Propylene butene copolymers and compositions made therefrom - Patents.com

Abstract

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

Description

[Technical Field]

[0001] (Related Applications) This application is based on and claims priority to U.S. Provisional Patent Application No. 63 / 050,770, filed July 11, 2020, which is incorporated herein by reference. [Background technology]

[0002] Polypropylene polymer is a highly versatile thermoplastic polymer that can be used in many different applications. For example, polypropylene polymer can be extruded to form a variety of different shapes, including films and fibers, and can be molded into articles with relatively simple or complex shapes. Polypropylene polymer is used to manufacture a variety of consumer products, including carpets, carpet backing, food packaging, rigid packaging, industrial parts such as automotive parts, waste and pressure pipes, as well as furniture parts, household goods, and toys. Polypropylene polymer can have, for example, low density, high stiffness, heat resistance, chemical inertness, good transparency, and is recyclable. The properties of polypropylene polymer can be modified and tailored to specific applications by combining propylene monomer with other monomers to impart various properties.

[0003] For example, copolymerizing propylene with a small amount of ethylene produces a random copolymer with unique properties. The resulting copolymer can have, for example, a lower crystallinity than polypropylene homopolymer, resulting in improved transparency, impact resistance, and a lower heat-sealing temperature. The transparency can be further enhanced by additives such as nucleating agents and clarifying agents. Random propylene-ethylene copolymers also generally have a lower melting temperature, which can limit their use in high-temperature applications. In addition, when exposed to high temperatures, the transparency of the polymer tends to decrease. For example, not only can further crystallization occur during aging, but blooming, which produces a cloudy surface layer, can also occur.

[0004] As described above, propylene-ethylene random copolymers have made great advances in the art, but the polymers have various drawbacks. Furthermore, attempts to improve one product property, such as reducing haze, can adversely affect another property, such as mechanical strength. Therefore, there is a need for propylene polymers that have an improved balance of mechanical properties and good optics. There is also a need for such propylene polymers that can be used to form a variety of articles by injection molding, blow molding, and thermoforming. Summary of the Invention

[0005] In general, the present disclosure is directed to propylene copolymers, particularly propylene-butene random copolymers, which have been found to have an excellent balance of properties. Additionally, the propylene copolymers can be made without the use of phthalate-based catalysts. The propylene-butene copolymers of the present disclosure have excellent optical properties and can be used to form transparent articles. Additionally, the polymers can be formulated for any suitable molding technique, such as extrusion blow molding and thermoforming. For example, articles can be formed from nucleated / clarified propylene-butene copolymers with lower haze and higher stiffness than articles previously made from nucleated / clarified propylene-ethylene random copolymers.

[0006] In one embodiment, by way of example, the present disclosure is directed to a propylene-butene copolymer containing propylene as the primary monomer. The copolymer can generally contain butene in an amount of about 1% to about 12% by weight, such as about 2% to about 10% by weight, such as about 5% to about 8% by weight. The propylene-butene copolymer can have a xylene-soluble fraction of about 1% to about 10% by weight, such as about 2% to about 8% by weight. The polymer can have a xylene-soluble fraction / butene content ratio of about 0.3 to about 3.0, such as about 0.3 to about 2.2, such as about 0.5 to about 1.0. The propylene-butene copolymer can be made from a non-phthalate Ziegler-Natta catalyst containing a substituted aromatic phenylenediester to produce a polymer having a molecular weight distribution greater than about 3.5, such as greater than about 4. Additionally, propylene-butene copolymers can have deflection temperatures under load of greater than about 70°C, and even greater than about 75°C, especially when the copolymer contains a lower amount of butene.

[0007] Propylene-butene copolymers made according to the present disclosure can be produced with specific melt flow rates that are compatible with subsequent melt processing conditions to produce polymeric articles. For example, in one embodiment, the propylene-butene copolymer can have a relatively low melt flow rate, such as from about 0.2 g / 10 min to about 4 g / 10 min. Alternatively, the propylene-butene copolymer can have a melt flow rate of from about 4 g / 10 min to about 220 g / 10 min.

