Polymeric compositions, articles made from such compositions, and methods for molding such compositions

Abstract

To provide a method for making a polymer composition suitable for production of a molding exhibiting a desirable combination of low haze and high gloss.SOLUTION: A method for making a polymer composition comprises the steps of: (a) providing a polypropylene random copolymer; (b) providing a polymer additive selected from a group consisting of nucleating agents, clarifying agents, and combinations thereof; (c) providing a fluoropolymer; and (d) mixing the polypropylene random copolymer, the polymer additive and the fluoropolymer and mechanically processing a mixture under shear conditions to produce the polymer composition having (i) apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 1,000 s-1 and a temperature of 190°C, and (ii) apparent melt viscosity of 2,550 Pa s or less at an apparent shear rate of 20 s-1 and a temperature of 190°C.SELECTED DRAWING: None

Description

TECHNICAL FIELD OF THEINVENTION

[0001]

[0001] The present invention relates to polymer compositions, articles made from such polymer compositions, and methods for molding such polymer compositions.

[0002]

[0002] As mentioned above, the present invention is generally directed to polymer compositions, articles (e.g., molded articles) made from such polymer compositions, and methods for molding such polymer compositions. When used to form molded articles, such as extrusion blow molded articles, the polymer compositions of the present invention, which include a synergistic blend of polymer additives and fluoropolymers and have certain desired melt properties (e.g., apparent melt viscosity), are believed to be particularly well suited for producing molded articles exhibiting desirable optical properties (e.g., haze and gloss). In particular, molded articles made using the polymer compositions of the present invention are believed to exhibit a desirable combination of low haze and high gloss compared to articles made using other polymer compositions. In view of these optical properties, the polymer compositions of the present invention and molded articles formed therefrom are believed to be particularly desirable for use in packaging and food containers.

[0003]

[0003] Without wishing to be bound by any particular theory, it is believed that the nucleating or clarifying agent acts to provide desirable optical properties (e.g., low haze) to the bulk or inner portion of the polymer, while the fluoropolymer works in concert with the nucleating or clarifying agent to provide a molded article with desirable surface properties, e.g., high gloss. More specifically, it is believed that the fluoropolymer acts to coat the working surfaces of the machinery used to process the polymer composition, and that the polymer composition flows more smoothly and at a higher rate in the vicinity of these coated surfaces. Furthermore, it is believed that the incorporation of the nucleating or clarifying agent reduces the size of the crystals that form when the polymer cools from the plasticized (molten) state, and that this smaller crystal size causes less pronounced and smaller disturbances on the polymer surface. Finally, it is believed that the melting properties of the polymer composition (as indicated by the apparent melt viscosity) result in a polymer composition that exhibits balanced properties for both extrusion and blow molding processes. In particular, the polymer composition exhibits a relatively low melt viscosity during the extrusion process, which is believed to correlate with the relatively low shear stress of the die wall, meaning that less of the fluoropolymer coating peels off from the die wall during the extrusion process.The polymer composition also exhibits a relatively low viscosity under the low shear stress conditions experienced when the parison is blown and spreads toward the surface of the mold cavity.It is believed that this relatively low viscosity allows the polymer composition to better match the texture of the molded finish (typically polished to a high gloss) and also allows the surface of the parison to be flattened or smoothed, thus reducing surface haze.However, the viscosity of the polymer composition is not so low that the parison cannot stand up under these low shear conditions.

[0004] In a first aspect, the present invention provides a method for producing a medicament for use in a pharmaceutical composition comprising: (a) a thermoplastic polymer; (b) a polymer additive selected from the group consisting of nucleating agents, clarifiers, and combinations thereof; (c) fluoropolymer; A polymer composition comprising: The polymer composition comprises: (i) 1,000 s -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 and a temperature of 190°C.

[0005] In a second aspect, the present invention provides a thermoplastic molded article comprising at least one wall defining a cavity, the wall having an opening therein providing access to the cavity, the thermoplastic molded article comprising a polymer composition comprising a thermoplastic polymer, a polymer additive selected from the group consisting of a nucleating agent, a clarifier and combinations thereof, and a fluoropolymer. The polymer composition preferably comprises: (i) 1,000 s -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 and a temperature of 190°C, it has an apparent melt viscosity of 2,550 Pa·s or less.

[0006] In a third aspect, the present invention provides a method for producing a polymer composition, the method comprising: (a) providing a first thermoplastic polymer; (b) providing a masterbatch composition, the masterbatch composition comprising: (i) a second thermoplastic polymer; (ii) a polymeric additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof; and (iii) a fluoropolymer; and (c) mixing the first thermoplastic polymer and the masterbatch composition to produce a polymer composition, the polymer composition being: (i) 1,000 s -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 and a temperature of 190°C, the process The present invention provides a method comprising:

[0007] In a fourth aspect, the present invention provides a method for molding a polymer composition. In particular, the method comprises: (a) providing an apparatus including a die and a mold cavity, the mold cavity having an interior surface defining a shape of a molded article; (b) providing a polymer composition comprising: (i) a thermoplastic polymer; (ii) a polymer additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof; and (iii) a fluoropolymer; -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 and a temperature of 190° C.; (c) heating the polymer composition to a temperature sufficient to melt the polymer composition such that it may be extruded through a die; (d) extruding the molten polymer composition through a die to form a parison; (e) capturing the parison in a mold cavity; (f) blowing a pressurized fluid into the parison under sufficient pressure to expand the parison and conform it to the interior surface of the mold cavity to produce a molded article; (g) cooling the molded article to a temperature at which the polymer composition at least partially solidifies such that the molded article retains its shape; and (h) Removing the molded product from the mold cavity Detailed Description of the Invention

[0008] In a first aspect, the present invention provides a polymer composition comprising a thermoplastic polymer, a polymer additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof, and a fluoropolymer.

[0009]

[0009] The polymer composition may contain any suitable polymer. For example, the polymer composition may contain a thermoplastic polymer, such as a polyolefin. Suitable polyolefins include, but are not limited to, polypropylene homopolymers, polypropylene copolymers (e.g., polypropylene random copolymers), polypropylene impact copolymers, and combinations thereof. Suitable polypropylene copolymers include, but are not limited to, random copolymers made from the polymerization of propylene in the presence of a comonomer selected from the group consisting of ethylene, but-1-ene (i.e., 1-butene) and hex-1-ene (i.e., 1-hexene). In such polypropylene random copolymers, the comonomer may be present in any suitable amount, but is typically present in an amount of less than about 10% by weight (e.g., about 1 to about 7% by weight). Suitable polypropylene impact copolymers include, but are not limited to, those made by the addition of a copolymer selected from the group consisting of ethylene-propylene rubber (EPR), ethylene propylene-diene monomer (EPDM), polyethylene, and plastomer to a polypropylene homopolymer or polypropylene random copolymer. In such polypropylene impact copolymers, the copolymer may be present in any suitable amount, but is typically present in an amount of about 5 to about 25% by weight. In certain possibly preferred embodiments, the polymer is a polypropylene random copolymer made from the copolymerization of propylene and ethylene, with the ethylene amount being from about 1 to about 7 weight percent.

[0010]

[0010] As mentioned above, the polymer additive is selected from the group consisting of nucleating agents, clarifiers, and combinations thereof. As utilized herein, the term "nucleating agent" is used to refer to an additive that forms nuclei in a polymer or provides sites for crystal formation and / or growth as the polymer solidifies from the molten state. When present, the nucleating agent in the polymer composition may be any suitable nucleating agent. Suitable nucleating agents include, but are not limited to, 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphates (e.g., sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate or aluminum 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate), bicyclo[2.2.1]heptane-2,3-dicarboxylates (e.g., disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate and calcium bicyclo[2.2.1]heptane-2,3-dicarboxylate), cyclohexane-1,2-dicarboxylates (e.g., calcium cyclohexane-1,2-dicarboxylate, monobasic aluminum cyclohexane-1,2-dicarboxylate, dilithium cyclohexane-1,2-dicarboxylate, strontium cyclohexane-1,2-dicarboxylate), and combinations thereof. For bicyclo[2.2.1]heptane-2,3-dicarboxylate and cyclohexane-1,2-dicarboxylate, the carboxylate moieties may be configured in either the cis or trans configuration, although the cis configuration is preferred.

