Polymer compositions suitable for high-temperature sterilization, possessing excellent haze properties.

Abstract

Propylene and butene random copolymers are disclosed that have excellent stiffness properties and excellent transparency characteristics, especially when combined with one or more nucleating agents. The propylene-butene copolymers can be made with different melt flow characteristics that make them well suited for use in injection molding, blow molding, and thermoforming applications.

Description

[Technical Field]

[0001] (Related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 050,771, filed on 11 July 2020, which is incorporated herein by reference. [Background technology]

[0002] Transparency, along with rigidity, is a highly desirable property for many polymer applications. For example, polymers can be used to manufacture a variety of different products, such as packaging or containers, where transparency can be very beneficial to the user. In many situations, for instance, it is very advantageous for the contents of the packaging or container to be visible through the walls of the packaging or container. In addition to packaging and containers, a variety of other molded articles, including medical devices, can benefit from a certain degree of transparency.

[0003] One type of polymer that can be made highly transparent is semi-crystalline polypropylene polymer. Polypropylene polymers are generally semi-transparent due to their high crystallinity and large spherulites. The transparency of polypropylene polymers can be improved by incorporating ethylene into the polymer chain to produce polypropylene-ethylene random copolymers, and can be further improved by adding nucleating agents (clarifying agents).

[0004] Nucleated (clarified) polypropylene-ethylene random copolymers exhibit excellent initial transparency properties, but when exposed to high temperatures for a certain period, small molecules within the polymer are known to migrate to the surface, a phenomenon defined as blooming. Blooming can adversely affect the functional and optical properties of the polymer and articles made from it. For example, blooming can negatively impact transparency, which can be measured as haze. Many nucleated (clarified) propylene-ethylene random copolymers, for example, exhibit low haze at room temperature but undergo a substantial increase in haze after exposure to high temperatures.

[0005] Considering the drawbacks mentioned above, propylene-ethylene random copolymer is not well-suited for use in applications requiring exposure to high temperatures. For example, propylene-ethylene random copolymer is not necessarily well-suited for manufacturing molded articles such as food packaging, medical packaging, and medical devices that are subjected to high-temperature sterilization, such as steam sterilization, and retort processing.

[0006] Considering the above, there is a need for polypropylene polymers and polypropylene compositions that can maintain excellent transparency characteristics even when subjected to thermal cycling or high temperatures during use. [Overview of the Initiative]

[0007] Generally, this disclosure relates to polymer compositions containing propylene-butene copolymers. These polymer compositions can be used to produce a number of different articles, including food packaging, medical packaging, medical devices, and various containers. The propylene-butene copolymers of this disclosure have been found to possess not only excellent rigidity properties but also significant optical properties, particularly low haze when containing nucleating agents. Among the specific advantages, nucleated propylene-butene copolymers have been found to have bloom resistance, and therefore can maintain their clarity even when exposed to higher temperatures, such as during sterilization processes. Thus, the propylene-butene copolymers of this disclosure offer various advantages over many conventional propylene-ethylene copolymers developed in the past.

[0008] In one embodiment, for example, the present disclosure relates to a polymer composition containing a propylene-butene copolymer. The propylene-butene copolymer may contain propylene as the main monomer and may contain butene in an amount of about 1% to about 12% by weight, for example, about 2% to about 8% by weight, for example, about 3% to about 6% by weight. The propylene-butene copolymer may have a xylene-soluble fraction of about 1% to about 8% by weight, for example, about 2% to about 6% by weight. The polymer may have a xylene-soluble fraction / butene content ratio of about 0.3 to about 3.0, for example, about 0.3 to about 2.0, for example, about 0.5 to about 1.0. The copolymer may be formed using a non-phthalate Ziegler-Natta catalyst and may have a molecular weight distribution greater than about 3.5.

[0009] In addition to the propylene-butene copolymer, the polymer composition may also contain nucleating agents such as clarifying agents. The polymer composition may exhibit a haze of 1 mm with less than about 25%, for example less than about 20%, for example less than about 18%, for example less than about 15%, for example less than about 13%, for example less than about 10%, for example even less than about 8%. The polymer composition may exhibit a haze of 0.7 mm with less than about 20%, for example less than about 18%, for example less than about 15%, for example less than about 13%, for example less than about 12%, for example even less than about 10%. In addition, when subjected to thermal aging at 121°C for 30 minutes or at 55°C for 24 hours, the haze of the polymer composition may increase by only about 35% or less, for example about 30% or less, for example about 20% or less, for example about 18% or less, for example about 15% or less, for example about 10% or less.

[0010] Propylene-butene copolymers can also have excellent heat resistance properties, especially when they contain a smaller amount of butene. The polymer can generally have a thermal deflection temperature above about 70°C. When containing less than about 8% by weight of butene, for example less than 6% by weight, the copolymer can have a thermal deflection temperature above about 75°C and a melting point above about 135°C, for example, about 143°C to about 165°C, or for example, about 145°C to about 155°C. Propylene-butene copolymers can have melt flow rates of about 0.2 g / 10 min to about 220 g / 10 min, for example, about 2 g / 10 min to about 60 g / 10 min.

[0011] The polymer composition may generally contain more than about 70% by weight of propylene-butene copolymer, for example more than about 80% by weight, for example more than about 90% by weight, for example more than about 95% by weight. The nucleating agent combined with the propylene-butene copolymer may be a clarifying agent such as nonitol. The nucleating agent may be present in the polymer composition in an amount of more than about 100 ppm, for example more than about 300 ppm, for example more than about 1000 ppm, for example more than about 2000 ppm, and generally less than about 20,000 ppm, for example less than about 10,000 ppm, for example less than about 4000 ppm.

[0012] The polymer compositions of this disclosure can be used to manufacture a wide variety of polymer articles using any suitable melting technique. For example, the articles can be injection molded, blow molded, or thermoformed. The polymer compositions can be used to manufacture, for example, containers, food packaging materials, medical packaging materials, medical devices, and the like.

[0013] Other features and aspects of this disclosure are discussed in more detail below. [Modes for carrying out the invention]

[0014] This disclosure relates to polymer compositions having excellent optical properties in general. The polymer compositions can also be formulated to have excellent rigidity characteristics. The polymer compositions of this disclosure generally contain propylene-butene copolymers. Clarified propylene-butene copolymers have been found to have excellent haze characteristics even after exposure to high temperatures. As a result, the polymer compositions are particularly well suited for producing transparent articles that are typically subjected to high temperatures during use. For example, many food packaging materials, medical packaging materials, and medical devices are subjected to high-temperature sterilization, such as steam sterilization, and / or retort processing.

[0015] In the past, nucleated (clarified) propylene-ethylene random copolymers were typically chosen to produce articles with transparency. However, to produce polymer articles that retain their transparency over time, propylene-ethylene copolymers were typically formulated to contain a very small amount of xylene-soluble fraction, and typically required to have a low xylene-to-ethylene content ratio to minimize blooming during thermal aging. In contrast, the propylene-butene copolymers of this disclosure have been found to have greater resistance to haze degradation, even when subjected to high temperatures.

[0016] Polymer compositions prepared in accordance with this disclosure can be formulated by combining a propylene-butene random copolymer with a nucleating agent or clarifying agent. The resulting polymer compositions may exhibit a haze of less than 25%, e.g., less than 20%, e.g., less than 18%, e.g., less than 15%, e.g., less than 13%, e.g., less than 12%, e.g., less than 10%, e.g., less than 8% at 1 mm. The resulting polymer compositions may exhibit a haze of less than 20%, e.g., less than 18%, e.g., less than 15%, e.g., less than 13%, e.g., less than 12%, e.g., less than 10% at 0.7 mm. Articles made from this polymer, such as containers, cups, and bottles, may exhibit a haze of less than 10%, e.g., less than 8%, e.g., less than 7%, e.g., less than 6%, e.g., less than 4% at wall thicknesses of less than 0.5 mm. The haze is generally greater than 0.5%. Among the specific advantages, when subjected to thermal aging at 121°C for 30 minutes, the haze of the polymer composition increases by only about 35% or less, e.g., about 30% or less, e.g., about 25% or less, e.g., about 20% or less, e.g., about 15% or less, e.g., about 12% or less, e.g., about 10% or less, e.g., about 8% or less. When subjected to thermal aging at 55°C for 24 hours, the haze of the polymer composition increases by only about 30% or less, e.g., about 25% or less, e.g., about 20% or less, e.g., about 17% or less, e.g., about 15% or less, e.g., about 13% or less, e.g., about 10% or less. These results are dramatic compared to many propylene-ethylene random copolymers produced in the past.