[0008] The propylene-butene copolymers prepared according to the present disclosure can have relatively high stiffness values. For example, the polymers can have flexural moduli greater than about 1100 MPa, such as greater than about 1300 MPa, such as greater than about 1400 MPa, or greater than about 1500 MPa. The polymers can have relatively high melting temperatures. For example, the primary melting point can be greater than about 135°C, such as about 145°C to about 155°C.

[0009] The random propylene copolymer of the present disclosure can be used to form polymer compositions for forming various molded articles. For example, the random propylene-butene copolymer can be present in the composition in an amount greater than about 70% by weight, such as greater than about 80% by weight, such as greater than about 90% by weight, such as greater than about 95% by weight, such as greater than about 98% by weight, such as greater than about 99% by weight. The composition can contain various other additives and ingredients, including antioxidants, acid scavengers, and / or antistatic agents. In one embodiment, the polymer composition can contain a nucleating agent. The nucleating agent can, for example, include nonitol.

[0010] The polymer composition can be formulated to have excellent transparency properties. For example, the composition can exhibit a haze of about 15% or less, such as less than about 8% at 0.7 mm.

[0011] The present disclosure also relates to molded articles made from the above-described polymer compositions. For example, the polymer compositions of the present disclosure can be formulated to be used to produce injection-molded articles, particularly blow-molded and thermoformed articles. For example, the present disclosure can be used to produce blow-molded bottles, thermoformed cups, and thermoformed containers. The polymers of the present disclosure are also particularly well suited for the production of packaging, including food packaging. For example, the propylene-butene copolymers of the present disclosure can be used to produce packaging films. The polymer compositions can also be used for fibers. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present disclosure is directed to propylene alpha-olefin copolymer compositions and methods for producing the propylene copolymer compositions. The compositions can include propylene-butene random copolymers. For example, the polymers of the present disclosure can be made from only propylene and butene monomers, or can be made from propylene, butene, and relatively small amounts of one or more other alpha-olefin monomers.

[0013] Propylene-butene copolymers made according to the present disclosure have been found to have an excellent balance of properties. For example, the copolymers can exhibit improved stiffness, high heat distortion resistance, and good optics, especially compared to many conventional propylene-ethylene copolymers. For example, the propylene-butene copolymers of the present disclosure can be formulated with additives to have excellent optical properties, exhibiting very low haze even at thicknesses of 0.7 mm. Propylene-butene copolymers are also extremely versatile, being able to be formulated over a wide range of melt flow rates, making the polymers well suited for use in all different types of molding processes, such as injection molding, extrusion blow molding, or thermoforming.

[0014] The propylene-butene copolymers of the present disclosure can also be formed using Ziegler-Natta catalysts, which impart a relatively broad molecular weight distribution to the polymer. In one embodiment, non-phthalate catalysts containing substituted aromatic phenylenediesters can be used, making the polymer more suitable for contact with food and beverages. The polymers are also well suited for use in medical applications.

[0015] The propylene-butene copolymers of the present disclosure can be incorporated into various polymer compositions containing other additives, including clarifiers and nucleating agents. The polymer compositions can then be used to make a wide variety of articles. For example, the polymer compositions of the present disclosure can be used to manufacture all kinds of packaging products, including food packaging. For example, in one aspect, a polymer composition containing a propylene-butene copolymer can be used to manufacture a polymer film with low haze for packaging food. In addition, the polymer composition can be used to manufacture all kinds of strong containers that combine excellent rigidity properties with excellent optical properties. The polymer compositions of the present disclosure containing a propylene-butene copolymer can also be used to manufacture blow-molded bottles, thermoformed cups, fibers, and the like.

[0016] I. Definitions and Test Procedures The term "propylene-butene copolymer," as used herein, is a copolymer containing a majority weight percent of propylene monomer with butene monomer as a minor constituent. A "propylene-butene copolymer" (also called a polypropylene-butene random copolymer) is a polymer with individual repeat units of butene monomer present in a random or statistical distribution in the polymer chain.

