serve to illustrate the invention. It will be appreciated that variations in the proportions and alternatives in the elements of the components of the invention will be apparent to those skilled in the art and are within the scope of the present invention.
EXAMPLES
The following procedure and characterization steps were performed for the following examples and comparative example.
Procedure step 1: Preparation of the catalyst standard batch (MB)
This master batch is used as an additive in stage two or three of the process for the preparation of an oxygen scavenging resin. A Leistritz 18mm co-rotating twin screw extruder, equipped with a K-tron volumetric feeder, was used to prepare the catalyst master batch. The screw used in this procedure was designed with three mixing zones and a ventilation zone. A mixture of nylon 6 pellets (Honeywell B73ZP) and cobalt stearate pellets (from Shepherd Chemical Co.) was fed into the throat of the extruder at a rate of ten (10) pounds (4.65 kilograms) per hour. The mix ratio was 95 weight percent PA-6 (Honeywell B73ZP) and five (5) weight percent cobalt stearate (Shepherd Chemical). After mixing in the extruder, the extrudate was passed through a die plate and quenched in a water bath and finally granulated.
Process step 2: Preparation of resin products by melt extrusion
A Leistritz 18 mm co-rotating twin screw extruder, equipped with a K-Tron volumetric feeder, was used. Blends of MXD6 / MXDI copolyamide (EMS XS-0501) with a) nylon 6 polyamide (Honeywell H73ZP), b) nylon 6 nanoclay polymer (Honeywell 4% nanoclay PA6, XA2979) or a standard batch of nylon 6 and nanoclay
ES 2 379 484 T3 at 15.7% (Nanocor® nano-polyamide concentrate (NPC)) were fed into the throat, covered with a nitrogen blanket, from the extruder at a rate of 4.65 kilograms per hour. The extruder was equipped with two mixing zones consisting mainly of kneading elements. The extruder was equipped with a vacuum zone subsequent to the second mixing zone and in front of the die plate. The extrudate was quenched in a water bath and then granulated.
Stage 3 of the procedure: Preparation of oxygen scavenging composition
A Leistritz 18 mm co-rotating twin screw extruder, equipped with a K-Tron volumetric feeder, was used. A polybutadiene (maleic anhydride functionalized polybutadiene - Ricon 131MA5) is stored in a sealed drum container and metered with a Nichols-Zenith pump directly into the extruder barrel downstream of the feed throat. The polybutadiene is injected directly into the extruder in front of the first (of two) mixing zones through a Leistritz direct liquid injection nozzle. A blend of an MXD6 / MXDI copolyamide (EMS XS-0501), at least one of a nylon 6 nanocomposite, 4% nylon 6, or a 15.7% nylon nanocomposite, and the standard batch of nylon stearate. Cobalt from step 1 of the process are fed into the throat, covered with a nitrogen blanket, from the extruder at a rate of 4.65 kilograms per hour. The blend consists of approximately 98 weight percent polyamides and 2 weight percent cobalt standard batch. The polybutadiene is pumped at such a rate that weight percentages of 1% to 5% of polybutadiene are added. The extruder is equipped with two mixing zones consisting mainly of kneading elements. The extruder is equipped with a vacuum zone subsequent to the second mixing zone and in front of the die plate. The extrudate is then quenched in a water bath and granulated.
Step 4 of the procedure: Preparation of mixed products in granules
Compositions can be prepared by a granule mixing strategy rather than melt mixing. Mixing was accomplished by weighing the required amount of each of the polyamide materials into a large container. The container was tumbled for approximately 5 minutes to ensure thorough mixing of the two components. These mixtures were subsequently used as feedstock for film or container processing.
Step 5 of the procedure: Preparation of a monolayer film
A 19 mm Haake single screw extruder, equipped with a six-inch (152.4 mm) wide film die, was fed to overflow with granules, such as those from process 2, 3, or 4. The temperature of the extruder was set at approximately 260 ° C. The extrudate passed through the die slot and onto a heated Killion casting roll. The thickness of the film was adjusted through the casting roll speed and / or the number of revolutions (rpm) of the spindle to prepare a film with a thickness of about 0.001 inches to about 0.004 inches (0.0254 to 0, 1016 mm).