[0011]

[0011] When present in the polymer composition, the nucleating agent may be present in any suitable amount. As will be appreciated by those skilled in the art, the amount of the nucleating agent suitable for use in the polymer composition depends on several factors, such as the composition of the nucleating agent and the desired properties of the polymer composition. For example, the nucleating agent may be present in the polymer composition in an amount of about 0.001 wt% or more, about 0.0025 wt% or more, about 0.01 wt% or more, about 0.05 wt% or more, about 0.075 wt% or more, or about 0.1 wt% or more, based on the total weight of the polymer composition. The nucleating agent may be present in the polymer composition in an amount of about 10 wt% or less, about 5 wt% or less, about 1 wt% or less, about 0.5 wt% or less, about 0.4 wt% or less, or about 0.3 wt% or less. In certain possibly preferred embodiments, the nucleating agent is present in the polymer composition in an amount of from about 0.01 to about 1 weight percent, from about 0.05 to about 0.5 weight percent, from about 0.075 to about 0.4 weight percent, or from about 0.1 to about 0.3 weight percent, based on the total weight of the polymer composition.

[0012]

[0012] When present in the composition, the clarifier may be any suitable clarifier. In certain possibly preferred embodiments, the clarifier is selected from the group consisting of trisamides and acetal compounds which are condensation products of polyhydric alcohols and aromatic aldehydes.Suitable trisamide clarifiers include, but are not limited to, amide derivatives of benzene-1,3,5-tricarboxylic acid, derivatives of N-(3,5-bis-formylamino-phenyl)-formamide (e.g., N-[3,5-bis-(2,2-dimethyl-propionylamino)-phenyl]-2,2-dimethyl-propionamide), derivatives of 2-carbamoyl-malonamide (e.g., N,N'-bis-(2-methyl-cyclohexyl)-2-(2-methyl-cyclohexylcarbamoyl)-malonamide), and combinations thereof.In certain possibly preferred embodiments, the clarifier comprises an acetal compound which is a condensation product of polyhydric alcohols and aromatic aldehydes. Suitable polyhydric alcohols include acyclic polyols such as xylitol and sorbitol, and acyclic deoxypolyols (e.g., 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol). Suitable aromatic aldehydes typically contain a single aldehyde group, with the remaining five positions of the benzene ring either substituted or unsubstituted. Thus, suitable aromatic aldehydes include benzaldehyde and substituted benzaldehydes (e.g., 3,4-dimethyl-benzaldehyde or 4-propyl-benzaldehyde). The acetal compounds produced by the above reaction may be monoacetal, diacetal or triacetal compounds (i.e., compounds containing one, two or three acetal groups, respectively).

[0013] In certain, possibly preferred embodiments, the clarifier comprises an acetal compound conforming to the structure of formula (I):

[0014] [ka]

[0015] In the structure of formula (I), R 1 is selected from the group consisting of hydrogen, alkyl groups, alkenyl groups, hydroxyalkyl groups, alkoxy groups, and halogenated alkyl groups. 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, and a halogen. 12 is -CH 2 OH and -CHOHCH 2 OH. In certain embodiments, R 1 is selected from the group consisting of alkyl and alkenyl groups; R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are hydrogen, and R 12 HA-CHOHCH 2 OH and R 4 and R 9 is selected from the group consisting of alkyl and alkoxy groups. In certain more specific embodiments, R 1 is an alkyl group (preferably n-propyl), R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are hydrogen, and R 12 HA-CHOHCH 2 OH and R 4 and R 9 Each is an alkyl group (preferably n-propyl). In certain other embodiments, R 1 , R 2 , R5 , R 6 , R 7 , R 8 and R 11 are hydrogen, and R 12 HA-CHOHCH 2 OH and R 3 , R 4 , R 9 and R 10 Each of R is an alkyl group (preferably, a methyl group). 1 , R 2 , R 5 , R 6 , R 7 , R 8 and R 11 are hydrogen, and R 12 HA-CHOHCH 2 OH and R 3 , R 4 , R 9 and R 10 is each a halogen (preferably a chlorine atom).

[0016]

[0014] When present in the composition, the clarifier may be present in any suitable amount. As will be understood by those skilled in the art, the amount of the clarifier suitable for use in the polymer composition depends on several factors, such as the composition of the clarifier and the desired optical properties of the polymer composition. For example, the clarifier may be present in the polymer composition in an amount of about 0.001 wt% or more, about 0.0025 wt% or more, about 0.01 wt% or more, about 0.05 wt% or more, about 0.075 wt% or more, or about 0.1 wt% or more, based on the total weight of the polymer composition. The clarifier may be present in the polymer composition in an amount of about 10 wt% or less, about 5 wt% or less, about 1 wt% or less, about 0.7 wt% or less, about 0.6 wt% or less, or about 0.5 wt% or less. In certain possibly preferred embodiments, the clarifier is present in the polymer composition in an amount of about 0.01 to about 1 weight percent, about 0.05 to about 0.7 weight percent, about 0.075 to about 0.6 weight percent, or about 0.1 to about 0.5 weight percent, based on the total weight of the polymer composition. Thus, in certain possibly preferred embodiments, for example, the clarifier is represented by formula (I), where R1 is an alkyl group (e.g., n-propyl), and R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are hydrogen, and R 12 HA-CHOHCH 2 OH and R 4 and R 9 In the case where the clarifier comprises an acetal compound conforming to the structure of formula (I), where R 1 , R 2 , R 5 , R 6 , R 7 , R 8 and R 11 are hydrogen, and R 12 HA-CHOHCH 2 OH and R 3 , R 4 , R 9 and R 10 In the case of an acetal compound according to the structure:

[0017]

[0015] The fluoropolymer present in the polymer composition may be any suitable fluoropolymer (e.g., fluoroplastic or fluoroelastomer). Suitable fluoropolymers include, but are not limited to, polymers made from at least one monomer selected from the group consisting of vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, perfluoro(alkyl vinyl ether), and combinations thereof. In certain possibly preferred embodiments, the fluoropolymer is a polymer selected from the group consisting of (i) a copolymer of vinylidene fluoride and a comonomer selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, 1-hydropentafluoropropylene and 2-hydropentafluoropropylene, (ii) a terpolymer of vinylidene fluoride and a comonomer selected from the group consisting of tetrafluoroethylene and hexafluoropropylene, 1-hydropentafluoropropylene and 2-hydropentafluoropropylene, (iii) a copolymer of tetrafluoroethylene and propylene, (iv) a copolymer of tetrafluoroethylene, propylene and vinylidene fluoride, and (v) a combination of two or more of (i) to (iv). In certain more specific possibly preferred embodiments, the fluoropolymer is a terpolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene.

[0018]

[0016] The fluoropolymer suitable for use in the polymer composition may have any suitable molecular weight. However, in certain possibly preferred embodiments, the fluoropolymer has a relatively high molecular weight. Without wishing to be bound by any particular theory, it is believed that fluoropolymers having a relatively high molecular weight are particularly well suited for use in the polymer composition of the present invention, at least in part, due to the ability of such fluoropolymers to form and maintain coatings on the working surfaces of the equipment used to process the polymer composition. It is further believed that the coatings formed on these working surfaces help improve the appearance (e.g., improve gloss) of the molded article produced from the polymer composition by preventing defects on these working surfaces from causing defects on the surface of the molded article, or at least reducing the degree of defects formed on the molded article.