[0017] Melt flow rate (MFR), as used herein, is measured for propylene-based polymers at 230°C with a weight of 2.16 kg according to ASTM D 1238 test method. Melt flow rate can be measured in pellet form or on reactor powder. When measuring reactor powder, a stabilization package can be added containing 2000 ppm CYANOX 2246 antioxidant (methylene bis(4-methyl-6-tert-butylphenol), 2000 ppm IRGAFOS 168 antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), and 1000 ppm acid scavenger ZnO.

[0018] Xylene soluble (XS) is defined as the weight percent of resin remaining in solution after dissolving a sample of polypropylene random copolymer resin in hot xylene and cooling the solution to 25° C. This is also referred to as the gravimetric XS method according to ASTM D5492-06 using a 60 minute settling time, and is also referred to herein as the "wet method."

[0019] The ASTM D5492-06 method described above can be adapted to determine the xylene-soluble fraction. Generally, the procedure involves weighing 2 g of sample and dissolving it in 200 mL of o-xylene in a 400 mL flask equipped with a 24 / 40 fitting. The flask is connected to a water-cooled condenser, and the contents are stirred and heated to reflux under nitrogen (N2), then maintained at reflux for an additional 30 minutes. The solution is then cooled in a temperature-controlled water bath at 25 °C for 60 minutes to allow the xylene-insoluble fraction to crystallize. Once the solution is cooled and the insoluble fraction precipitates from the solution, separation of the xylene-soluble fraction (XS) from the xylene-insoluble fraction (XI) is achieved by filtration through 25-micrometer filter paper. 100 mL of the filtrate is collected in a pre-weighed aluminum pan, and the o-xylene is evaporated from this 100 mL filtrate under a stream of nitrogen. Once the solvent has evaporated, the pan and contents are placed in a vacuum oven at 100°C for 30 minutes or until dry. The pan is then cooled to room temperature and weighed. The xylene soluble portion is calculated as XS (wt%) = [(m3 - m2) * 2 / m1] * 100, where m is the original weight of the sample used, m is the weight of the empty aluminum pan, and m is the weight of the pan and residue (asterisks are used here and elsewhere in this disclosure). * indicates that the identified term or value is to be multiplied).

[0020] XS can also be measured according to the Viscotek method as follows: 0.4 g of polymer is dissolved in 20 mL of xylene and stirred at 130°C for 60 minutes. The solution is then cooled to 25°C, and after 60 minutes, the insoluble polymer fraction is filtered off. The resulting filtrate is analyzed by flow-injection polymer analysis using a Viscotek ViscoGEL H-100-3078 column with a THF mobile phase flowing at 1.0 mL / min. The column is coupled to a Viscotek Model 302 Triple Detector Array equipped with light scattering, viscometer, and refractometer detectors operated at 45°C. Instrument calibration is maintained with Viscotek PolyCAL™ polystyrene standards. A polypropylene (PP) homopolymer, such as biaxially oriented polypropylene (BOPP) grade Dow 5D98, is used as a reference material to ensure that the Viscotek instrument and sample preparation procedures provide consistent results. The reference polypropylene homopolymer values ​​are first obtained from testing using the ASTM method described above.

[0021] The term "tacticity" generally refers to the relative stereochemistry of adjacent chiral centers within a macromolecule or polymer. For example, in a propylene-based polymer, the enantiomers of adjacent monomers, such as two propylene monomers, can be either like or opposite configuration. The term "diad" is used to designate two consecutive monomers, and three adjacent monomers are called a "triad." If the enantiomers of adjacent monomers are of the same relative configuration, the diad is considered isotactic; if they are of opposite configuration, they are called syndiotactic. Another way to describe the configurational relationship is that consecutive pairs of monomers with the same enantiomers are meso (m) and racemic (r) of opposite configuration.

[0022] The tacticity or stereochemistry of polymers in general, and polypropylene or polypropylene random copolymers in particular, can be described or quantified by reference to triad concentration. An isotactic triad, typically identified by the abbreviation "mm," is composed of two adjacent meso diads with the same configuration; therefore, the tacticity of the triad is identified as "mm." If two adjacent monomers in a three-monomer sequence have the same enantiomerism but differ from the relative configuration of the third unit, the triad has an "mr" tacticity. An "rr" triad has a middle monomer unit with the opposite configuration to either neighbor. The fraction of each type of triad in a polymer can be determined, and when multiplied by 100, indicates the percentage of that type found in the polymer. The mm percentage is used to identify and characterize the polymers herein.