Procedure 6: Preparation of a multilayer film
Three Killion single screw extruders, equipped with a twelve inch (304.8 mm) wide film co-extrusion die, are used to prepare a three, four or seven layer multilayer film. An extruder is fed to overflow with granules from process 2, 3 or 4, and they are made into an inner layer. The second extruder is fed to overflow with one or more of, for example, polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, ethylene-vinyl alcohol, or nylon and extruded into two outer layers. The third extruder is fed to overflow with a coextrusion adhesive resin that can effectively bond incompatible polymers together such as a core polyamide layer from the first extruder and outer layers from the second extruder. Extruder temperatures are approximately 150 ° C - 300 ° C, in all three extruders, depending on the composition of the polymeric film. The extrudates are passed through the slit die over a heated, cast-molded roll. The thickness of the film is adjusted through the speed of the cast roll and / or the number of revolutions per minute of the spindle to prepare a film.
Procedure 7: Multilayer bottles (co-injection stretch blow molding)
A three-layer co-injection stretch blow molding process was used to prepare multi-layer beverage bottles with the following structure: PET / polyamide blend / PET. The total content in the polyamide blend was 5 percent by weight of the total weight of the preform. Preforms were prepared with an Arburg co-injection press equipped with a co-injection head / pipe and a multilayer preform mold. The
ES 2 379 484 T3 PET extruder temperature settings were about 280 ° C. The extruder temperature settings for the polyamide blend compositions were approximately 260 ° C. The finished bottles were prepared on Sidel stretch blow molding equipment with a preheat temperature of the preform of approximately 90-110 ° C. In each case, conventional processing techniques were used.
Oxygen transmission measurements
Oxygen transmission rate (OTR) measurements were performed on film samples on a Mocon Oxtran 2/20 apparatus equipped with SL sensors. The tests were carried out at a relative humidity (RH) of 65% using 100% oxygen and a test temperature of 23 ° C. Data was collected and recorded in units of cc / 100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day.
Carbon dioxide transmission measurements
Carbon dioxide transmission rate (CO<sub>2</sub>TR) were performed on film samples in a Mocon Permatran C440 apparatus at 80% RH (CO side<sub>2</sub> set at 80% RH, nitrogen carrier gas side was dry), at 23 ° C. Data was collected and recorded in units of cc / mil / 100 in.<sup>2 </sup>(645.16 cm<sup>2</sup>)/day.
Carbon dioxide measurement measurements were likewise made on bottle samples. The bottles were carbonated with dry ice to obtain 4.0 volumes of CO gas.<sub>2</sub>. The amount of CO gas<sub>2</sub> contained in each of the bottles was determined by measuring the peak of CO absorption<sub>2</sub> using Fourier transform infrared analysis (FTIR). This information was used to estimate the amount of time required for the bottles to achieve a carbonation loss of 17.5%.
In addition to the FTIR test, the bottles were carbonated with water and placed in the Mocon Permatran unit to determine the carbon dioxide permeation rate in cc / pkg / day. The bottles were carbonated to 4.0 volumes of CO<sub>2</sub> and were kept within a chamber in the permeation tester. The chamber was continuously flushed with dry purge gas and evaluated for its CO content.<sub>2</sub>.
EXAMPLE 1 (COMPARISON)
Comparative Example 1 illustrates a polyamide 6 composition that does not include the MXDA-IPA copolymers of the invention. A polyamide composition is formed, formulation comprising 100 weight percent nylon
6. This formulation was prepared through step five of the process, and subsequently cast into a film using conventional techniques. The OTR of this nylon was 3 cc / 100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The CO<sub>2</sub>TR of this nylon was measured at 14 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day.
EXAMPLE 2
A mixture of 70% by weight of MXD6 / MXDI copolyamides (i.e., adipic acid-MXDA-isophthalic acid copolyamides) and 30% by weight of nylon 6 was formed and processed through steps 2, 4, 5 and 7 of the procedure. A 16 oz, 24 gram, 28 mm bottle was formed with a straight wall and a petaloid base. The bottle was tested for OTR and CO<sub>2</sub>TR. OTR was measured at 0.9 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. TRCO2 was measured at 1.5 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The OTR and CO2TR were significantly better than the nylon 6 homopolymer of Comparative Example 1. The CO2 permeation test in a Mocon Permatran unit as described above revealed a CO permeation rate.<sub>2</sub> 0.21 cc / pkg / day. The bottle had a shelf life of 16 weeks.