[0019]

[0017] As will be appreciated by those skilled in the art, the molecular weight of polymers, including fluoropolymers, such as those used in the polymer composition of the present invention, may be measured and expressed in many different ways, but due to the complexity of measuring the molecular weight of the polymer chains in a polymer system, measurements based on a correlation between the average molecular weight and one or more physical properties of the polymer are commonly used. One such measurement is based on a correlation between the average molecular weight and the flow rate of the molten polymer (e.g., Melt Flow Index (MFI)). Another such measurement is based on a correlation between the average molecular weight and the shear torque resisting the rotation of a cylindrical metal disk or rotor embedded in the polymer (i.e., Mooney viscosity).

[0020]

[0018] Fluoropolymers suitable for use in the polymer composition may have any suitable melt flow index (MFI). In certain possibly preferred embodiments, the fluoropolymer has an MFI of about 2 g / 10 min or more, about 3 g / 10 min or more, about 4 g / 10 min or more, or about 5 g / 10 min or more, measured according to ASTM D1238-04c at 265°C using a 5 kg weight. In certain possibly preferred embodiments, the fluoropolymer has an MFI of about 2 to about 50 g / 10 min, about 3 to about 40 g / 10 min, or about 4 to about 30 g / 10 min, measured according to ASTM D1238-04c at 265°C using a 5 kg weight. In certain possibly more preferred embodiments, the fluoropolymer has an MFI of about 5 to about 25 g / 10 min, measured according to ASTM D1238-04c at 265°C using a 5 kg weight.

[0021]

[0019] The fluoropolymer suitable for use in the polymer composition may have any suitable Mooney viscosity. In certain possibly preferred embodiments, the Mooney viscosity of the fluoropolymer is about 25 or more, or about 28 or more, measured according to ASTM standard D1646-07 at 121°C, large rotor, condition ML 1+10 minutes. In certain possibly preferred embodiments, the Mooney viscosity of the fluoropolymer is about 80 or less, about 70 or less, about 60 or less, about 50 or less, or about 40 or less (e.g., about 38 or less), measured according to ASTM standard D1646-07 at 121°C, large rotor, condition ML 1+10 minutes. Thus, in certain possibly preferred embodiments, the fluoropolymer has a Mooney viscosity of from about 25 to about 80, from about 25 to about 70, from about 25 to about 60, from about 25 to about 50, or from about 25 to about 40 (e.g., from about 28 to about 38) when measured according to ASTM standard D1646-07 at 121° C., large rotor, condition ML 1+10 minutes.

[0022]

[0020] Suitable fluoropolymers for use in the polymer composition include multimodal fluoropolymers. As used herein, the term "multimodal" is used to refer to a fluoropolymer having at least two components that are distinct and have different molecular weights (e.g., distinct and have different average molecular weights). Suitable multimodal fluoropolymers are described, for example, in International Patent Application Publication WO2000 / 69967. In such multimodal fluoropolymers, each of the components may be amorphous or semicrystalline, or one component may be amorphous and another component may be semicrystalline.

[0023]

[0021] The fluoropolymer may be present in the polymer composition of the present invention in any suitable amount. In order to avoid or reduce adverse effects on the optical properties of articles manufactured using the polymer composition of the present invention, the inventors have found that the fluoropolymer should typically be present in the polymer composition in a relatively small amount. In certain possibly preferred embodiments, the fluoropolymer is present in the polymer composition in an amount of about 1,000 ppm or less, about 750 ppm or less, about 500 ppm or less, or about 250 ppm or less (e.g., about 200 ppm or less), based on the total weight of the polymer composition. In certain possibly preferred embodiments, the fluoropolymer may be present in the polymer composition in an amount such that the ratio of the amount of polymer additive present in the polymer composition to the amount of fluoropolymer present in the polymer composition is about 4:1 to about 100:1, about 8:1 to about 100:1, about 10:1 to about 100:1, or about 20:1 to about 100:1, based on the total weight of the polymer additive and the fluoropolymer present in the polymer composition.

[0024] Many commercially available fluoropolymers sold as polymer processing aids contain small amounts of at least one interfacial agent, such as a polyalkylene oxide (e.g., poly(ethylene glycol) or poly(ethylene oxide)), which is believed to improve the performance of the polymer processing aid by wetting the surfaces of the fluoropolymer particles in the polymer processing aid. However, despite the benefits typically associated with the use of interfacial agents, such as poly(ethylene glycol), it is believed that such interfacial agents may actually reduce the favorable optical properties of molded articles produced using the polymer compositions of the present invention. Thus, in certain possibly preferred embodiments, the polymer compositions of the present invention are substantially free of poly(ethylene glycol) or substantially free of any interfacial agent. More specifically, in certain possibly preferred embodiments, the polymer compositions contain less than 100 ppm poly(ethylene glycol), less than 50 ppm poly(ethylene glycol), less than 25 ppm poly(ethylene glycol), less than 10 ppm poly(ethylene glycol), or less than 5 ppm poly(ethylene glycol).

[0025]

[0023] The polymeric compositions may have any suitable apparent melt viscosity. The apparent melt viscosity of the polymeric compositions may be measured using any suitable method. For example, the apparent melt viscosity may be determined using the test method described in ASTM Test Method D3835-08 entitled "Standard Test Method for Determination of Properties of Polymeric Materials by Means of a Capillary Rheometer". Although this test method suggests that 230°C is a test temperature typically used to test polypropylene compositions, applicants believe that 190°C is a more suitable temperature because it better approximates the lower processing temperatures that applicants intend to enable with the disclosed compositions and methods. Thus, the apparent melt viscosity of the polymeric compositions recited herein is preferably determined using the test method referenced above at a temperature of 190°C. The apparent melt viscosity of the polymeric compositions may be measured at any suitable apparent shear rate. It is believed to be useful to measure the apparent melt viscosity at two or more different apparent shear rates that approximate the shear conditions that the polymeric compositions will experience during processing. For example, at 50 s -1 , 20s -1 , and 15s -1 An apparent shear rate of 1,000 s is considered to approximate the relatively gentle shear conditions experienced by a polymer composition when, for example, a parison is blown and spreads against the inner surface of a mold cavity. -1It is believed that the apparent shear rate of, for example, approximates the relatively high shear conditions that the polymer composition experiences when it exits the die orifice. When measuring the apparent melt viscosity of the polymer composition, the capillary rheometer preferably includes a capillary die having a diameter of 1.00 mm and a length to diameter ratio of 30:1. In addition, the polymer composition is preferably allowed to remain in the capillary rheometer for a residence time of 6 minutes before the start of the test. Preferably, the measurement of the apparent melt viscosity is repeated at least three times, and the values ​​of such measurements are averaged. Finally, the apparent melt viscosity of the polymer composition is preferably determined after the polymer, the polymer additive, the fluoropolymer, and any components (e.g., peroxide) are melt processed (e.g., passed through an extruder).

[0026] In a preferred embodiment, the polymer composition is -1 In another preferred embodiment, the polymer composition has an apparent melt viscosity of about 200 Pa·s or less at an apparent shear rate of 20 s and a temperature of 190° C. -1 In another preferred embodiment, the polymer composition has an apparent melt viscosity of 2,550 Pa·s or less at an apparent shear rate of 50 s and a temperature of 190° C. -1 In yet another preferred embodiment, the polymer composition has an apparent melt viscosity of 1,500 Pa·s or less at an apparent shear rate of 15 s and a temperature of 190° C. -1 and a temperature of 190° C. In a particularly preferred embodiment, the polymer composition has an apparent melt viscosity of 3000 Pa s or less at an apparent shear rate of 1,000 s -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 In another particularly preferred embodiment, the polymer composition has an apparent melt viscosity of 2,550 Pa·s or less at an apparent shear rate of 1,000 s and a temperature of 190° C. -1 (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s and a temperature of 190 °C; -1and a temperature of 190°C; and (iii) an apparent melt viscosity of 50 s -1 In another particularly preferred embodiment, the polymer composition has an apparent melt viscosity of 1,500 Pa·s or less at an apparent shear rate of 1,000 s or less and a temperature of 190° C. -1 (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s and a temperature of 190 °C; -1 and a temperature of 190°C; and (iii) an apparent melt viscosity of 15 s -1 In yet another particularly preferred embodiment, the polymer composition has an apparent melt viscosity of 3000 Pa·s or less at an apparent shear rate of 1,000 s and a temperature of 190° C. -1 (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s and a temperature of 190 °C; -1 (iii) an apparent melt viscosity of 2,550 Pa s or less at an apparent shear rate of 50 s and a temperature of 190 °C; -1 and a temperature of 190°C; and (iv) an apparent melt viscosity of 1,500 Pa s or less at an apparent shear rate of 15 s -1 and a temperature of 190°C, it has an apparent melt viscosity of 3000 Pa·s or less.