[0023] The sequence distribution of the monomers in the polymer is 13 C-NMR, which can also identify the position of the butene residues relative to adjacent propylene residues. 13 C NMR can be used to measure butene content, triad distribution, and triad tacticity and is performed as follows:

[0024] Samples are 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 sample in a Norell 1001-7 10 mm 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.

[0025] Data are collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe. Data are acquired with 512 transients per data file, 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 unspun samples in locked mode. Samples are allowed to thermally equilibrate for 10 minutes prior to data acquisition. The percent mm tacticity and weight percent butene are calculated according to methods commonly used in the art, which are briefly summarized below.

[0026] For measuring the chemical shifts of the resonances, the methyl group of the third unit in a sequence of five consecutive propylene units consisting of head-to-tail bonds and having the same relative enantiomerism is set to 21.83 ppm. The chemical shifts of the other carbon resonances are determined using the above values ​​as a reference. The spectrum for the methyl carbon region (17.0-23 ppm) can be divided 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 with reference to literature sources, such as the articles in "Polymer", T. Tsutsui et al., Vol. 30, No. 7 (1989), pp. 1350-1356 and / or "Macromolecules", H.N. Cheng, Vol. 17 (1984), pp. 1950-1955, the contents of which are incorporated herein by reference.

[0027] For convenience, the butene content may also be determined by the primary method described above. 13The butene content is measured using Fourier Transform Infrared (FTIR) spectroscopy, which correlates with the butene content determined using C NMR. The relationship and agreement between measurements made using the two methods is described, for example, in J.R. Padson and J.C. Sandall, "Quantitative Measurement of Ethylene Incorporation into Propylene Copolymers by Carbon-13 Nuclear Magnetic Resonance and Infrared Spectroscopy," Analytical Chemistry, Vol. 50, No. 13, November 1978, pp. 1777-1780.

[0028] Flexural modulus is determined according to ASTM D790-10, Method A, at 1.3 mm / min using Type 1 specimens of ASTM 3641 and molded according to ASTM D4101.

[0029] Izod impact strength is measured according to ASTM D 256 and D4101.

[0030] Haze is determined according to ASTM Test D1003, Procedure A, using the latest version of the test. Haze can be measured on test plaques or on molded articles such as bottles, cups, containers, or films. Haze can be measured before and after heat aging. Haze can be measured using a BYK Gardner Haze-Gard Plus 4725 instrument. Injection-molded test specimens tested for haze measurement can be injection molded at temperatures between 200°C and 230°C when nonitol is present as a nucleating agent, between 250°C and 260°C when sorbitol is present as a nucleating agent, or between 200°C and 260°C when an insoluble particulate nucleating agent is present. Heat aging is performed by placing the specimen in an oven at the desired temperature (e.g., 121°C) for the desired time (e.g., 30 minutes) and then retesting for haze.

[0031] Heat distortion temperature (HDT) is determined according to ASTM test D648, entitled Distortion Temperature of Plastics Under Flexural Load, at 66 psi, on specimens prepared / aged according to D4101.

[0032] The melting point or melting temperature and crystallization temperature are determined using differential scanning calorimetry (DSC). The melting point is the first peak formed during the test, and typically the second peak formed. The term "crystallinity" refers to the order of the arrangement of atoms or molecules that form a crystalline structure. Polymer crystallinity can be determined using DSC. me means the temperature at which melting ends, and T max means the peak melting temperature, both of which are determined by one skilled in the art from DSC analysis using data from the final heating step. One suitable method for DSC analysis uses a 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 without any sample in the aluminum DSC pan. A 7-milligram fresh indium sample is then analyzed by heating the sample to 180°C, cooling the sample to 140°C at a cooling rate of 10°C / min, subsequently holding the sample isothermally at 140°C for 1 minute, and subsequently heating the sample from 140°C to 180°C at a heating rate of 10°C / min. The heat of fusion and onset of melting of the indium sample are determined, confirming that the onset of melting is within 0.5°C of 156.6°C and the heat of fusion is within 0.5 J / g of 28.71 J / g. Deionized water is then analyzed by cooling a small drop of fresh sample in a DSC pan from 25 °C to -30 °C at a cooling rate of 10 °C / min. The sample is held isothermally at -30 °C for 2 min 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 °C to 0.5 °C.