[0017] Another advantage of the polymer compositions of this disclosure is that they can produce propylene-butene random copolymers over a very wide range of melt flow rates. For example, the melt flow rate can be about 0.2 g / 10 min to about 220 g / 10 min, for example, about 1 g / 10 min to about 60 g / 10 min. Thus, the polymer compositions are well suited for use in all different types of molding processes. For example, the polymer compositions can be used for injection molding, blow molding, and thermoforming. For example, blow-molded or thermoformed articles can be made from polymer compositions having a melt flow rate of about 0.2 g / 10 min to about 6 g / 10 min. Articles that can be made according to this disclosure include all different types of films, food packaging materials, medical device packaging materials, medical devices, all different types of containers, and the like.

[0018] I. Definitions and Test Procedures As used herein, the term "propylene copolymer" refers to a copolymer containing a majority by weight percentage of propylene monomer with butene monomers as secondary components. A "propylene-butene copolymer" (also called a polypropylene-butene random copolymer) is a polymer having individual repeating units of butene monomers present in a random or statistical distribution within the polymer chain.

[0019] The melt flow rate (MFR), as used herein, is measured for propylene polymers at 230°C at a weight of 2.16 kg according to the ASTM D1238 test method. The melt flow rate can be measured in pellet form or in reactor powder form. When measuring reactor powder, a stabilizing package containing 2000 ppm of CYANOX2246 antioxidant (methylenebis(4-methyl-6-tert-butylphenol)), 2000 ppm of IRGAFOS168 antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), and 1000 ppm of acid scavenger ZnO may be added.

[0020] Xylene solubles (XS) are defined as the weight percentage of resin remaining in the solution after dissolving a sample of polypropylene random copolymer resin in high-temperature xylene and cooling the solution to 25°C. This is also known as the gravimetric XS method according to ASTM D5492-06, which uses a 60-minute precipitation time, and is referred to herein as the “wet method”.

[0021] The ASTM D5492-06 method described above can be adapted to determine the xylene-soluble portion. Generally, the procedure consists of weighing 2 g of the sample and dissolving the sample in 200 mL of o-xylene in a 400 mL flask fitted with a 24 / 40 fitting. The flask is connected to a water condenser, the contents are stirred, and the mixture is heated under nitrogen (N2) reflux, and reflux is maintained for a further 30 minutes. The solution is then cooled in a temperature-controlled water bath at 25°C for 60 minutes to allow crystallization of the xylene-insoluble fraction. Once the solution has cooled and the insoluble fraction has precipitated from the solution, the separation of the xylene-soluble portion (XS) from the xylene-insoluble portion (XI) is achieved by filtration through 25 micrometer filter paper. 100 mL of the filtrate is collected in a pre-weighed aluminum pan, and o-xylene is evaporated from this 100 mL of filtrate under a stream of nitrogen. Once the solvent has evaporated, place the pan and contents in a 100°C vacuum oven for 30 minutes or until dry. Then, let the pan cool to room temperature and weigh it. The xylene-soluble portion is XS (wt%) = [(m³-m²)] * 2 / m1] * Calculated as 100, where m1 is the original weight of the sample used, m2 is the weight of the empty aluminum pan, and m3 is the weight of the pan and residue (asterisks elsewhere in this and the disclosure). * (This indicates that the identified terms or values ​​are multiplied.)

[0022] XS can also be measured according to the Viscotek method as follows: Dissolve 0.4 g of polymer in 20 mL of xylene with stirring at 130 °C for 60 minutes. Then, cool the solution to 25 °C, and after 60 minutes, filter off the insoluble polymer fraction. Analyze the obtained filtrate by flow injection polymer analysis using a Viscotek ViscoGEL H-100-3078 column with a THF mobile phase flowing at 1.0 mL / min. Couple the column to a Viscotek Model 302 Triple Detector Array equipped with a light scattering viscometer and refractometer detector operating at 45 °C. Maintain instrument calibration with Viscotek PolyCAL® polystyrene standards. Use a polypropylene (PP) homopolymer such as biaxially oriented polypropylene (BOPP) grade Dow 5D98 as a reference material to ensure that the Viscotek instrument and sample preparation procedure provide consistent results. The values ​​for reference polypropylene homopolymers such as 5D98 are first derived from tests using the ASTM method identified above.

[0023] The term "tacticity" generally refers to the relative stereochemistry of adjacent chiral centers in a polymer or macromolecule. For example, in propylene polymers, the chirality of adjacent monomers, such as two propylene monomers, can be either similar or opposite configurations. The term "diploid" is used to describe two consecutive monomers, and three adjacent monomers are called "triploids." If the chirality of adjacent monomers is the same relative configuration, a diploid is considered isotactic. If the configurations are opposite, it is called syndiotactic. Another way to describe the stereochemical relationship is to refer to a pair of monomers with the same chirality as meso(m) and a pair of monomers with opposite configurations as racemic(r).

[0024] In general, the tacticity or stereochemistry of polymers, particularly polypropylene or polypropylene random copolymers, can be described or quantified by reference to the concentration of triplets. An isotactic triplet, typically identified by the abbreviation "mm," is constructed of two adjacent meso-diplexes having the same stereoconfiguration; therefore, the stereoregularity of the triplet is identified as "mm." A triplet has "mr" tacticity when two adjacent monomers in a sequence of three monomers have the same chirality, differing from the relative stereoconfiguration of the third unit. An "rr" triplet has a central monomer unit with a stereoconfiguration opposite to either of its adjacent units. The fraction of each type of triplet in a polymer can be determined, and multiplying it by 100 reveals the percentage of that type found in the polymer. The percentage of mm is used to identify and characterize polymers herein.

[0025] The arrangement distribution of monomers in a polymer is 13 This can be determined by 1C-NMR, which also allows for the localization of the butene residue in relation to adjacent propylene residues. 13 13C NMR can be used to measure butene content, triplet distribution, and triplet tacticity, and is performed as follows:

[0026] The sample is prepared by adding approximately 2.7 g of a 50 / 50 mixture of tetrachloroethane-d2 / orthodichlorobenzene containing 0.025 M Cr(AcAc)3 to 0.20 g of the sample in a 10 mm Norell 1001-7 NMR tube. The sample is dissolved and homogenized by heating the tube and its contents to 150°C using a heating block. Each sample is visually inspected to ensure homogeneity.

[0027] Data are acquired using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe. Data are acquired per data file using 512 transients, a 6-second pulse repetition delay, a 90-degree flip angle, and reverse gate decoupling at a sample temperature of 120°C. All measurements are performed on non-spin samples in locked mode. Samples are thermally equilibrated for 10 minutes prior to data acquisition. The percentage of mm tacticity and the weight percentage of butene are calculated according to methods commonly used in the art, which can be summarized concisely as follows:

[0028] Regarding the measurement of the resonance chemical shift, the methyl group of the third unit in a sequence of five consecutive propylene units consisting of head-tail bonds and having the same relative chirality is set to 21.83 ppm. By using the above value as a reference, the chemical shifts of other carbon resonances are determined. The spectrum for the methyl carbon region (17.0-23 ppm) can be classified into the first region (21.1-21.9 ppm), the second region (20.4-21.0 ppm), the third region (19.5-20.4 ppm), and the fourth region (17.0-17.5 ppm). Each peak in the spectrum is assigned by reference to literature sources such as, for example, the papers in Polymer, T. Tsutsui et al., Vol. 30, Issue 7, (1989) 1350-1356 and / or Macromolecules, HNCheng, 17 (1984) 1950-1955 (the contents of which are incorporated herein by reference).

[0029] For convenience, the butene content was also measured using the Fourier Transform Infrared method (FTIR), which is the first method described above. 13The butene values ​​are correlated with those determined using 13C NMR. The relationship and agreement between measurements performed using the two methods are described, for example, in JRPaxson, JCRandall, "Quantitative Measurement of Ethylene Incorporation into Propylene Copolymers by Carbon-13 Nuclear Magnetic Resonance and Infrared Spectroscopy," Analytical Chemistry, Vol. 50, No. 13, Nov. 1978, 1777-1780.

[0030] The flexural modulus was determined at 1.3 mm / min using a Type 1 specimen of ASTM 3641 according to Method A of ASTM D790-10, and formed according to ASTM D4101.

[0031] IZOD impact strength is measured according to ASTM D 256 and D4101.