[0027] The values ​​given above represent maximum values ​​for the apparent melt viscosity of the polymer composition at several different apparent shear rates. In certain embodiments, the apparent melt viscosity of the polymer composition preferably does not fall below a certain minimum value, which value depends on the apparent shear rate. For example, in a preferred embodiment, the polymer composition has an apparent melt viscosity of 1,000 s -1 At an apparent shear rate of 50 Pa·s or more and a temperature of 190° C., the polymer composition has an apparent melt viscosity of about 50 Pa·s or more, more preferably about 100 Pa·s or more. -1 At an apparent shear rate of 20 s and a temperature of 190° C., the polymer composition has an apparent melt viscosity of about 500 Pa·s or more, more preferably about 700 Pa·s or more.-1 At an apparent shear rate of 15 s and a temperature of 190° C., the polymer composition has an apparent melt viscosity of about 500 Pa·s or more, more preferably about 800 Pa·s or more. -1 and a temperature of 190° C., the apparent melt viscosity is about 800 Pa·s or more, more preferably about 1,000 Pa·s or more.

[0028] In one set of preferred embodiments, the polymer composition preferably comprises: (i) 1,000 s -1 and a temperature of 190° C.; and (ii) an apparent melt viscosity of about 50 Pa s to about 200 Pa s (e.g., about 100 Pa s to about 200 Pa s). -1 and a temperature of 190° C. of about 500 Pa·s to 2,550 Pa·s (e.g., about 800 Pa·s to 2,550 Pa·s). In another particularly preferred embodiment, the polymer composition has an apparent melt viscosity of about 1,000 s -1 and a temperature of 190°C; (ii) an apparent melt viscosity of about 50 Pa s to about 200 Pa s (e.g., about 100 Pa s to about 200 Pa s); -1 and a temperature of 190° C.; and (iii) an apparent melt viscosity of about 500 Pa·s to 2,550 Pa·s (e.g., about 800 Pa·s to 2,550 Pa·s). -1 and a temperature of 190° C. of about 500 Pa·s to 1,500 Pa·s (e.g., about 700 Pa·s to 1,500 Pa·s). In another particularly preferred embodiment, the polymer composition has an apparent melt viscosity of about 1,000 s -1 (ii) an apparent melt viscosity of about 50 Pa s to about 200 Pa s (e.g., about 100 Pa s to about 200 Pa s) at an apparent shear rate of 20 s and a temperature of 190 °C; -1 and a temperature of 190° C.; and (iii) an apparent melt viscosity of about 500 Pa·s to 2,550 Pa·s (e.g., about 800 Pa·s to 2,550 Pa·s). -1and a temperature of 190° C. of about 800 Pa·s to 3,000 Pa·s (e.g., about 1,000 Pa·s to 3,000 Pa·s). In yet another particularly preferred embodiment, the polymer composition has an apparent melt viscosity of about 1,000 s -1 and a temperature of 190°C; (ii) an apparent melt viscosity of about 50 Pa s to about 200 Pa s (e.g., about 100 Pa s to about 200 Pa s); -1 and a temperature of 190°C; (iii) an apparent melt viscosity of about 500 Pa·s to 2,550 Pa·s (e.g., about 800 Pa·s to 2,550 Pa·s); -1 and a temperature of 190° C.; and (iv) an apparent melt viscosity of about 500 Pa·s to 1,500 Pa·s (e.g., about 700 Pa·s to 1,500 Pa·s). -1 and a temperature of 190° C., has an apparent melt viscosity of about 800 Pa·s to 3,000 Pa·s (e.g., about 1,000 Pa·s to 3,000 Pa·s).

[0029] The polymer (e.g., polypropylene polymer) used in the composition may be a polymer manufactured to have the apparent melt viscosity, melt flow rate and / or flow rate ratio described herein for the polymer composition. For example, polypropylene polymers suitable for use in the composition include those manufactured in such a way that the polymer sold by the manufacturer has one or more of the apparent melt viscosity values ​​described herein for the polymer composition. Alternatively, a polymer (e.g., polypropylene polymer) that does not have the desired properties may be modified through treatment with one or more additives, by mechanical processing, or by blending the polymer with one or more additional polymers to achieve the desired apparent melt viscosity, melt flow rate and / or flow rate ratio. For example, the polymer may be combined with an organic peroxide or a visbreaking agent and then melt processed (e.g., extruded) to modify one or more properties of the polymer. Examples of organic peroxides suitable for such use include 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy))hexyne-3,3,6,6,9,9-pentamethyl-3-(ethyl acetate)-1,2,4,5-tetraoxycyclononane, tert-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, tert-butylperoxyisopropyl carbonate, di-tert-butyl peroxide, p-chlorobenzoyl peroxide, peroxide, dibenzoyl diperoxide, tert-butyl cumyl peroxide, tert-butyl hydroxyethyl peroxide, di-tert-amyl peroxide, 2,5-dimethylhexene-2,5-diperisononanoate, acetylcyclohexanesulfonyl peroxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl-perneodecanoate, tert-butyl perpivalate, tert-amyl perpivalate, bis(2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, bis(4-chlorobenzoyl) peroxide, tert-butyl perisobutyrate, tert-butyl permaleate, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclo-hexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxyisopropylcarbonate, tert-butyl perisononanoate, 2,5-dimethylhexane 2,5-dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl perbenzoate, 2,2 bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane 2,5-di-tert-butylperoxide, 3-tert-butylperoxy-3-phenylphthalide, di-tert-amyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, 3,5-bis(tert-butylperoxy)-3,5-dimethyl-1,2-dioxolane, di-tert-butyl peroxide, 2,5-dimethylhexyne 2,5-di-tert-butyl peroxide, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide and tert-butyl hydroperoxide.

[0030] If used, any suitable amount of organic peroxide or visbreaking agent may be added to the polymer composition prior to melt processing. As will be appreciated by those skilled in the art, organic peroxides or visbreaking agents typically decompose during melt processing (e.g., extrusion), and thus the organic peroxides or visbreaking agents are typically no longer present in detectable amounts in the polymer composition after melt processing. The suitable amount of organic peroxide added prior to melt processing depends on several factors, such as the particular polymer used in the composition, the starting properties of the polymer, and the desired change in the properties of the polymer. In a preferred embodiment, the organic peroxide may be present in the polymer composition (prior to melt processing) in an amount of about 10 ppm or more, about 50 ppm or more, or about 100 ppm or more, based on the total weight of the polymer composition prior to melt processing. In another preferred embodiment, the organic peroxide may be present in the polymer composition (before melt processing) in an amount of about 1% by weight (10,000 ppm) or less, about 0.5% by weight (5,000 ppm) or less, about 0.4% by weight (4,000 ppm) or less, about 0.3% by weight (3,000 ppm) or less, about 0.2% by weight (2,000 ppm) or less, or about 0.1% by weight (1,000 ppm) or less, about 0.05% by weight (500 ppm) or less, based on the total weight of the polymer composition before melt processing. Thus, in a series of preferred embodiments, the organic peroxide may be present in the polymer composition (before melt processing) in an amount of about 10 to about 5,000 ppm, about 50 to about 3,000 ppm, about 50 to about 2,000 ppm, or about 100 to about 1,000 ppm, based on the total weight of the polymer composition before melt processing.