[0033] Mw / Mn (also referred to as "MWD") and Mz / Mw are measured by gel permeation chromatography (GPC) according to the Polypropylene Analysis Method. Polymers are analyzed on a Polymer Char High Temperature GPC equipped with an IR5 MCT (cadmium mercury telluride high sensitivity, thermoelectrically cooled IR detector), a Polymer Char four-capillary viscometer, a Wyatt octagonal MALLS, and three Agilent Plgel Olexis (13 μm). The oven temperature is set to 150°C. The solvent is nitrogen-purged 1,2,4-trichlorobenzene (TCB) containing approximately 200 ppm of 2,6-di-t-butyl-4-methylphenol (BHT). The flow rate was 1.0 mL / min, and the injection volume was 200 μL. A sample concentration of 2 mg / mL is prepared by dissolving the sample in N 2 purged and preheated TCB (containing 200 ppm BHT) at 160° C. for 2 hours with gentle stirring.

[0034] The GPC column set was calibrated by running 20 narrow molecular weight distribution polystyrene standards. The molecular weights (MW) of the standards ranged from 266 to 12,000,000 g / mol, and the standards were contained in six "cocktail" mixtures. Each standard mixture had at least 10 years of separation between the individual molecular weights. The polystyrene standards were prepared at 0.005 g in 20 mL of solvent for molecular weights ≥ 1,000,000 g / mol and 0.001 g in 20 mL of solvent for molecular weights < 1,000,000 g / mol. The polystyrene standards were dissolved at 160 °C for 60 min with stirring. The narrow standard mixture was run first, in order of highest molecular weight component to minimize the effects of degradation. A logarithmic molecular weight calibration was generated using a fourth-order polynomial fit as a function of elution volume. The equivalent polypropylene molecular weight was calculated using the reported Mark-Houwink coefficients for polypropylene (Th. G. Scholte, N.L. J. Meijerink, H.M. Schoffeleers, and A.M. G. Brands, J. Appl. Polym. Sci., 29, 3763-3782 (1984)) and polystyrene (E.P. Tocka, R.J. Roe, N.Y. Hellman, P.M. Muglia, Macromolecules, 4, 507 (1971)) using the following formula:

[0035]

number

[0036] [Table 1]

[0037] II. Propylene-Butene Random Copolymers and Compositions The propylene-butene copolymers of the present disclosure can contain a majority weight percent of propylene monomer with butene monomer as a minor constituent. The butene content of the propylene-butene copolymers of the present disclosure can be from about 1 wt% to about 12 wt%, including total increments of 0.1 wt% therebetween. For example, the propylene-butene copolymers can contain butene in an amount greater than about 1.5 wt%, such as greater than about 2 wt%, such as greater than about 2.3 wt%, such as greater than about 3 wt%, such as greater than about 4 wt%, such as greater than about 4.5 wt%, or such as greater than about 5 wt%. The butene content of the propylene-butene copolymers is generally less than about 11 wt%, such as less than about 10 wt%, such as less than about 9 wt%, such as less than about 8 wt%, such as less than about 7.8 wt%, such as less than about 7 wt%, such as less than about 6 wt%, or such as less than about 5 wt%. The amount of butene incorporated into the copolymer can be varied to alter various physical properties of the polymer.