[0032] Haze is determined using the latest version of the test, following procedure A of ASTM test D1003. Haze can be measured on a test plaque or on molded articles such as containers, cups, or bottles. Haze can be measured before and after thermal aging. Haze can be measured using the BYK Gardner Haze-Gard Plus 4725 instrument. Injection-molded test specimens to be tested for haze measurement can be injection-molded at a temperature of 200-230°C when nonitol is present as a nucleating agent, at a temperature of 250-260°C when sorbitol is present as a nucleating agent, or at a temperature of 200-260°C when an insoluble particulate nucleating agent is present. Thermal aging is performed by placing the specimen in an oven at a desired temperature (e.g., 121°C or 55°C) and for a desired time (e.g., 30 minutes or 24 hours), and then retesting for haze.

[0033] The heat distortion temperature (HDT) is determined according to ASTM test D648, titled "Heat distortion temperature of plastic under a bending load of 66 psi for a sample prepared / aged according to D4101."

[0034] The melting point or melting temperature and the crystallization temperature are determined using differential scanning calorimetry (DSC). The melting point is the primary peak formed during the test, and is typically a secondary peak. The term "crystallinity" refers to the regularity of the arrangement of atoms or molecules that form the crystal structure. Polymer crystallinity can be investigated using DSC. me This refers to the temperature at which melting ends, T max θ refers to the peak melting temperature, and both are determined by those skilled in the art from DSC analysis using data from the final heating step. One preferred method for DSC analysis is to use the Model Q1000™ DSC from TA Instruments, Inc. Calibration of the DSC is performed in the following manner: First, a baseline is obtained by heating the cell from -90°C to 290°C in an aluminum DSC pan with no sample in it. Next, 7 milligrams of fresh indium sample is analyzed by heating the sample to 180°C, cooling the sample to 140°C at a cooling rate of 10°C / min, then keeping the sample isothermally at 140°C for 1 minute, and then heating the sample from 140°C to 180°C at a heating rate of 10°C / min. The heat of fusion and the onset of melting of the indium sample are determined, and it is confirmed that the onset of melting is within 0.5°C from 156.6°C and the heat of fusion is within 0.5 J / g from 28.71 J / g. Next, deionized water is analyzed by cooling a small droplet of fresh sample in a DSC pan from 25°C to -30°C at a cooling rate of 10°C / min. The sample is kept isothermally at -30°C for 2 minutes and then heated to 30°C at a heating rate of 10°C / min. The onset of melting is determined and confirmed to be within 0.5°C to 0°C.

[0035] II. Propylene-butene random copolymer and composition The propylene-butene copolymers of this disclosure may contain a majority weight percent of propylene monomer having butene monomer as a secondary component. The butene content of the propylene-butene copolymers of this disclosure may range from about 1% to about 12% by weight, including all increments of 0.1% by weight in between. For example, the propylene-butene copolymers may contain butene in amounts greater than about 1.5% by weight, e.g., greater than about 2% by weight, e.g., greater than about 2.3% by weight, e.g., greater than about 3% by weight, e.g., greater than about 4% by weight, e.g., greater than about 4.5% by weight, e.g., greater than about 5% by weight. The butene content of the propylene-butene copolymers is generally less than about 11% by weight, e.g., less than about 10% by weight, e.g., less than about 9% by weight, e.g., less than about 8% by weight, e.g., less than about 7.8% by weight, e.g., less than about 7% by weight, e.g., less than about 6% by weight, e.g., less than 5% by weight. The amount of butene incorporated into the copolymer can be changed to alter various physical properties of the polymer.

[0036] The xylene-soluble fraction (XS) of the copolymers of this disclosure may be 8.0% by weight or less (≦), or ≦7.0% by weight, more preferably ≦6.0% by weight, and even more preferably ≦5.0% by weight. The xylene-soluble fraction is generally greater than about 0.5% by weight, for example greater than about 1% by weight. The xylene-soluble fraction (XS) is preferably in the range of 1.0% to 8.0% by weight, for example 2% to 7% by weight. The polymers may have a xylene-soluble fraction / butene content ratio of about 0.3 to about 3.0, for example about 0.3 to about 2.0, for example about 0.5 to about 1.0, or less than 1.0. Among the particular advantages, the propylene-butene copolymers of this disclosure can have a xylene-soluble content of more than about 3% by weight while still having excellent clarity properties.

[0037] The melt flow rate of propylene-butene copolymers prepared according to this disclosure can be modified. For example, the melt flow rate may range from about 0.2 g / 10 min to about 220 g / 10 min, including all increments of 1 in between. For example, the melt flow rate of a polymer can be modified and controlled based on various factors and the desired application. When the polymer is incorporated into a composition and blow-molded, for example, a lower melt flow rate may be desirable. For example, in one embodiment, the melt flow rate of a propylene-butene copolymer may be less than about 20 g / 10 min, e.g., less than about 15 g / 10 min, e.g., less than about 10 g / 10 min, e.g., less than about 8 g / 10 min, e.g., less than about 6 g / 10 min, e.g., less than about 4 g / 10 min, and generally greater than about 1 g / 10 min, e.g., greater than about 2 g / 10 min. However, when the polymer is used for injection molding and / or thermoforming, a higher melt flow rate may be desirable. For example, in one embodiment, the polymer melt flow rate may be greater than about 10 g / 10 min, for example, greater than about 20 g / 10 min, for example, greater than about 30 g / 10 min, for example, greater than about 40 g / 10 min, and generally less than about 110 g / 10 min, for example less than 80 g / 10 min, for example less than about 60 g / 10 min.

[0038] The copolymers of this disclosure generally have a relatively broad molecular weight distribution. For example, the molecular weight distribution (Mw / Mn) is generally greater than about 3.5, e.g., greater than about 3.8, e.g., greater than about 4, e.g., greater than about 4.3, e.g., greater than about 4.5, e.g., greater than about 4.8, e.g., greater than about 5, e.g., greater than about 5.2, e.g., greater than about 5.5, e.g., greater than about 5.7, e.g., greater than about 6, and generally less than about 10, e.g., less than about 8, e.g., less than about 7.5. The weight-average molecular weight is measured by GPC.

[0039] In one embodiment, the propylene-butene copolymer can be formulated to have excellent rigidity properties. For example, the copolymer can have a flexural modulus of over about 1000 MPa, for example, over 1100 MPa, for example, over 1150 MPa, for example, over 1200 MPa, for example, over 1250 MPa, for example, over 1300 MPa, for example, over 1350 MPa, for example, over 1400 MPa, for example, over 1450 MPa, for example, over 1500 MPa. The flexural modulus is generally less than about 3000 MPa, for example, less than about 2000 MPa.

[0040] Among its specific advantages, propylene-butene random copolymers can exhibit high heat deflection resistance, particularly when the polymer is formulated to contain a smaller amount of butene. Generally, polymers can have a heat deflection temperature (HDT) above about 70°C. When butene is contained in amounts less than 8% by weight, e.g., less than 6% by weight, e.g., less than 5% by weight, the HDT may be above about 75°C, e.g., above 76°C, e.g., above 77°C, and generally below about 90°C. In addition, polymers can be formulated to have a melting point above about 135°C, e.g., above 143°C, e.g., above 145°C, e.g., above 147°C, e.g., above 149°C, e.g., above 150°C, e.g., above 151°C, and generally below about 165°C. In one embodiment, the polymer can have a primary melting point of 147°C or higher.

[0041] In addition to excellent rigidity and heat resistance properties, propylene-butene copolymers can also possess good toughness properties. For example, copolymers can have IZOD impact strengths of over approximately 40 J / m, e.g., over 45 J / m, e.g., over 50 J / m, e.g., over 55 J / m, e.g., over 60 J / m, e.g., over 65 J / m, e.g., over 70 J / m, e.g., over 75 J / m, e.g., over 80 J / m, e.g., over 85 J / m, e.g., over 90 J / m. Impact strengths are generally less than approximately 200 J / m, e.g., less than 150 J / m.

[0042] III. Formation of Propylene-Butene Random Copolymer In one embodiment, the propylene-butene copolymer of the present disclosure can be produced using a non-phthalate Ziegler-Natta catalyst. Non-phthalate catalysts include catalyst systems that do not contain phthalate compounds, such as catalyst supports, internal electron donors, external electron donors, activity limiters, and activators, all of which are phthalate-free. Phthalates have historically been used as internal electron donors. Examples of non-phthalate internal electron donors include diethers, succinates, ethyl benzoates, and phenylenediesters. The use of non-phthalate catalysts makes the polymer suitable for food contact and medical applications. In addition, the use of Ziegler-Natta catalysts can produce a broad molecular weight distribution that offers numerous advantages and benefits.