EXAMPLE 3
A blend of 80% by weight of MXD6 / MXDI copolyamides and 20% by weight of nylon 6 was formed and processed through steps 2 and 5 of the process. A film of the composition was tested for OTR and CO<sub>2</sub>TR. OTR was measured at 0.7 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The CO<sub>2</sub>TR was measured at 1.1 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The OTR and CO2TR were significantly better than the nylon 6 homopolymer of Comparative Example 1.
EXAMPLE 4
A blend of 90% by weight of MXD6 / MXDI copolyamides and 10% by weight of nylon 6 was formed and processed through 12
ES 2 379 484 T3 steps 2 and 5 of the process. A film of the composition was tested for OTR and CO<sub>2</sub>TR. OTR was measured at 0.4 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The CO<sub>2</sub>TR was measured at 0.6 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The OTR and CO2TR were significantly better than the nylon 6 homopolymer of Comparative Example 1.
EXAMPLE 5
A mixture of 70% by weight of MXD6 / MXDI copolyamides and 30% by weight of a nylon 6 nanocomposite material containing 4% nanoclay (4% nanoclay PA6, Honeywell XA2979) was formed and processed through the steps 2 and 5 of the procedure. A film of the composition was tested for OTR and CO2TR. OTR was measured at 0.6 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. TRCO2 was measured at 1.2 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The OTR and CO2TR were significantly better than the nylon 6 homopolymer of Comparative Example 1.
EXAMPLE 6
A blend of 70% by weight of MXD6 / MXDI copolyamides, 15% by weight of a nylon 6 nanocomposite containing 4% nanoclay (4% PAG nanoclay, Honeywell's XA2979) and 15% by weight of a nanocomposite Nylon 6 containing 15.7% nanoclay (Nanocor® nanopolyamide concentrate (NPC)) was formed and processed through steps 2 and 5 of the procedure. A film of the composition was tested for OTR and CO<sub>2</sub>TR. OTR was measured at 0.5 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. TRCO2 was measured at 1.2 cc.mil/100 in.<sup>2</sup> (645.16 cm<sup>2</sup>)/day. The OTR and CO2TR were significantly better than the nylon 6 homopolymer of Comparative Example 1.
The above data is summarized in Table 1 below.
TABLE 1
<td>Example number</td><td>Stages of the procedure</td><td>% by weight PA6</td><td>% in weigh 4% nano PA6</td><td>% in weigh 15.7% nano PA6</td><td>wt% MXD6 / MXDI copolyamide</td><td>wt% MB catalyst</td><td>wt% PBD</td><td>OTR</td><td> -1 <sup>n</sup>* Or</td>
<td> 1</td><td> 5</td><td> 100</td><td></td><td></td><td></td><td></td><td></td><td> 3</td><td> 14</td>
<td> 2</td><td> 2,4,5,7</td><td> 30</td><td> 0</td><td> 0</td><td> 70</td><td></td><td></td><td> 0,9</td><td> 1,5</td>
<td> 3</td><td> 2,5</td><td> 20</td><td> 0</td><td> 0</td><td> 80</td><td></td><td></td><td> 0,7</td><td> 1,1</td>
<td> 4</td><td> 2,5</td><td> 10</td><td> 0</td><td> 0</td><td> 90</td><td></td><td></td><td> 0,4</td><td> 0,6</td>
<td> 5</td><td> 2,5</td><td> 0</td><td> 30</td><td> 0</td><td> 70</td><td></td><td></td><td> 0,6</td><td> 1,2</td>
<td> 6</td><td> 2,5</td><td> 15</td><td> 0</td><td> 15</td><td> 70</td><td></td><td></td><td> 0,5</td><td> 1,2</td>
EXAMPLES 7-12
Additional polymer blends were formed through steps 2, 3, 5, and 7 of the process, providing desirable results. Additional mixtures of this type are formed as in the following Table 2 below:
ES 2 379 484 T3
TABLE 2
<td>Example number</td><td>Stages of the procedure</td><td>% by weight PA6</td><td>wt% PA6 4% nanoclay</td><td>% in weigh PA6 nanoclay 15.7%</td><td>wt% MXD6 / MXDI copolyamide</td><td>wt% MB catalyst</td><td>% in weigh by PBD</td>
<td> 7</td><td> 2,3,5,7</td><td> 25</td><td></td><td></td><td> 70</td><td> 2</td><td> 3</td>
<td> 8</td><td> 2,3,5,7</td><td> 15</td><td></td><td></td><td> 80</td><td> 2</td><td> 3</td>
<td> 9</td><td> 2,3,5,7</td><td> 5</td><td></td><td></td><td> 90</td><td> 2</td><td> 2</td>
<td> 10</td><td> 2,3,5,7</td><td></td><td> 25</td><td></td><td> 70</td><td> 2</td><td> 3</td>
<td> 11</td><td> 2,3,5,7</td><td></td><td> 15</td><td></td><td> 80</td><td> 2</td><td> 3</td>
<td> 12</td><td> 2,3,5,7</td><td> 10</td><td></td><td> 15</td><td> 70</td><td> 2</td><td> 3</td>
EXAMPLE 13
A three-layer PET / polyamide blend / PET structure is formed following the techniques of procedure 6.