[0038] The xylene soluble (XS) fraction of the copolymer of the present invention can be (≦) 8.0 wt% or less, or ≦7.0 wt%, more preferably ≦6.0 wt%, and even more preferably ≦5.0 wt% of the copolymer. The xylene soluble fraction is generally greater than about 0.5 wt%, such as greater than about 1 wt%. The xylene soluble (XS) fraction is preferably in the range of 1.0 wt% to 8.0 wt%, such as in the range of 2 wt% to 7 wt%. Particularly advantageously, propylene-butene copolymers according to the present disclosure can have a xylene soluble content greater than about 3 wt% while still possessing excellent low haze properties. The polymer can have a xylene soluble fraction / butene content ratio of about 0.3 to about 3.0, such as about 0.3 to about 2.0, such as about 0.5 to about 1.0, or less than 1.0.

[0039] The melt flow rate of propylene-butene copolymers made according to the present disclosure can vary. For example, the melt flow rate can be from about 0.2 g / 10 min to about 220 g / 10 min, including 0.1 total increments therebetween. For example, the melt flow rate of the polymer can be modified and controlled based on various factors and the desired application. For example, a lower melt flow rate may be desired when the polymer is incorporated into a composition to be blow molded or thermoformed. For example, in one embodiment, the melt flow rate of the propylene-butene copolymer may be less than about 20 g / 10 min, such as less than about 15 g / 10 min, such as less than about 10 g / 10 min, such as less than about 8 g / 10 min, such as less than about 6 g / 10 min, such as less than about 4 g / 10 min, and generally greater than about 1 g / 10 min, such as greater than about 1.5 g / 10 min. However, when the polymer is used for injection molding, a higher melt flow rate may be desired. For example, in one embodiment, the melt flow rate of the polymer may be greater than about 10 g / 10 min, such as greater than about 20 g / 10 min, such as greater than about 30 g / 10 min, such as greater than about 40 g / 10 min, and generally less than about 110 g / 10 min, such as less than 80 g / 10 min, such as less than about 60 g / 10 min.

[0040] The copolymer of the present disclosure generally has a relatively broad molecular weight distribution.For example, the molecular weight distribution (Mw / Mn) is generally greater than about 3.5, such as greater than about 3.8, for example, greater than about 4, such as greater than about 4.3, for example, greater than about 4.5, for example, greater than about 4.8, for example, greater than about 5, such as greater than about 5.2, for example, greater than about 5.5, for example, greater than about 5.7, for example, greater than about 6, and generally less than about 10, for example, less than about 8, for example, less than about 7.5.The weight average molecular weight is determined by GPC.

[0041] In one embodiment, the propylene-butene copolymer can be formulated to have excellent stiffness properties. For example, the copolymer can have a flexural modulus of greater than about 1100 MPa, such as greater than about 1150 MPa, such as greater than about 1200 MPa, such as greater than about 1250 MPa, such as greater than about 1300 MPa, such as greater than about 1350 MPa, such as greater than about 1400 MPa, such as greater than about 1450 MPa, or such as greater than about 1500 MPa. The flexural modulus is generally less than about 3000 MPa, such as less than about 2000 MPa.

[0042] Particularly advantageously, propylene-butene random copolymers can have high heat distortion resistance, especially when the polymer is formulated to contain a lower amount of butene. Generally, the polymer can have a deflection temperature under load (HDT) greater than about 70°C. When butene is contained in an amount less than 8% by weight, such as less than 6% by weight, for example, less than 5% by weight, the HDT can be greater than about 75°C, such as greater than about 76°C, such as greater than about 77°C, and generally less than about 90°C. Additionally, the polymer can be formulated to have a melting point greater than about 135°C, such as greater than about 145°C, such as greater than about 147°C, such as greater than about 148°C, such as greater than about 149°C, such as greater than about 150°C, such as greater than about 151°C, and generally less than about 165°C. In one embodiment, the polymer can have a primary melting point of 147°C or greater.

[0043] In addition to excellent stiffness and heat resistance, propylene-butene copolymers can also have good toughness. For example, the copolymer can have an Izod impact strength of greater than about 40 J / m, such as greater than about 45 J / m, such as greater than about 50 J / m, such as greater than about 55 J / m, such as greater than about 60 J / m, such as greater than about 65 J / m, such as greater than about 70 J / m, such as greater than about 75 J / m, such as greater than about 80 J / m, such as greater than about 85 J / m, or such as greater than about 90 J / m. The impact strength is generally less than about 200 J / m, such as less than about 150 J / m.