[0043] Propylene-butene copolymers can generally be produced in any suitable reactor using any suitable process for producing propylene-based polymers. This includes the UNIPOL® gas-phase process using a supported Ziegler-Natta catalyst. Particularly preferred is the CONSISTA® catalyst, available from WRGrace & Co. (Columbia, Maryland). Suitable polypropylene random copolymers can be produced using a single reactor or multiple reactors. Examples of processes that may be used are described in U.S. Patent No. 9,624,323 and U.S. Patent Publication No. 2016 / 0289357, which are incorporated herein by reference.

[0044] Suitable pro-catalyst compositions for use in the production of polypropylene random copolymers include the Ziegler-Natta pro-catalyst composition. In some embodiments, the Ziegler-Natta pro-catalyst composition contains a titanium moiety such as titanium chloride, a magnesium moiety such as magnesium chloride, and an internal electron donor.

[0045] In certain embodiments, the internal electron donor comprises a substituted phenylene aromatic diester. In certain embodiments, a 1,2-phenylene aromatic diester is provided. The substituted 1,2-phenylene aromatic diester has the following structure (I),

[0046] [Chemical formula]

[0047] wherein, R1 to R 14 are the same or different. Each of R1 to R 14 is selected from hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof. At least one of R1 to R 14 is not hydrogen.

[0048] As used herein, the terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, fused, or acyclic species, and combinations thereof. Non-limiting examples of hydrocarbyl groups include alkyl groups, cycloalkyl groups, alkenyl groups, alkadienyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, alkylaryl groups, and alkynyl groups.

[0049] As used herein, the terms “substituted hydrocarbyl” and “substituted hydrocarbon” refer to a hydrocarbyl group substituted with one or more non-hydrocarbyl substituents. Non-limiting examples of non-hydrocarbyl substituents are heteroatoms. As used herein, “heteroatom” refers to an atom other than carbon or hydrogen. Heteroatoms can be non-carbon atoms from groups IV, V, VI, and VII of the periodic table. Non-limiting examples of heteroatoms include halogens (F, Cl, Br, I), N, O, P, B, S, and Si. Substituted hydrocarbyl groups also include halohydrocarbyl groups and silicon-containing hydrocarbyl groups. As used herein, the term “halohydrocarbyl” group refers to a hydrocarbyl group substituted with one or more halogen atoms. As used herein, the term “silicon-containing hydrocarbyl group” refers to a hydrocarbyl group substituted with one or more silicon atoms. The silicon atoms may or may not be present in the carbon chain.

[0050] Procatalyst precursors may include (i) magnesium, (ii) transition metal compounds of elements from groups IV to VIII of the periodic table, (iii) halides, oxyhalides, and / or alkoxides of (i) and / or (ii), and (iv) combinations of (i), (ii), and (iii). Non-limiting examples of suitable procatalyst precursors include halides, oxyhalides, and alkoxides of magnesium, manganese, titanium, vanadium, chromium, molybdenum, zirconium, hafnium, and combinations thereof.

[0051] In some embodiments, the pro-catalyst precursor is a magnesium moiety (MagMo), a mixed magnesium-titanium compound (MagTi), or a benzoate-containing magnesium chloride compound (BenMag). In some embodiments, the pro-catalyst precursor is a magnesium moiety ("MagMo") precursor. The "MagMo precursor" contains magnesium as the sole metallic component. The MagMo precursor contains a magnesium moiety. Non-limiting examples of preferred magnesium moieties include anhydrous magnesium chloride and / or its alcohol adducts, magnesium alkoxides or aryl oxides, mixed magnesium alkoxy halides, and / or carboxylated magnesium dialkoxides or aryl oxides. In one embodiment, the MagMo precursor is a magnesium di(C) 1~4 ) is an alkoxide. In further embodiments, the MagMo precursor is diethoxymagnesium.

[0052] In one embodiment, the procatalyst precursor is a mixed magnesium / titanium compound ("MagTi"). The "MagTi precursor" is a compound of the formula Mg d Ti(OR e ) f X g It has, in the formula, R e COR' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and each OR eThe groups are the same or different, X is independently chlorine, bromine, or iodine, preferably chlorine, d is 0.5 to 56, or 2 to 4, f is 2 to 116, or 5 to 15, and g is 0.5 to 116, or 1 to 3. The precursor is prepared by controlled precipitation, removing the alcohol from the reaction mixture used for its preparation. In some embodiments, the reaction medium includes a mixture of aromatic liquids, particularly chlorinated aromatic compounds, most particularly chlorobenzene, and alkanols, particularly ethanol. Suitable halogenating agents include titanium tetrabromide, titanium tetrachloride, or titanium trichloride, particularly titanium tetrachloride. Removal of the alkanol from the solution used for halogenation precipitates a solid precursor, which has a particularly desirable shape and surface area. Furthermore, the resulting precursor has a particularly uniform particle size.

[0053] In one embodiment, the pro-catalyst precursor contains magnesium as the sole metal component. Non-limiting examples include anhydrous magnesium chloride and / or its alcohol adducts, magnesium alkoxides and / or aryl oxides, mixed magnesium alkoxyhalides, and / or carboxylated magnesium dialkoxides or aryl oxides.

[0054] In one embodiment, the pro-catalyst precursor is an alcohol adduct of anhydrous magnesium chloride. The anhydrous magnesium chloride adduct is generally defined as MgCl2-nROH, where n is in the range of 1.5 to 6.0, preferably 2.5 to 4.0, and most preferably 2.8 to 3.5 moles of total alcohol. ROH is a linear or branched C1-C4 alcohol, or a mixture of alcohols. Preferably, ROH is ethanol or a mixture of ethanol and a higher alcohol. If ROH is a mixture, the molar ratio of ethanol to the higher alcohol is at least 80:20, preferably 90:10, and most preferably at least 95:5.

[0055] In one embodiment, substantially spherical MgCl2-nEtOH adducts can be formed by a spray crystallization process. In one embodiment, the spherical MgCl2 precursor has an average particle size between about 15-150 micrometers, preferably 20-100 micrometers, and most preferably 35-85 micrometers (Malvern d 50 ) has.

[0056] In one embodiment, the procatalyst precursor contains a transition metal compound and a magnesium metal compound. The transition metal compound has the general formula TrX x The formula has the following characteristics, where Tr is a transition metal and X is a halogen or C 1~10 X is a hydrocarboxyl or hydrocarbyl group, where x is the number of such X groups in the compound combined with the magnesium metal compound. Tr can be a group IV, group V, or group VI metal. In one embodiment, Tr is a group IV metal such as titanium. X is a chloride, bromide, or C 1~4 It may be an alkoxide, a phenoxide, or a mixture thereof. In one embodiment, X is a chloride.

[0057] The procatalyst compositions of the present invention may also contain internal electron donors. As used herein, an internal electron donor is a compound added during the formation of a procatalyst composition that donates a pair of electrons to one or more metals present in the resulting procatalyst composition. While not bound by any particular theory, internal electron donors are thought to help regulate the formation of the active site and thereby enhance the stereoselectivity of the catalyst. In some embodiments, the internal electron donor includes a substituted phenylene aromatic diester of structure (I) identified above.

[0058] In one embodiment, a procatalyst composition is provided comprising a combination of a magnesium moiety, a titanium moiety, and an internal electron donor. The internal electron donor comprises a substituted phenylene aromatic diester. The procatalyst composition is produced by a halogenation procedure described in detail in U.S. Patent No. 8,536,372, incorporated herein by reference, which converts the procatalyst precursor and the substituted phenylene aromatic diester donor into a combination of a magnesium moiety and a titanium moiety incorporating the internal electron donor. The procatalyst precursor from which the procatalyst composition is formed may be a magnesium moiety precursor, a mixed magnesium / titanium precursor, or a benzoate-containing magnesium chloride precursor.

[0059] In one embodiment, the magnesium portion is a magnesium halide. In another embodiment, the magnesium halide is magnesium chloride or a magnesium chloride alcohol adduct. In one embodiment, the titanium portion is a titanium halide such as titanium chloride. In another embodiment, the titanium portion is titanium tetrachloride. In yet another embodiment, the procatalyst composition comprises a magnesium chloride support on which titanium chloride is deposited, and an internal electron donor is incorporated thereon.

[0060] In one embodiment, the internal electron donor of the procatalyst composition comprises a substituted phenylene aromatic diester of the structure (I) shown above, where R1 to R 14 They are either the same or different, R1~R 14 Each of these is selected from hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, R1 to R 14 At least one of them is not hydrogen.

[0061] In one embodiment, at least one (or two, three, or four) R groups of R1 to R4 are selected from substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof.

[0062] In one embodiment, R5~R 14 At least one (or some or all) of the R groups are selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof. In another embodiment, at least one of R5 to R9 and R 10 ~R 14 At least one of these is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof.