[0031] As discussed above, a polymer that does not initially have the desired apparent melt viscosity, melt flow rate, and / or flow rate ratio may be machined in such a way as to modify any of these properties to be within the desired parameters. For example, the polymer may be processed under relatively vigorous, high shear conditions (e.g., using a twin-screw compounding extruder operating at high screw speeds, e.g., 250 rpm or higher). It is believed that such high shear conditions can modify the melt properties of the polymer to an apparent melt viscosity, melt flow rate, and / or flow rate ratio in the desired ranges described herein.

[0032] As mentioned above, a polymer that does not initially have the desired apparent melt viscosity, melt flow rate and / or flow rate ratio may be combined with one or more additional polymers so that the properties of the resulting mixture are within the desired parameters. For example, a polymer with a relatively high apparent melt viscosity (i.e., an apparent melt viscosity above the maximum listed for the range above) may be combined with a second polymer with a lower apparent melt viscosity to achieve the desired properties. The amount of additional polymer required for such use may depend on several factors, such as the initial properties of the first polymer (e.g., the apparent melt viscosity of the first polymer), the properties of the additional polymer (e.g., the apparent melt viscosity of the second polymer) that will be combined with the first polymer, and the desired properties of the resulting mixture. In a particularly preferred embodiment, a polymer that does not initially have the desired apparent melt viscosity, melt flow rate and / or flow rate ratio may be combined with a masterbatch composition comprising a second polymer, a polymeric additive, and a fluoropolymer. The second polymer contained in the masterbatch acts as a carrier for the other components of the masterbatch, but also functions as a second polymer to modify the apparent melt viscosity, melt flow rate and / or flow rate ratio of the mixture so that it is within a desired range. In such embodiments, the masterbatch composition does not necessarily include only one polymer. For example, the masterbatch may include a combination of two or more different polymers that impart desired properties to the masterbatch composition.

[0033]

[0031] The polymer composition may have any suitable melt flow rate. The melt flow rate of the polymer composition may be determined using any suitable method. For example, the melt flow rate of the polymer composition may be determined using procedure B of ASTM standard D1238-10, entitled "Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer". The melt flow rate of the polymer composition is preferably measured using the aforementioned standard test method. Preferably, the polymer composition has a melt flow rate of 2.0 g / 10 min or more. More preferably, the polymer composition has a melt flow rate of about 2.1 g / 10 min or more, about 2.2 g / 10 min or more, about 2.3 g / 10 min or more, about 2.4 g / 10 min or more, or about 2.5 g / 10 min or more. The polymer composition has a melt flow rate of about 10 g / 10 min or less, more preferably about 8 g / 10 min or less. As in measuring the apparent melt viscosity, the melt flow rate of a polymer composition is preferably determined after the polymer, polymer additives, fluoropolymer and any optional components (e.g., peroxide) have been melt processed (e.g., passed through an extruder).

[0034] As will be appreciated by those skilled in the art, a polymer contains a population of distinct polymer chains, which have different lengths and molar masses. The statistical distribution of the lengths / molar masses of the polymer chains contained in a polymer is generally referred to as the molar mass distribution or molecular weight distribution. The polymers used in the compositions described herein may have any suitable molar mass distribution. For example, the polymer may have a molar mass distribution that exhibits a single mode, or the molar mass distribution may exhibit multiple modes (e.g., bimodal, trimodal, etc.). The breadth of the molar mass distribution of a polymer can be expressed using a polydispersity index. The polydispersity index is calculated by measuring the number-average molar mass and mass-average molar mass (i.e. weight-average molar mass) of a polymer and then dividing the mass-average molar mass of the polymer by the number-average molar mass of the polymer. The result is a dimensionless unit that quantifies the broadness of the molar mass distribution, with higher values ​​indicating a broader molar mass distribution. The broadness of the molar mass distribution can also be quantified indirectly by measuring the melt flow rates of the polymer (or compositions containing the polymer) under different conditions and comparing them to obtain the flow rate ratio (FRR). This method is described, for example, in the "Standard Test Method The FRR is set forth in procedure D of ASTM standard D1238 entitled "Melt Flow Rates for Thermoplastics by Extrusion Plastometer." Preferably, the FRR is set forth in procedure D of the standard (MFR 10 ) measured using a 10 kg weight as specified in the specification (MFR 2 The FRR is calculated using the melt flow rate measured using a 2 kg weight as specified in the JIS C 1991 1991 standard. The polymer compositions described herein may have any suitable FRR. Preferably, the polymer compositions have an FRR (MFR) of about 20 or less. 10 / MFR 2 More preferably, the polymer composition has an FRR (MFR) of about 19 or less, or about 18 or less. 10 / MFR 2As in the measurements of apparent melt viscosity and melt flow rate, the flow rate ratio of the polymer composition is preferably determined after the polymer, polymer additive, fluoropolymer and any optional components (e.g., peroxide) have been melt processed (e.g., passed through an extruder).

[0035]

[0033] As noted above, the present invention also provides a thermoplastic molded article comprising at least one wall defining a cavity, the wall having an opening therein providing access to the cavity, the wall being formed from a polymeric composition, such as any of the polymeric composition embodiments described above, comprising a polymer, a polymeric additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof, and a fluoropolymer.

[0036] As mentioned above, it is believed that the polymer compositions of the present invention are particularly well suited for use in producing molded articles exhibiting desirable optical properties, such as high gloss (both internal and external gloss) and low haze. In particular, it is believed that molded articles produced using the polymer compositions of the present invention may exhibit gloss values ​​that are 5, 10, 15, or even 20 gloss units higher than molded articles produced using comparative polymer compositions that do not contain each of the components described in this application, when the gloss of the molded article is measured according to ASTM standard D523 at an angle of 60°.

[0037]

[0035] The thermoplastic molded article of the present invention may be formed by any suitable method. However, it is believed that the polymer composition of the present invention is particularly well suited for use in an extrusion blow molding process. Thus, in a third aspect, the present invention provides a method that generally includes the steps of providing an apparatus including a die and a mold cavity, providing a polymer composition, heating the polymer composition to a temperature sufficient to plasticize (melt) the polymer composition so that it may be extruded through the die of the apparatus, extruding the plasticized (molten) polymer composition through the die to form a parison, capturing the parison in the mold cavity, blowing a pressurized fluid into the parison under a pressure sufficient to expand the parison and conform it to the inner surface of the mold cavity and produce a molded article, allowing the molded article to cool to a temperature at which the polymer composition at least partially solidifies so that the molded article retains its shape, and removing the molded article from the mold cavity. The polymer composition used in the method includes a polymer, a polymer additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof, and a fluoropolymer, such as any of the polymer composition embodiments described above.

[0038] The apparatus used to carry out the method of the present invention may be any suitable extrusion blow molding apparatus. Suitable extrusion blow molding apparatuses include continuous extrusion blow molding apparatuses, such as rotary wheel extrusion blow molding apparatuses and shuttle extrusion blow molding apparatuses, and non-continuous extrusion blow molding apparatuses, such as reciprocating screw extrusion blow molding apparatuses and accumulator head extrusion blow molding apparatuses. As described above, the apparatus includes a die through which the plasticized (molten) polymer composition is extruded to form a parison. The apparatus also includes a mold having a mold cavity. The mold cavity or the inner surface of the mold cavity defines the shape of the molded article produced by the apparatus. More specifically, the inner surface of the mold cavity defines the outer surface of the molded article produced by the apparatus.