[0044] III. Preparation of Propylene-Butene Random Copolymer In one embodiment, the propylene-butene copolymers of the present disclosure can be produced using a non-phthalate Ziegler-Natta catalyst. A non-phthalate catalyst includes a catalyst system that does not contain phthalate compounds. For example, the catalyst support, internal electron donor, external electron donor, activity limiter, and activator are all non-phthalate. Phthalates have been used as internal electron donors in the past. Non-phthalate internal electron donors include diethers, succinates, ethyl benzoate, and phenylenediesters. The use of a non-phthalate catalyst makes the polymer suitable for food contact and medical applications. Additionally, the use of a Ziegler-Natta catalyst can produce a broad molecular weight distribution, which can offer numerous advantages and benefits.

[0045] Propylene-butene copolymers can generally be made in any suitable reactor using any suitable process for producing propylene-based polymers. This includes the UNIPOL® PP gas-phase process, which uses a supported Ziegler-Natta catalyst. The CONSISTA® catalyst, available from WRGrace & Co. (Columbia, Maryland), is particularly preferred. Suitable polypropylene random copolymers can be produced using a single reactor or multiple reactors. Examples of processes that can be used are described in U.S. Pat. No. 9,624,323 and U.S. Patent Application Publication No. 2016 / 0289357, which are incorporated herein by reference.

[0046] Suitable precatalyst compositions for use in producing polypropylene random copolymers include Ziegler-Natta precatalyst compositions. In one embodiment, the Ziegler-Natta precatalyst composition contains a titanium moiety, such as titanium chloride, a magnesium moiety, such as magnesium chloride, and an internal electron donor.

[0047] In one embodiment, the internal electron donor comprises a substituted phenylene aromatic diester. In one embodiment, a 1,2-phenylene aromatic diester is provided. The substituted 1,2-phenylene aromatic diester has the following structure (I):

[0048] [ka] In the formula, R1~R 14 are the same or different. R1~R 14 Each of R1 to R2 is selected from hydrogen, 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. 14 At least one of these is not hydrogen.

[0049] 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, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkylaryl, and alkynyl groups.

[0050] As used herein, the terms "substituted hydrocarbyl" and "substituted hydrocarbon" refer to a hydrocarbyl group substituted with one or more non-hydrocarbyl substituents. A non-limiting example of a non-hydrocarbyl substituent is a heteroatom. As used herein, "heteroatom" refers to an atom other than carbon or hydrogen. A heteroatom can be a non-carbon atom 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" is a hydrocarbyl group substituted with one or more silicon atoms. The silicon atom may or may not be in the carbon chain.

[0051] The procatalyst precursor may include (i) magnesium, (ii) a transition metal compound of an element from Groups IV-VIII of the Periodic Table, (iii) a halide, oxyhalide, and / or alkoxide of (i) and / or (ii), and (iv) a combination 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.

[0052] In one embodiment, the procatalyst precursor is a magnesium moiety compound (MagMo), a mixed magnesium titanium compound (MagTi), or a benzoate-containing magnesium chloride compound (BenMag). In one embodiment, the procatalyst precursor is a magnesium moiety ("MagMo") precursor. A "MagMo precursor" contains magnesium as the only metal component. A MagMo precursor comprises a magnesium moiety. Non-limiting examples of suitable magnesium moieties include anhydrous magnesium chloride and / or its alcohol adducts, magnesium alkoxides or aryloxides, mixed magnesium alkoxyhalides, and / or carboxylated magnesium dialkoxides or aryloxides. In one embodiment, the MagMo precursor is a magnesium di(C 1~4 ) alkoxide. In a further embodiment, the MagMo precursor is diethoxymagnesium.

[0053] In one embodiment, the procatalyst precursor is a mixed magnesium / titanium compound (“MagTi”). A “MagTi precursor” is defined as a compound of the formula Mg d Ti(OR e ) f X g wherein R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, or COR', where R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and each OR eThe groups may be 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 alcohol from the reaction mixture used in its preparation. In one embodiment, the reaction medium comprises a mixture of an aromatic liquid, particularly a chlorinated aromatic compound, most particularly chlorobenzene, and an alkanol, particularly ethanol. Suitable halogenating agents include titanium tetrabromide, titanium tetrachloride, or titanium trichloride, particularly titanium tetrachloride. Removal of the alkanol from the solution used in the halogenation precipitates a solid precursor, which has a particularly desirable shape and surface area. Furthermore, the resulting precursor has a particularly uniform particle size.