[0063] In one embodiment, at least one of R1 to R4 and R5 to R 14 At least one of these is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof. In another embodiment, at least one of R1 to R4, at least one of R5 to R9, and R 10 ~R 14 At least one of these is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof.

[0064] In one embodiment, any consecutive R groups R1 to R4, and / or any consecutive R groups R5 to R9, and / or R 10 ~R 14Any consecutive R groups may be linked to form an interring or intraring structure. The interring / intraring structure may be aromatic or non-aromatic. In some embodiments, the interring / intraring structure is a C5 or C6 membered ring.

[0065] In one embodiment, at least one of R1 to R4 is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and combinations thereof. Optionally, R5 to R 14 At least one of them may be a halogen atom or an alkoxyl group having 1 to 20 carbon atoms. Optionally, R1 to R4, and / or R5 to R9, and / or R 10 ~R 14 These may be linked together to form an interring structure or an intraring structure. The interring structure and / or intraring structure may be aromatic or non-aromatic.

[0066] In one embodiment, R1~R4 and / or R5~R9 and / or R 10 ~R 14 Any consecutive R groups within can be members of a C5-C6 membered ring.

[0067] In one embodiment, structure (I) includes R1, R3, and R4 as hydrogen atoms. R2 is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and combinations thereof. R5-R 14 They are either the same or different, R5~R 14 Each of these is selected from hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a halogen, and combinations thereof.

[0068] In some embodiments, R2 is selected from C1-C8 alkyl groups, C3-C6 cycloalkyl groups, or substituted C3-C6 cycloalkyl groups. R2 may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an isobutyl group, a sec-butyl group, a 2,4,4-trimethylpentan-2-yl group, a cyclopentyl group, or a cyclohexyl group.

[0069] In one embodiment, structure (I) includes R2 which is methyl, and R5~R 14 Each of them is hydrogen. In one embodiment, structure (I) includes R2 which is ethyl, and R5~R 14 Each of them is hydrogen. In one embodiment, structure (I) includes R2 which is t-butyl, and R5~R 14 Each of them is hydrogen. In one embodiment, structure (I) includes R2 which is an ethoxycarbonyl, and R5~R 14 Each of them is hydrogen.

[0070] In one embodiment, structure (I) includes R2, R3, and R4 as hydrogen atoms, and R1 is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and combinations thereof. 14 These are either the same or different, each selected from hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a halogen, and combinations thereof.

[0071] In one embodiment, structure (I) includes R1 which is methyl, and R5~R 14 Each of them is hydrogen.

[0072] In one embodiment, structure (I) comprises R2 and R4, which are hydrogen atoms, and R1 and R3 are the same or different. Each of R1 and R3 is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and combinations thereof. R5~R 14They are either the same or different, R5~R 14 Each of these is selected from a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a halogen, and combinations thereof.

[0073] In one embodiment, structure (I) comprises the same or different R1 and R3. Each of R1 and R3 is selected from C1-C8 alkyl groups, C3-C6 cycloalkyl groups, or substituted C3-C6 cycloalkyl groups. R5-R 14 They are either the same or different, R5~R 14 Each of these is selected from hydrogen, C1-C8 alkyl groups, and halogens. Non-limiting examples of preferred C1-C8 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, n-hexyl, and 2,4,4-trimethylpentan-2-yl groups. Non-limiting examples of preferred C3-C6 cycloalkyl groups include cyclopentyl and cyclohexyl groups. In further embodiments, R5-R 14 At least one of them is a C1-C8 alkyl group or halogen.

[0074] In one embodiment, structure (I) includes R1, which is a methyl group, and R3, which is a t-butyl group. R2, R4, and R5-R 14 Each of them is hydrogen.

[0075] In one embodiment, structure (I) includes R1 and R4 as methyl groups, one of R3 or R2 is hydrogen, and the other is a cycloalkyl group such as a cyclohexal group.

[0076] In one embodiment, structure (I) includes isopropyl groups R1 and R3, R2, R4, and R5-R 14 Each of them is hydrogen.

[0077] In one embodiment, structure (I) is R1, R5, and R 10 Each of these contains a methyl group, and R3 is a t-butyl group. R2, R4, R6~R9, and R 11 ~R 14 Each of them is hydrogen.

[0078] In one embodiment, structure (I) is R1, R7, and R 12 Each of these contains a methyl group, and R3 is a t-butyl group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0079] In one embodiment, structure (I) includes R1 as a methyl group and R3 as a t-butyl group. R7 and R 12 Each of these is an ethyl group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0080] In one embodiment, structure (I) is R1, R5, R7, R9, R 10 , R 12 , and R 14 Each of these contains a methyl group, and R3 is a t-butyl group. R2, R4, R6, R8, R 11 , and R 13 Each of them is hydrogen.

[0081] In one embodiment, structure (I) contains R1 as a methyl group and R3 is a t-butyl group. R5, R7, R9, R 10 , R 12 , and R 14 Each of these is an i-propyl group. R2, R4, R6, R8, R 11 , and R 13 Each of them is hydrogen.

[0082] In certain embodiments, the substituted phenylene aromatic diester has a structure selected from the group consisting of structures (II)-(V) and includes each alternative of R1-R 14 as described in U.S. Patent No. 8,536,372, which is incorporated herein by reference in its entirety.

[0083] In certain embodiments, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. Each of R7 and R 12 is an ethoxy group. Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 is hydrogen.

[0084] In certain embodiments, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. Each of R7 and R 12 is a fluorine atom. Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 is hydrogen.

[0085] In certain embodiments, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. Each of R7 and R 12 is a chlorine atom. Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 is hydrogen.

[0086] In certain embodiments, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. Each of R7 and R 12 is a bromine atom. Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 is hydrogen.

[0087] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is an iodine atom. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0088] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R6, R7, R 11 , and R 12 Each of these is a chlorine atom. R2, R4, R5, R8, R9, R 10 , R 13 , and R 14 Each of them is hydrogen.

[0089] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R6, R8, R 11 , and R 13 Each of these is a chlorine atom. R2, R4, R5, R7, R9, R 10 , R 12 , and R 14 Each of them is hydrogen.

[0090] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R2, R4, and R5~R 14 Each of these is a fluorine atom.

[0091] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is a trifluoromethyl group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0092] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12Each of these is an ethoxycarbonyl group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0093] In one embodiment, R1 is a methyl group and R3 is a t-butyl group. R7 and R 12 Each of these is an ethoxy group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0094] In one embodiment, structure (I) includes a methyl group R1, and R3 is a t-butyl group. R7 and R 12 Each of these is a diethylamino group. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of them is hydrogen.

[0095] In one embodiment, structure (I) includes a methyl group R1, and R3 is a 2,4,4-trimethylpentan-2-yl group. R2, R4, and R5~R 14 Each of them is hydrogen.

[0096] In one embodiment, structure (I) comprises R1 and R3, each of which is a sec-butyl group. R2, R4, and R5~R 14 Each of them is hydrogen.

[0097] In one embodiment, structure (I) includes R1 and R4, which are methyl groups, respectively. R2, R3, R5-R9, and R 10 ~R 14 Each of them is hydrogen.

[0098] In one embodiment, structure (I) includes R1, which is a methyl group. R4 is an i-propyl group. R2, R3, R5-R9, and R10 ~R 14 Each of them is hydrogen.

[0099] In one embodiment, structure (I) comprises R1, R3, and R4, each of which is an i-propyl group. R2, R5-R9, and R 10 ~R 14 Each of them is hydrogen.

[0100] In one embodiment, another procatalyst composition is provided. The procatalyst composition comprises a combination of a magnesium moiety, a titanium moiety, and a mixed internal electron donor. As used herein, the “mixed internal electron donor” is (i) a substituted phenylene aromatic diester, (ii) an electron donor component that donates electron pairs to one or more metals present in the resulting procatalyst composition, and (iii) optionally, another component. In one embodiment, the electron donor component is a diether, a benzoate, or a combination thereof. Procatalyst compositions having a mixed internal electron donor can be produced by procatalyst production procedures as disclosed in previously granted patents and publications identified herein.

[0101] For example, suitable catalyst compositions include procatalyst compositions, cocatalysts, and external electron donors or mixed external electron donors (M-EEDs) of two or more different components. Suitable external donors include one or more activity limiting agents (ALAs), one or more selectivity control agents (SCAs), or both ALAs and SCAs. As used herein, “external electron donors” are compositions comprising components, or mixtures of components, that are added independently of procatalyst formation that modifies catalytic performance. As used herein, “activity limiting agents” are compositions that reduce catalytic activity as the polymerization temperature rises above a threshold temperature (e.g., above about 85°C) in the presence of the catalyst. “Selectivity control agents” are compositions that improve the tacticity of a polymer, and improved tacticity is generally understood to mean increased tacticity, decreased xylene soluble content, or both. The above definitions are not mutually exclusive, and it should be understood that a single compound may be classified as both, for example, an activity limiter and a selectivity regulator.