[0039] In certain possibly preferred embodiments, the equipment used in carrying out the method may be pre-prepared for the production of molded articles by first flowing a polymer composition containing a fluoropolymer (e.g., a masterbatch containing a fluoropolymer) through the working surfaces of the equipment, such as the die and mold. More specifically, when a masterbatch is used, the masterbatch is placed in a carrier polymer, mixed, and the resulting mixture is flowed through the equipment. Typically, the masterbatch is placed in the carrier polymer at a ratio or rate that produces a mixture containing a greater amount of fluoropolymer than the amount of fluoropolymer present in the polymer composition used to produce the molded article. Without wishing to be bound by any particular theory, it is believed that flowing this mixture containing a relatively large amount of fluoropolymer through the equipment helps to completely coat the working surfaces of the equipment with fluoropolymer. It is also believed that this coating helps to improve the optical properties of the molded article, at least in part, by eliminating or at least reducing defects in the molded article caused by imperfections or irregularities in the working surfaces of the equipment (e.g., the die and mold cavity). The fluoropolymer and carrier polymer used in the above procedure may be any suitable fluoropolymer and carrier polymer, such as the fluoropolymer and thermoplastic polymer described above. Furthermore, the fluoropolymer and carrier polymer may be the same as those contained in the polymer composition used to produce the molded article, or the fluoropolymer and / or carrier polymer may be different from those contained in the polymer composition used to produce the molded article.

[0040] When used prior to the manufacture of molded articles according to the method of the present invention, the polymer composition (e.g., masterbatch composition) described in the preceding paragraph may be flowed through the equipment for any suitable length of time. Typically, the composition (e.g., masterbatch composition) is flowed through the equipment for a sufficient length of time (e.g., about 5 minutes or more, about 10 minutes or more, or about 15 minutes or more) for the composition (e.g., masterbatch composition) to be processed through the internal parts of the equipment (e.g., extruder screw) and begin to coat the working surfaces of the equipment. After the composition (e.g., masterbatch composition) has been flowed through the equipment for the desired length of time, the equipment may be disassembled so that any char and / or molten polymer may be removed from the working surfaces of the equipment (e.g., die). After these surfaces are cleaned, the equipment may be reconstructed and the composition (e.g., masterbatch and carrier polymer mixture) may be flowed through the equipment for an additional time (e.g., an additional 60 minutes or more), if desired. Once a desired amount of the composition (e.g., the masterbatch and carrier polymer mixture) has been flowed through the apparatus, the apparatus may be purged by flowing the carrier polymer (i.e., carrier polymer without the masterbatch) through the apparatus for a length of time sufficient to purge the masterbatch and carrier polymer mixture from the apparatus (e.g., about 15 minutes or more). The carrier polymer used in this purging step is typically the same as the carrier polymer that is mixed with the masterbatch composition, although they are not necessarily, and need not be, the same.

[0041]

[0039] When following the above preparation procedure, the apparatus is purged for a desired length of time, and the polymer composition comprising the polymer additive and the fluoropolymer is fed into the apparatus. As will be understood by those skilled in the art, the step of heating the polymer composition to a temperature sufficient to plasticize (melt) the composition is typically achieved, at least in part, by friction caused by the extruder screw used to feed the polymer composition into the die of the apparatus. This frictional heating is typically assisted by using a heater that allows the polymer composition to be heated under more controlled conditions to a temperature at which the polymer composition is more easily extruded through the die.

[0042]

[0040] Once the polymer composition is heated to this temperature, it is extruded through the die of the device to form a parison. The resulting parison is then captured in the mold cavity of the device. The mold typically contains a single opening that allows access to the mold cavity. The parison is captured in the mold so that the open end of the parison is aligned with the opening of the mold. Once the parison is captured in the mold, a pressurized fluid (e.g., air) is blown into the parison under sufficient pressure to expand the parison and conform it to the inner surface of the mold cavity to form the desired molded article. Once the parison has been blown to form the desired molded article, the article is left in the mold for a sufficient length of time for the polymer to solidify to such an extent that the article will retain its shape when removed from the mold. The mold of the device is typically cooled so that this cooling can be accomplished more quickly, reducing cycle time.

[0043] The following examples further illustrate the above subject matter but, of course, should not be construed as in any way limiting its scope.

[0044] Example 1 This example demonstrates a method for producing a thermoplastic article in accordance with the present invention. Five kilogram batches of six polypropylene random copolymer samples (Samples 1A-1F) were compounded according to the formulations shown below in Table 1. Five kilograms of a polymer composition (Polymer Composition A) was prepared according to the formulation shown below in Table 2.

[0045]

[0043] The fluoropolymer used in this example is Dynamar® FX 5911 polymer processing additive manufactured by 3M. The fluoropolymer is believed to be a terpolymer of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene, which exhibits a melt flow rate of approximately 10.8 grams per 10 minutes, measured according to ASTM D1238-04c at 265°C using a 5 kg weight. Dynamar® FX 5911 is also believed to be substantially free of surfactants. The peroxide used in this example is Trigonox® 101, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane manufactured by Akzo Nobel. The polypropylene random copolymer used in Samples 1A-1F and Polymer Composition A was Tipplen R® 605 manufactured by MOL Petrochemicals Co. Ltd, which exhibits a melt flow rate of approximately 2 g per 10 min when measured according to ISO 1133 at 230° C. using a 2.16 kg weight.

[0046] [Table 1]

[0047] [Table 2]

[0048] Polymer composition A was compounded by blending the components in a Kenwood KM800 low intensity mixer for a scheduled time of 5 minutes at dial setting 1. The samples were then melt compounded in a Leistritz Micro27 GL-40D twin screw compounding extruder with two 27 mm diameter screws and a length / diameter ratio of 40:1. The extruder barrel temperature was increased from approximately 200° C. to approximately 230° C., the throughput was set at 40 kg / h, and the screw speed was set at 450 rpm. The extrudates (in the form of four strands) for each sample were cooled in a water bath and subsequently pelletized.

[0049] Each of the polypropylene random copolymer samples was compounded by blending the ingredients in a Kenwood KM800 low intensity mixer for a scheduled time of 5 minutes at dial setting 1. The mixture was then melt compounded in a Leistritz Micro27 GL-40D twin screw compounding extruder with a length / diameter ratio of 40:1, equipped with two 27 mm diameter screws. The barrel temperature of the extruder was increased from approximately 200°C to approximately 230°C, the throughput was set at 40 kg / h, and the screw speed was set at 450 rpm. The extrudate (in the form of four strands) for each sample was cooled in a water bath and subsequently pelletized.

[0050]

[0046] The melt flow rates (MFR) of Samples 1A-1F were measured on pellets at 230°C using a 2.16 kg weight according to ISO 1133. The results are shown in Table 3 below.

[0051]

[0047] The apparent melt viscosities of Samples 1A-1F were measured using a Goettfert Rheo-Tester 2000 capillary rheometer in accordance with ASTM D3835-08. The apparent melt viscosities were measured from 10 to 1000 s using a 1.00 mm diameter capillary die with a length to diameter ratio of 30:1. -1(The samples were conditioned in the rheometer for a residence time of 6 minutes before testing.) The apparent melt viscosity of Sample 1 at various shear rates is shown in Table 3.

[0052] [Table 3]

[0053] Following the preparation sequence as described above, each of the polypropylene random copolymer samples 1A-1F was blown into 300 mL shampoo bottles on a single shuttle, single station W. Mueller extrusion blow molding machine. The barrel temperature was ramped from approximately 180°C to approximately 190°C, and the extrusion head was maintained at a temperature of approximately 180°C. The manifold temperature was maintained at approximately 190°C. The die temperature was set at 180°C. The molten polymer parison was extruded at a melt temperature of approximately 190°C into a fine glass bead blasted blow mold, which was maintained at a mold temperature of approximately 12°C. The cycle time was set at 12.2 seconds. The final polypropylene bottle weighed approximately 22 grams and measured a thickness of 0.95 mm. The produced bottles were then tested as described below.

[0054]

[0049] The percent haze and percent transparency for the bottle sidewalls were measured according to ASTM standard D1103-92 using BYK-Gardner Haze-Guard Plus. The gloss of both the inside and outside of the bottle sidewalls was measured according to ASTM standard D523 using BYK-Gardner micro-TRI-gloss at a 60° angle. The measured percent haze, percent transparency and gloss values ​​for the bottles are shown in Table 4 below.