EXAMPLE 14
A seven-layer structure of PE / coextrusion adhesive / EVOH / polyamide composition / EVOH / coextrusion adhesive / PE is formed following the techniques of procedure 6.
EXAMPLE 15
A seven-layer structure of PE / coextrusion adhesive / EVOH / polyamide blend / EVOH / coextrusion adhesive / PE is formed following the techniques of procedure 6.
Contents24
13 members in 8 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 321575 | United States of America | – | |
| 32157505 | United States of America | A | |
| 32157505 | United States of America | A | |
| 2006038409 | United States of America | W | |
| 2006038409 | United States of America | W | |
| 321575 | – | – | – |
| PCTUS2006038409 | – | – | – |
| US20050321575 | – | – | – |
| WO2006US38409 | – | – | – |
Members13
| Document | Office | Kind | |
|---|---|---|---|
| US2007154668A1 | United States of America | A1 | |
| WO2007078366A1 | World Intellectual Property Organization (WIPO) | A1 | |
| KR20080083029A | Republic of Korea | A | |
| EP1969061A1 | European Patent Office (EPO) | A1 | |
| US7427430B2 | United States of America | B2 | |
| CN101389709A | China | A | |
| CN101389709B | China | B | |
| EP1969061B1 | European Patent Office (EPO) | B1 | |
| AT543875T | Austria | T | |
| ATE543875T1 | Austria | T1 | |
| PT1969061E | Portugal | E | |
| ES2379484T3This record | Spain | T3 | |
| KR101272057B1 | Republic of Korea | B1 |
Numbers
- Publication
- 2379484
- Publication, DOCDB
- 2379484
- Publication, EPODOC
- ES2379484T
- Application
- 6804291
- Application, DOCDB
- 06804291
- Application, EPODOC
- ES20060804291T
Titles2
- Spanish
- Composición de mezcla de poliamidas con excelente comportamiento de barrera a los gases
- English
- Composition of polyamide mixture with excellent gas barrier behavior
Classification
- CPC, 38
- C08G69/265
- C08L77/00
- B32B27/34
- C08G69/26
- C08J5/18
- C08J2377/00
- C08K3/346
- C08K5/092
- C08L9/00
- C08L15/00
- C08L77/06
- B32B27/08
- B32B27/20
- B32B27/306
- B32B27/32
- B32B27/36
- B32B2270/00
- B32B2307/514
- B32B2307/704
- B32B2307/7242
- B32B2307/7244
- B32B2307/738
- B32B2307/74
- B32B2439/60
- B32B2439/70
- B32B2439/80
- Y10S428/91
- C08K2201/008
- Y10T428/1352
- Y10T428/3175
- Y10T428/31728
- Y10T428/31725
- Y10T428/31736
- Y10T428/31739
- Y10T428/31743
- Y10T428/31746
- C08K3/34
- C08K5/098
- IPC, 6
- C08L77 00
- C08J5 18
- C08K3 34
- C08K5 098
- C08L9 00
- C08L21 00