[0102] In one embodiment, the external electron donor includes an alkoxysilane. The alkoxysilane has the following general formula: SiR m (OR') 4-m (I) In the formula, R is independently a hydrocarbyl or amino group substituted, for each occurrence, with hydrogen or one or more substituents optionally containing one or more heteroatoms of groups 14, 15, 16, or 17, wherein R contains up to 20 atoms excluding hydrogen and halogens, and R' is C 1~4 It is an alkyl group, and m is 0, 1, 2, or 3. In some embodiments, R is C 6~12 Arylalkyl or aralkyl, C 3~12 Cycloalkyl, C 3~12 Branched alkyl, or C 3~12 It is a cyclic or acyclic amino group, and R' is C 1~4It is an alkyl group, and m is either 1 or 2.

[0103] Non-limiting examples of suitable silane compositions include dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, and dimethyldimethoxysilane. In one embodiment, the silane composition is dicyclopentyldimethoxysilane (DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), or n-propyltrimethoxysilane (NPTMS), or any combination thereof.

[0104] In some embodiments, the selectivity control agent may be a mixture of two or more alkoxysilanes. In further embodiments, the mixture may be dicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane and tetraethoxysilane, or dicyclopentyldimethoxysilane and n-propyltriethoxysilane. In some embodiments, the mixed external electron donor may include benzoates, succinates, and / or diol esters. In some embodiments, the mixed external electron donor includes 2,2,6,6-tetramethylpiperidine as the SCA. In other embodiments, the mixed external electron donor includes diethers as both the SCA and ALA.

[0105] Mixed external electron donating systems may also include activity limiting agents (ALAs). ALAs suppress or otherwise prevent reactor malfunctions and ensure the continuation of the polymerization process. Typically, the activity of a Ziegler-Natta catalyst increases as the reactor temperature rises. Ziegler-Natta catalysts also typically maintain high activity near the melting point of the polymer produced. The heat generated by exothermic polymerization can cause polymer particles to form aggregates, which can ultimately lead to the interruption of the polymer formation process. ALAs reduce catalytic activity at high temperatures, thereby preventing reactor malfunctions, reducing (or preventing) particle aggregation, and ensuring the continuation of the polymerization process.

[0106] Activity limiters may be carboxylic acid esters, diethers, poly(alkene glycols), diol esters, and combinations thereof. Carboxylic acid esters may be aliphatic or aromatic, mono or polycarboxylic acid esters. Non-limiting examples of suitable monocarboxylic acid esters include ethyl benzoate and methyl benzoate, ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl p-isopropoxybenzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, ethyl p-chlorobenzoate, hexyl p-aminobenzoate isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate, and propyl pivalate.

[0107] Non-limiting examples of suitable polycarboxylic acid esters include diethyl terephthalate, dioctyl terephthalate, and bis[4-(vinyloxy)butyl]terephthalate.

[0108] Aliphatic carboxylic acid esters can be C6 aliphatic acid esters, mono or poly(two or more) esters, linear or branched, saturated or unsaturated, and any combination thereof. 30 Aliphatic acid esters may also be substituted with substituents containing one or more heteroatoms of group 14, 15, or 16. Preferred C6-C 30 Non-limiting examples of aliphatic acid esters include aliphatic C 6~30 Ci of monocarboxylic acids -2 O alkyl ester, aliphatic C 8~20 C of monocarboxylic acid 1~20 Alkyl esters, aliphatic C 4~20 C of monocarboxylic acids and dicarboxylic acids 1~4 Allyl mono and diesters, aliphatic C 8~20 C of monocarboxylic acids and dicarboxylic acids 1~4 Alkyl esters, and C 2~100 (Poly)glycol or C 2~100 (Poly)glycol ether C 6~20Examples include mono- or polycarboxylate derivatives. In further embodiments, C6-C 30 Aliphatic acid esters include laurate, myristate, palmitate, stearate, oleate, sebacate, (poly)(alkylene glycol) mono or diacetate, (poly)(alkylene glycol) mono or dimyristate, (poly)(alkylene glycol) mono or dilaurate, (poly)(alkylene glycol) mono or dioleate, glyceryl tri(acetate), C 2~40 This may be glyceryl triesters of aliphatic carboxylic acids, and mixtures thereof. In further embodiments, C6-C 20 The aliphatic ester is isopropyl myristate or di-n-butyl sebacate.

[0109] In one embodiment, the activity limiting agent includes a diether. The diether has the following structure (VI):

[0110] [ka] It may be a 1,3-diether compound represented by the formula, where R1 to R4 are independently alkyl, aryl, or aralkyl groups having up to 20 carbon atoms, and may optionally contain heteroatoms of groups 14, 15, 16, or 17, R i R1 and R2 may be hydrogen atoms. The dialkyl ether may be linear or branched and may contain one or more of the following groups: alkyl, alicyclic, aryl, alkylaryl, or arylalkyl radical having 1 to 18 carbon atoms, and hydrogen. R1 and R2 may be linked to form a cyclic structure such as cyclopentadiene or fluorene.

[0111] In one embodiment, the activity limiting agent has the following structure (VII):

[0112] [ka] The succinate composition comprises the formula R and R', where R and R' may be the same or different, and R and / or R' comprises one or more of the following groups: hydrogen, a linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group optionally containing a heteroatom. One or more ring structures may be formed via one or both of the carbon atoms at positions 2 and 3.

[0113] In one embodiment, the activity limiting agent has the following structure (VIII):

[0114] [ka] The diol ester is represented by the formula, where n is an integer from 1 to 5. R1 and R2 may be the same or different, and each may be selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, allyl, phenyl, or halophenyl groups. R3, R4, R5, R6, R7, and R8 may be the same or different, and each may be selected from hydrogen, halogen, substituted or unsubstituted hydrocarbyl having 1 to 20 carbon atoms. R1 to R6 groups may optionally contain one or more heteroatoms that replace carbon, hydrogen, or both, and the heteroatoms may be selected from nitrogen, oxygen, sulfur, silicon, phosphorus, and halogens. R7 and R8 may be the same or different, and may be bonded to any carbon atom at positions 2, 3, 4, 5, and 6 of any phenyl ring.

[0115] Each external electron donor component can be added to the reactor separately, or two or more can be mixed together beforehand and then added to the reactor as a mixture. In the mixture, two or more selectivity control agents or two or more activity limiting agents can be used. In one embodiment, the mixture is dicyclopentyl dimethoxysilane and isopropyl myristate, diisopropyl dimethoxysilane and isopropyl myristate, dicyclopentyl dimethoxysilane and poly(ethylene glycol) laurate, dicyclopentyl dimethoxysilane and isopropyl myristate and poly(ethylene glycol) dioleate, methylcyclohexyl dimethoxysilane and isopropyl myristate, n-propyl trimethoxysilane and isopropyl myristate, dimethyl dimethoxysilane and methylcyclohexyl dimethoxysilane and isopropyl myristate, dicyclopentyl dimethoxysilane and n-propyl triethoxysilane and isopropyl myristate, diisopropyl dimethoxysilane and n-propyl triethoxysilane and isopropyl myristate, as well as dicyclopentyl dimethoxysilane and tetraethoxysilane and isopropyl myristate, dicyclopentyl dimethoxysilane and diisopropyl dimethoxysilane and n-propyl triethoxysilane and isopropyl myristate, and combinations thereof.

[0116] The catalyst composition includes a co-catalyst. The co-catalyst for use with the Ziegler-Nattapro catalyst composition may be an aluminum-containing composition. Non-limiting examples of suitable aluminum-containing compositions include organoaluminum compounds such as trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum alkoxide, and alkylaluminum dialkoxide (compounds containing 1 to 10 or 1 to 6 carbon atoms in each alkyl or alkoxide group). In some embodiments, the co-catalyst is C such as triethylaluminum (TEA). 1~4The catalyst composition contains aluminum (Al) to (SCA+ALA) molar ratios of 0.5 to 25:1, or 1.0 to 20:1, or 1.5 to 15:1, or less than about 6.0, or less than about 5, or less than 4.5. In some embodiments, the Al:(SCA+ALA) molar ratio is 0.5 to 4.0:1. The total SCA to ALA molar ratio is 0.01 to 20:1, 0.10 to 5.00:1, 0.43 to 2.33:1, or 0.54 to 1.85:1, or 0.67 to 1.5:1.