[0055] [Table 4]

[0056] As can be seen from the data in Table 4, the samples having the desired apparent melt viscosity (e.g., Samples 1E and 1F) exhibited a desirable combination of low haze, high clarity, and high gloss (both inside and outside). In fact, the outside gloss for Samples 1E and 1F was dramatically higher than the gloss for other samples, such as Sample 1D, which contained a similar additive combination as Samples 1E and 1F but did not have the desired apparent melt viscosity value. This improvement in gloss resulted in a bottle with significantly improved aesthetics.

[0057] Example 2 This example demonstrates a method for producing a thermoplastic article in accordance with the present invention.

[0058] ISPLEN® RC530 polypropylene random copolymer was used in this example. The resin as received was labeled Sample 2A. The same resin was used to prepare Samples 2B-2D. All Samples 2A-2D contain approximately 2000 ppm NX8000K clarifier and approximately 90 ppm Dynamar™ FX5911 polymer processing aid.

[0059]

[0053] Samples 2B-2D were melt compounded in a Leistritz Micro27 GL-40D twin screw compounding extruder with two 27 mm diameter screws and a length / diameter ratio of 40:1. The extruder barrel temperature was set at approximately 230°C along the entire barrel (flat temperature profile), the throughput was set at 30 kg / h, and the screw speed was set at 265 rpm for Sample 2B, 415 rpm for Sample 2C, and 495 rpm for Sample 2D. The extrudates (in the form of four strands) for each sample were cooled in a water bath and subsequently pelletized.

[0060]

[0054] The melt flow rates (MFR) of Samples 2A-2D were measured on pellets at 230°C using a 2.16 kg weight according to ISO 1133. The results are shown in Table 5 below.

[0061]

[0055] The apparent melt viscosities of Samples 2A-2D were measured using a Goettfert Rheo-Tester 2000 capillary rheometer in accordance with ASTM D3835-08. The apparent melt viscosities were measured from 10 to 1000 s using a 1.00 mm diameter capillary die with a length to diameter ratio of 30:1. -1 The apparent melt viscosities of Samples 2A-D at various shear rates in the range of 190° C. (The samples were conditioned in the rheometer for a residence time of 6 minutes before testing.) The apparent melt viscosities of Samples 2A-D at various shear rates are shown in Table 5.

[0062] [Table 5]

[0063] Each of the polypropylene random copolymer samples 2A-2D was blown into 300 mL shampoo bottles on a single shuttle, single station W. Mueller extrusion blow molding machine. The barrel temperature was ramped from approximately 180°C to approximately 190°C, and the extrusion head was maintained at a temperature of approximately 180°C. The manifold temperature was maintained at approximately 190°C. The die temperature was set at 180°C. The molten polymer parison was extruded at a melt temperature of approximately 190°C into a fine glass bead blasted blow mold, which was maintained at a mold temperature of approximately 12°C. The cycle time was set at 10.2 seconds. The final polypropylene bottles weighed approximately 20 grams and measured a thickness of 1.0 mm. The produced bottles were then tested as described below.

[0064]

[0057] The percent haze and percent transparency for the bottle sidewalls were measured according to ASTM standard D1103-92 using BYK-Gardner Haze-Guard Plus. The gloss of both the inside and outside of the bottle sidewalls was measured according to ASTM standard D523 using BYK-Gardner micro-TRI-gloss at a 60° angle. The measured percent haze, percent transparency and gloss values ​​for the bottles are shown in Table 6 below.

[0065] [Table 6]

[0066] As can be seen from the data in Table 6, samples having the desired apparent melt viscosity (e.g., Sample 2D) exhibited a desirable combination of low haze, high clarity, and high gloss (both inside and outside). In fact, the outside gloss of Sample 2D was dramatically higher than the gloss for all other samples that contained similar additive combinations as Sample 2D but did not have the desired apparent melt viscosity values. This improvement in gloss resulted in a bottle with significantly improved aesthetics.

[0067]

[0059] All references cited herein, including publications, patent applications, and patents, are incorporated by reference herein to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0068]

[0060] In the context of describing the subject matter of this application (particularly in the context of the claims below), the use of the terms "a," "an," and "the," and similar referents, should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise noted. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referring to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually listed herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better clarify the subject matter of the present application and does not limit the scope of the subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element or as essential to the practice of the subject matter described herein.

[0069]

[0061] Preferred embodiments of the subject matter of this application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of these preferred embodiments may become apparent to those of skill in the art upon reading the foregoing description. The inventors anticipate that those of skill in the art will adopt such variations as appropriate, and the inventors intend for the subject matter described herein to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by this disclosure unless otherwise indicated herein or otherwise clearly contradicted by context. The following describes embodiments of the present invention. 1. (a) a thermoplastic polymer; (b) a polymer additive selected from the group consisting of nucleating agents, clarifiers, and combinations thereof; (c) fluoropolymer; A polymer composition comprising: The polymer composition comprises: (i) 1,000 s -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 and a temperature of 190°C. 2. The polymer composition according to 1, wherein the thermoplastic polymer is a polyolefin. 3. The polymer composition according to claim 2, wherein the thermoplastic polymer is selected from the group consisting of polypropylene homopolymer, polypropylene copolymer, and combinations thereof. 4. The polymer composition according to 3, wherein the thermoplastic polymer is a polypropylene random copolymer. 5. The polymer additive has the following formula (I): [ka] (In the formula, R 1 is selected from the group consisting of hydrogen, alkyl groups, alkenyl groups, hydroxyalkyl groups, alkoxy groups, and halogenated alkyl groups; R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R11 are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, and a halogen; R 12 is -CH 2 OH and -CHOHCH 2 OH) 5. The polymer composition according to any one of 1 to 4, wherein the clarifier comprises an acetal compound having the structure: 6. R 1 is selected from the group consisting of alkyl and alkenyl groups; R 2 、R 3 、R 5 、R 6 、R 7 、R 8 、R 10 and R 11 are hydrogen, and R 12 Ga-CHOHCH 2 OH and R 4 and R 9 6. The polymer composition according to claim 5, wherein is selected from the group consisting of alkyl groups and alkoxy groups. 7. R 1 、R 4 and R 9 7. The polymer composition according to claim 6, wherein is an n-propyl group. 8. The polymer composition according to any one of 1 to 7, wherein the fluoropolymer has a melt flow index of about 4 to about 30 g per 10 minutes, measured according to ASTM D1238-04c at 265°C using a 5 kg weight. 9. The polymer composition according to any one of 1 to 8, wherein the fluoropolymer is a polymer produced from at least one monomer selected from the group consisting of vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, perfluoro(alkyl vinyl ether), and combinations thereof. 10. The polymer composition according to any one of 1 to 9, wherein the fluoropolymer is present in the polymer composition in an amount of about 200 ppm or less, based on the total weight of the polymer composition. 11. The polymer composition is -1 11. The polymer composition according to any one of 1 to 10, having an apparent melt viscosity of 1,500 Pa s or less at an apparent shear rate of 1000 μm and a temperature of 190° C. 12. The polymer composition is -1 12. The polymer composition according to any one of items 1 to 11, having an apparent melt viscosity of 3000 Pa·s or less at an apparent shear rate of 1000 μm and a temperature of 190° C. 13. A method for producing a polymer composition, said method comprising: (a) providing a first thermoplastic polymer; (b) providing a masterbatch composition, the masterbatch composition comprising: (i) a second thermoplastic polymer; (ii) a polymeric additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof; and (iii) a fluoropolymer; and (c) mixing the first thermoplastic polymer and the masterbatch composition to produce a polymer composition, the polymer composition being: (i) 1,000 s -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 and a temperature of 190°C, the process A method comprising: 14. A method for molding a polymer composition, said method comprising: (a) providing an apparatus including a die and a mold cavity, the mold cavity having an interior surface defining a shape of a molded article; (b) providing a polymer composition comprising: (i) a thermoplastic polymer; (ii) a polymer additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof; and (iii) a fluoropolymer; -1 and a temperature of 190°C; and (ii) an apparent melt viscosity of about 200 Pa s or less at an apparent shear rate of 20 s -1 and a temperature of 190° C.; (c) heating the polymer composition to a temperature sufficient to melt the polymer composition so that it can be extruded through the die; (d) extruding the molten polymer composition through the die to form a parison; (e) capturing the parison in the mold cavity; (f) injecting a pressurized fluid into the parison under sufficient pressure to expand the parison and conform it to the interior surface of the mold cavity to produce a molded article; (g) cooling the molded article to a temperature at which the polymer composition at least partially solidifies, thereby causing the molded article to retain its shape; and (h) removing the molded article from the mold cavity. A method comprising: 15. The method of claim 14, wherein the thermoplastic polymer is a polyolefin. 16. The method of claim 15, wherein the thermoplastic polymer is selected from the group consisting of polypropylene homopolymer, polypropylene copolymer, and combinations thereof. 17. The method of claim 16, wherein the thermoplastic polymer is a polypropylene random copolymer. 18. The polymer additive has the following formula (I):