[0117] IV.Applications The propylene-butene copolymers of this disclosure can be used in a wide variety of applications. As described above, the propylene-butene copolymers have excellent rigidity and transparency properties.

[0118] In one embodiment, the propylene-butene copolymer of the present disclosure can be incorporated into a composition for forming injection-molded articles such as containers. When used in injection molding, the polymer can have a melt flow rate of more than about 4 g / 10 min, for example more than about 20 g / 10 min, for example more than about 30 g / 10 min, for example more than about 35 g / 10 min. The container may have a bottom that defines a hollow interior and an upper part that includes a flange sealing the bottom. In addition to containers, any injection-molded article generally requiring a certain degree of rigidity along with good optics can be manufactured according to the present disclosure. For example, the propylene-butene copolymer of the present disclosure is particularly well suited for manufacturing packaging materials, including all different types of food packaging materials.

[0119] In addition to injection-molded articles, the propylene-butene copolymer of this disclosure can also be used for extrusion blow molding or thermoforming applications. For example, when formulated at a relatively low melt flow rate, the copolymer exhibits excellent melt strength, enabling the formation of a variety of different blow-molded articles having relatively thin walls. When used for blow molding or thermoforming, the polymer may have a melt flow rate of less than about 5 g / 10 min, e.g., less than about 4.5 g / 10 min, e.g., less than about 4 g / 10 min, e.g., less than 3.5 g / 10 min. The polymer may have a melt flow rate greater than about 0.2 g / 10 min, e.g., greater than about 1 g / 10 min.

[0120] Propylene-butene copolymers can be used, for example, to manufacture all different types of plastic bottles for holding beverages. As mentioned above, since the polymer can be formed from non-phthalate catalysts, it is exceptionally well suited for food contact applications.

[0121] In yet another embodiment, the propylene-butene copolymer of the present disclosure can be used in thermoforming applications. For example, the polymer can be used to manufacture thermoformed containers, including beverage cups. Beverage cups made according to the present disclosure may exhibit lower haze and higher rigidity compared, for example, cups made from ethylene random copolymer.

[0122] The propylene-butene copolymers of this disclosure can be combined with various other components and compounding elements when formulating polymer compositions for producing the molded articles described above. For example, in one embodiment, the polymer composition may contain antioxidants and acid scavengers, and in some applications, it may also preferably contain other additives such as mold release agents, antistatic agents, slip agents, anti-tack agents, processing aids, UV stabilizers, and colorants (pigments). The antioxidant may be a hindered phenol, which can be used together with a phosphite stabilizer. Possible acid scavengers include metal stearates such as calcium stearate, hydrotalcite, or mixtures thereof. Each additive may be present in the composition in an amount of about 0.01% to about 2% by weight, for example, about 0.1% to about 1% by weight.

[0123] In one embodiment, the copolymer composition may further contain a nucleating agent. The nucleating agent may be added to further improve the transparency properties of the composition. In one embodiment, the nucleating agent may be a clarifying agent that contains a compound capable of generating a gelling network within the composition.

[0124] In one embodiment, the nucleating agent may include a sorbitol compound such as a sorbitol acetal derivative. In one embodiment, for example, the nucleating agent may include dibenzyl sorbitol.

[0125] Regarding sorbitol acetal derivatives that can be used as additives in some embodiments, the sorbitol acetal derivative is shown by formula (I),

[0126] [ka] In the formula, R1 to R5 include the same or different parts selected from hydrogen and C1 to C3 alkyl groups.

[0127] In some embodiments, R1 to R5 are hydrogen atoms, and therefore the sorbitol acetal derivative is 2,4-dibenzylidene sorbitol ("DBS"). In some embodiments, R1, R4, and R5 are hydrogen atoms, and R2 and R3 are methyl groups, and therefore the sorbitol acetal derivative is 1,3:2,4-di-p-methyldibenzylidene-D-sorbitol ("MDBS"). In some embodiments, R1 to R4 are methyl groups, and R5 is hydrogen atoms, and therefore the sorbitol acetal derivative is 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol ("DMDBS"). In some embodiments, R2, R3, and R5 are propyl groups (-CH2-CH2-CH3), and R1 and R4 are hydrogen atoms, so the sorbitol acetal derivative is 1,2,3-trideoxy-4,6:5,7-bis-O-(4-propylphenylmethylene)nonitol ("TBPMN").

[0128] Other embodiments of nucleating agents that may be used include: 1,3:2,4-Dibenzylidenesorbitol, 1,3:2,4-Bis(p-methylbenzylidene)sorbitol, Di(p-methylbenzylidene)sorbitol, Di(p-ethylbenzylidene)sorbitol, and Bis(5',6',7',8'-tetrahydro-2-naphthylidene)sorbitol is one example.

[0129] In one embodiment, the nucleating agent may also include a bisamide such as benzenetrisamide. The nucleating agents described above can be used alone or in combination.

[0130] One or more nucleating agents may be present in the polymer composition in amounts greater than about 100 ppm, for example greater than about 300 ppm, for example greater than about 1000 ppm, for example greater than about 2000 ppm, and generally less than about 20,000 ppm, for example less than about 10,000 ppm, for example less than about 4000 ppm.

[0131] When one or more nucleating agents are clarifying agents, the clarifying agents may be added in amounts greater than approximately 1,500 ppm, for example, greater than approximately 1,800 ppm, for example, greater than approximately 2,000 ppm, for example, greater than approximately 2,200 ppm. One or more clarifying agents are generally present in amounts less than approximately 20,000 ppm, for example, less than approximately 15,000 ppm, for example, less than approximately 10,000 ppm, for example, less than approximately 8,000 ppm, for example, less than approximately 5,000 ppm.

[0132] As described above, the polymer compositions containing the propylene-butene copolymer of this disclosure have excellent low-haze characteristics, which can be achieved when one or more nucleating agents are added and combined with the polymer. For example, when measured at a thickness of 1 mm, the propylene-butene copolymer or the polymer composition containing the propylene-butene copolymer may have a haze of less than about 25%, e.g., less than 20%, e.g., less than 15%, e.g., less than 13%, e.g., less than 10%. When measured at a thickness of 0.7 mm, the propylene-butene copolymer or the polymer composition containing the propylene-butene copolymer may have a haze of less than about 18%, e.g., less than 15%, e.g., less than 15%, e.g., less than 12%, e.g., less than 10%. Molded articles such as bottles, containers, films, and cups made from this polymer may have a haze of less than about 10%, for example, less than about 7.5%, less than about 7%, less than about 6.5%, less than about 6%, or less than 5.5%. The haze is generally greater than about 1%.

[0133] V. Examples Example 1 Propylene-butene random copolymer samples were prepared and their properties were tested according to the procedure outlined above. The properties and experimental results are summarized in the table below.

[0134] Propylene-butene random copolymers were produced using a stereospecific sixth-generation Ziegler-Natta magnesium-supported / titanium catalyst. The catalyst contained a non-phthalate internal donor that produced polymers with a broader molecular weight distribution than those produced using metallocene catalysts. The process used to produce the polymers is described in the art as the UNIPOL gas-phase process. The catalyst used to produce the polymers contained a substituted phenylene aromatic diester internal electron donor. The catalyst used is commercially available from WRGrace and Company and is sold under the trade name CONSISTA. All copolymers were prepared using triethylaluminum as an external electron donor and co-catalyst.

[0135] With the exception of samples 1, 6, 10, and 14, which did not contain a nucleating agent, various different random copolymers were combined with nucleating agents. Two different nucleating agents were used. The nucleating agents are commercially available from Milliken Chemical, (1) TBPMN (Clarifying agent) and (2) HYPERFORM HPN-600ei (nucleating agent). Samples 2, 7, 11, and 15 contained HYPERFORM HPN-600ei at a concentration of 400 ppm. Samples 3, 8, 12, and 16 contained HYPERFORM HPN-600ei at a concentration of 2000 ppm. TBPMN It contains, and samples 4, 5, 9, 13, and 17 are at a concentration of 4000 ppm. TBPMN Each sample also contained a hindered phenol antioxidant, a phosphite antioxidant, and an acid scavenger (hydrotalcite).

[0136] The following results were obtained.

[0137] [Table 1]

[0138] [Table 2]

[0139] Example 2 Propylene-butene random copolymer samples were prepared and their properties were tested according to the procedure outlined above. The properties and experimental results are summarized in the table below.

[0140] Propylene-butene random copolymers were produced using a stereospecific sixth-generation Ziegler-Natta magnesium-supported / titanium catalyst. The catalyst contained a non-phthalate internal donor that produced polymers with a broader molecular weight distribution than those produced using metallocene catalysts. The process used to produce the polymers is described in the art as the UNIPOL gas-phase process. The catalyst used to produce the polymers contained a substituted phenylene aromatic diester internal electron donor. The catalyst used is commercially available from WRGrace and Company and is sold under the trade name CONSISTA. All copolymers were prepared using triethylaluminum as an external electron donor and co-catalyst.

[0141] Propylene-ethylene random copolymers were also produced. In the table below, for example, samples 20-28 and 32-36 relate to propylene-butene random copolymers, while samples 18, 19, 29-31, and 37-40 relate to propylene-ethylene random copolymers. Samples 18, 19, 37, and 38 were produced using the same catalyst used to produce the propylene-butene copolymers. Samples 29-31, 39, and 40 were prepared using a phthalate-based catalyst. Some of the polymers produced were combined with either 2000 ppm or 4000 ppm of a nucleating agent, i.e., TBPMN, while samples 20, 23, 26, 29, and 32 did not contain a nucleating agent. The polymer compositions were then injection molded into containers or blow molded into bottles. The following results were obtained.

[0142] [Table 3-1] [Table 3-2]

[0143] Furthermore, samples 19 and 22 were tested for haze in injection-molded articles one year after production and compared with commercially available grade propylene-ethylene random copolymers having the following characteristics.

[0144] [Table 4]

[0145] The following results were obtained.

[0146] [Table 5]

[0147] These and other modifications and changes to the present invention can be implemented by those skilled in the art without departing from the spirit and scope of the invention as more specifically described in the appended claims. In addition, it should be understood that the various embodiments may be interchangeable in whole or in part. Furthermore, those skilled in the art will understand that the foregoing description is merely illustrative and is not intended to limit the invention to what is further described in such appended claims. The present invention includes the following embodiments. [1] A polymer composition, A propylene-butene copolymer containing propylene as the main monomer, It contains approximately 1% to 12% by weight of butene. It contains a xylene-soluble fraction of approximately 1.0% to 8.0% by weight, A propylene-butene copolymer having a molecular weight distribution (Mw / Mn) greater than approximately 3.5, A nucleating agent is included, The polymer composition exhibits a haze of less than approximately 25% at 1 mm, and after thermal aging at 55°C for 24 hours, the haze increases by only about 30% or less. [2] The polymer composition according to claim 1, wherein the polymer composition exhibits a haze of less than about 20%, for example less than about 15%, for example less than 13%, for example less than 10% at 1 mm. [3] The polymer composition according to claim 1 or 2, wherein, after thermal aging at 55°C for 24 hours, the haze of the polymer composition increases by about 25% or less, for example, about 20% or less, for example, about 15% or less. [4] The polymer composition according to any one of claims 1 to 3, wherein, after thermal aging at 55°C for 24 hours, the haze of the polymer composition increases by only about 10% or less. [5] The polymer composition according to any one of claims 1 to 4, wherein the polymer has a xylene-soluble fraction / butene content ratio of about 0.3 to about 3.0, for example, about 0.5 to about 2.0. [6] The polymer composition according to any one of claims 1 to 4, wherein the nucleating agent comprises nonitol. [7] The polymer composition according to any one of claims 1 to 6, wherein the polymer composition has a melt flow rate of about 0.25 g / 10 min to about 225 g / 10 min. [8] The polymer composition according to any one of claims 1 to 7, wherein the polymer composition has a melt flow rate of about 1 g / 10 min to about 60 g / 10 min. [9] The polymer composition according to any one of claims 1 to 8, wherein the polymer composition exhibits a flexural modulus of more than about 1000 MPa, for example, more than about 1200 MPa.

[10] The polymer composition according to any one of claims 1 to 9, wherein the propylene-butene copolymer is catalyzed in the presence of a non-phthalate Ziegler-Natta catalyst.

[11] The polymer composition according to 10, wherein the Ziegler-Natta catalyst comprises an internal electron donor, and the internal electron donor comprises a substituted phenylenediester.

[12] The polymer composition according to any one of claims 1 to 11, wherein the propylene-butene copolymer is present in the polymer composition in an amount of more than about 70% by weight, for example more than about 80% by weight, for example more than about 90% by weight, for example more than about 95% by weight.

[13] The polymer composition according to any one of claims 1 to 12, wherein the propylene-butene copolymer contains butene in an amount of about 2% to about 8% by weight, for example, about 4% to about 6% by weight.

[14] The polymer composition according to 13, wherein the propylene-butene copolymer exhibits a heat distortion temperature greater than approximately 75°C.

[15] The polymer composition according to 13 or 14, wherein the propylene-butene copolymer has a melting point of about 143°C to about 155°C.

[16] The polymer composition according to any one of claims 1 to 15, wherein the propylene-butene copolymer has a xylene-soluble content of about 2% to about 6% by weight.

[17] The polymer composition according to any one of claims 1 to 16, further comprising at least one antioxidant and at least one acid scavenger.

[18] An injection-molded article made from a polymer composition described in any one of items 1 to 17.

[19] A blow-molded article made from a polymer composition described in any one of items 1 to 17.

[20] A thermoformed article made from a polymer composition described in any one of items 1 to 17.

[21] The blow-molded article according to 18 or the thermoformed article according to 17, wherein the polymer composition has a melt flow rate of less than about 4 g / 10 min.

[22] A container made from a polymer composition described in any one of items 1 to 17.

[23] Food packaging material made from a polymer composition described in any one of items 1 to 17.

[24] A medical device made from a polymer composition described in any one of items 1 to 17.

[25] The articles described in any one of paragraphs 18, 19, or 20, wherein the articles exhibit a haze of less than approximately 8%, for example, less than 6%, for example, less than 4%.

Claims

1. A polymer composition, A propylene-butene copolymer containing propylene as the main monomer, The propylene-butene copolymer is catalyzed in the presence of a non-phthalate Ziegler-Natta catalyst, the non-phthalate Ziegler-Natta catalyst comprises an internal electron donor, and the internal electron donor comprises a substituted phenylenediester. It contains 1% to 12% by weight of butene, It contains a xylene-soluble fraction of 1.0% to 8.0% by weight, A propylene-butene copolymer having a molecular weight distribution (Mw / Mn) greater than 3.5, A nucleating agent is included, A polymer composition that exhibits a haze of less than 25% at 1 mm.

2. The polymer composition according to claim 1, wherein the polymer composition exhibits a haze of less than 20% at 1 mm.

3. The polymer composition according to any one of claims 1 to 2, wherein the polymer has a xylene-soluble fraction / butene content ratio of 0.3 to 3.

0.

4. The polymer composition according to any one of claims 1 to 3, wherein the nucleating agent comprises nonitol.

5. The polymer composition according to any one of claims 1 to 4, wherein the polymer composition has a melt flow rate of 0.25 g / 10 min to 225 g / 10 min.

6. The polymer composition according to any one of claims 1 to 5, wherein the polymer composition has a melt flow rate of 1 g / 10 min to 60 g / 10 min.

7. The polymer composition according to any one of claims 1 to 6, wherein the polymer composition exhibits a flexural modulus of more than 1000 MPa.

8. The polymer composition according to any one of claims 1 to 7, wherein the propylene-butene copolymer is present in the polymer composition in an amount of more than 70% by weight.

9. The polymer composition according to any one of claims 1 to 8, wherein the propylene-butene copolymer contains butene in an amount of 2% to 8% by weight.

10. The polymer composition according to claim 9, wherein the propylene-butene copolymer exhibits a heat distortion temperature of more than 75°C.

11. The polymer composition according to claim 9 or 10, wherein the propylene-butene copolymer has a melting point of 143°C to 155°C.

12. The polymer composition according to any one of claims 1 to 11, wherein the propylene-butene copolymer has a xylene-soluble content of 2% to 6% by weight.

13. The polymer composition according to any one of claims 1 to 12, further comprising at least one antioxidant and at least one acid scavenger.

14. An injection-molded article made from a polymer composition according to any one of claims 1 to 13.

15. A blow-molded article made from a polymer composition according to any one of claims 1 to 13.

16. A thermoformable article made from a polymer composition according to any one of claims 1 to 13.

17. The blow-molded article according to claim 15 or the thermoformed article according to claim 16, wherein the polymer composition has a melt flow rate of less than 4 g / 10 min.

18. A container made from the polymer composition described in any one of claims 1 to 13.

19. A food packaging material made from a polymer composition according to any one of claims 1 to 13.

20. A medical device made from a polymer composition according to any one of claims 1 to 13.

21. The article according to claim 14, 15, or 16, wherein the article exhibits less than 8% haze.

Images