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Claims

1. 1. A method for producing a polymer composition, the method comprising: (a) providing a polypropylene random copolymer comprising 1 to 7 weight percent of a comonomer selected from the group consisting of ethylene, but-1-ene and hex-1-ene; (b) providing a polymeric additive selected from the group consisting of nucleating agents, clarifiers, and combinations thereof; (c) providing a fluoropolymer; and (d) mixing the polypropylene random copolymer, the polymer additive and the fluoropolymer, and mechanically processing the mixture under shear conditions; (i) mixing the mixture for 1,000 s －１ and a temperature of 190° C.; and (ii) an apparent melt viscosity of 50 Pa·s to 200 Pa·s at an apparent shear rate of 20 s －１ and a temperature of 190° C., said polymer composition having an apparent melt viscosity of 500 Pa·s to 2,550 Pa·s. The method of claim 1, wherein the polymer additive has the following formula (I): 【Chemistry 1】 wherein R 1 is selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxy group, and a halogenated alkyl group; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, and a halogen; and R 12 is a hydroxyalkyl group selected from the group consisting of -CH 2 OH and -CHOHCH 2 OH. The clarification agent comprises an acetal compound according to the structure:

2. R １ is selected from the group consisting of alkyl and alkenyl groups; R ２ , R ３ , R ５ , R ６ , R ７ , R ８ , R １０ and R １１ are each hydrogen, R １２ Ga-CHOHCH ２ OH and R ４ and R ９ 2. The method of claim 1 , wherein is selected from the group consisting of alkyl groups and alkoxy groups.

3. R １ , R ４ and R ９ The method of claim 2, wherein is an n-propyl group.

4. The method of any one of claims 1 to 3, wherein the fluoropolymer has a melt flow index of 4 to 30 g per 10 minutes, measured according to ASTM D1238-04c at 265°C using a 5 kg weight.

5. The method of any one of claims 1 to 4, wherein the fluoropolymer is a polymer made from at least one monomer selected from the group consisting of vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, perfluoro(alkyl vinyl ether), and combinations thereof.

6. The method of any one of claims 1 to 5, wherein the fluoropolymer is present in the polymer composition in an amount of less than or equal to 200 ppm, based on the total weight of the polymer composition.

7. The polymer composition is －１ The method according to any one of claims 1 to 6, wherein the polymer has an apparent melt viscosity of from 500 Pa·s to 1,500 Pa·s at an apparent shear rate of 1000 rpm and a temperature of 190°C.

8. The polymer composition is －１ The method according to any one of claims 1 to 7, wherein the polymer has an apparent melt viscosity of from 800 Pa·s to 3000 Pa·s at an apparent shear rate of 1000 rpm and a temperature of 190°C.

9. 1. A method for producing a polymer composition, the method comprising: (a) providing a polypropylene random copolymer comprising 1 to 7 weight percent of a comonomer selected from the group consisting of ethylene, but-1-ene and hex-1-ene; (b) providing a masterbatch composition, the masterbatch composition comprising: (i) a second thermoplastic polymer; (ii) a polymeric additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof; and (iii) a fluoropolymer; and (c) mixing the polypropylene random copolymer and the masterbatch composition to mechanically process the mixture under shear conditions to produce a polymer composition, the polymer composition being: (i) 1,000 s －１ and a temperature of 190° C.; and (ii) an apparent melt viscosity of 50 Pa·s to 200 Pa·s at an apparent shear rate of 20 s －１ and a temperature of 190° C., the polymer composition having an apparent melt viscosity of 500 Pa·s to 2,550 Pa·s, wherein the polymer additive is represented by the following formula (I): 【Chemistry 2】 wherein R 1 is selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxy group, and a halogenated alkyl group; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, and a halogen; and R 12 is a hydroxyalkyl group selected from the group consisting of -CH 2 OH and -CHOHCH 2 OH. The clarification agent comprises an acetal compound according to the structure:

10. 1. A method for molding a polymer composition, the method comprising: (a) providing an apparatus including a die and a mold cavity, the mold cavity having an interior surface defining a shape of a molded article; (b) providing a polymer composition comprising: (i) a polypropylene random copolymer comprising 1 to 7 weight percent of a comonomer selected from the group consisting of ethylene, but-1-ene, and hex-1-ene; (ii) a polymer additive selected from the group consisting of a nucleating agent, a clarifier, and combinations thereof; and (iii) a fluoropolymer; －１ and a temperature of 190° C.; and (ii) an apparent melt viscosity of 50 Pa·s to 200 Pa·s at an apparent shear rate of 20 s －１ and a temperature of 190° C.; (c) heating the polymer composition to a temperature sufficient to melt the polymer composition so that it can be extruded through the die; (d) extruding the molten polymer composition through the die to form a parison; (e) capturing the parison in the mold cavity; (f) injecting a pressurized fluid into the parison under sufficient pressure to expand the parison and conform it to the interior surface of the mold cavity to produce a molded article; (g) cooling the molded article to a temperature at which the polymer composition at least partially solidifies, thereby causing the molded article to retain its shape; and (h) removing the molded article from the mold cavity. The method of claim 1, wherein the polymer additive has the following formula (I): 【Chemistry 3】 wherein R 1 is selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkoxy group, and a halogenated alkyl group; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, and a halogen; and R 12 is a hydroxyalkyl group selected from the group consisting of -CH 2 OH and -CHOHCH 2 OH. The clarification agent comprises an acetal compound according to the structure:

11. R １ is selected from the group consisting of alkyl and alkenyl groups; R ２ , R ３ , R ５ , R ６ , R ７ , R ８ , R １０ and R １１ are each hydrogen, R １２ Ga-CHOHCH ２ OH and R ４ and R ９ The method of claim 10, wherein is selected from the group consisting of alkyl groups and alkoxy groups.

12. R １ , R ４ and R ９ The method of claim 11, wherein is an n-propyl group.

13. 13. The method of any one of claims 9 to 12, wherein the fluoropolymer has a melt flow index of 4 to 30 g per 10 minutes, measured according to ASTM D1238-04c at 265°C using a 5 kg weight.

14. The method of any one of claims 9 to 13, wherein the fluoropolymer is a polymer made from at least one monomer selected from the group consisting of vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, perfluoro(alkyl vinyl ether), and combinations thereof.

15. The method of any one of claims 9 to 14, wherein the fluoropolymer is present in the polymer composition in an amount of less than or equal to 200 ppm, based on the total weight of the polymer composition.

16. The polymer composition is －１ The method according to any one of claims 9 to 15, wherein the polymer has an apparent melt viscosity of from 500 Pa·s to 1,500 Pa·s at an apparent shear rate of 1000 rpm and a temperature of 190°C.

17. The polymer composition is －１ The method according to any one of claims 9 to 16, wherein the polymer has an apparent melt viscosity of from 800 Pa·s to 3000 Pa·s at an apparent shear rate of from 1000 to 10000 Pa·s and a temperature of 190°C.

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