[0054] In one embodiment, the procatalyst precursor contains magnesium as the only metal component. Non-limiting examples include anhydrous magnesium chloride and / or its alcohol adducts, magnesium alkoxides and / or aryloxides, mixed magnesium alkoxyhalides, and / or carboxylated magnesium dialkoxides or aryloxides.

[0055] In one embodiment, the procatalyst precursor is an alcohol adduct of anhydrous magnesium chloride. The anhydrous magnesium chloride adduct is generally defined as MgCl-nROH, where n ranges from 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 straight-chain or branched-chain C1-C4 alcohol or a mixture of alcohols. Preferably, ROH is ethanol or a mixture of ethanol and a higher alcohol. When ROH is a mixture, the molar ratio of ethanol to higher alcohol is at least 80:20, preferably 90:10, and most preferably at least 95:5.

[0056] In one embodiment, the substantially spherical MgCl-nEtOH adduct can be formed by a spray crystallization process. In one embodiment, the spherical MgCl precursor has an average particle size (Malvern diameter) of about 15-150 micrometers, preferably 20-100 micrometers, and most preferably 35-85 micrometers. 50 )

[0057] In one embodiment, the procatalyst precursor comprises a transition metal compound and a magnesium metal compound. The transition metal compound has the general formula TrX x wherein Tr is a transition metal and X is a halogen or C 1~10 is a hydrocarboxyl or hydrocarbyl group, and x is the number of such X groups in the compound in combination with the magnesium metal compound. Tr can be a Group IV, V, or VI metal. In one embodiment, Tr is a Group IV metal such as titanium. X can be chloride, bromide, C 1~4 It may be an alkoxide or a phenoxide, or a mixture thereof. In one embodiment, X is chloride.

[0058] The precursor catalyst composition of the present invention can also include an internal electron donor. As used herein, an "internal electron donor" is a compound added during the formation of the precursor catalyst composition that donates a pair of electrons to one or more metals present in the resulting precursor catalyst composition. Without being bound by any particular theory, it is believed that the internal electron donor helps regulate the formation of active sites, thus enhancing the stereoselectivity of the catalyst. In one embodiment, the internal electron donor comprises a substituted phenylene aromatic diester of structure (I) identified above.

[0059] In one embodiment, a procatalyst composition is provided that includes a combination of a magnesium moiety, a titanium moiety, and an internal electron donor. The internal electron donor includes a substituted phenylene aromatic diester. The procatalyst composition is prepared by a halogenation procedure detailed in U.S. Pat. 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 can be a magnesium moiety precursor, a mixed magnesium / titanium precursor, or a benzoic acid-containing magnesium chloride precursor.

[0060] In one embodiment, the magnesium moiety is a magnesium halide. In another embodiment, the magnesium halide is magnesium chloride or a magnesium chloride alcohol adduct. In one embodiment, the titanium moiety is a titanium halide, such as titanium chloride. In another embodiment, the titanium moiety is titanium tetrachloride. In another embodiment, the precatalyst composition comprises a magnesium chloride support on which titanium chloride is deposited and on which an internal electron donor is incorporated.

[0061] In one embodiment, the internal electron donor of the procatalyst composition comprises a substituted phenylene aromatic diester of structure (I) above, where R-R 14 are the same or different. R1~R 14 each of R to R is selected from hydrogen, 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; 14 At least one of these is not hydrogen.

[0062] In one embodiment, at least one (or two, or three, or four) R groups of R1-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.

[0063] In one embodiment, R to R 14 In another embodiment, at least one (or some, or all) of the R groups is 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. 10 ~R 14 At least one of is 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.

[0064] In one embodiment, at least one of R1 to R4 and R5 to R 14 At least one of R1-R4, at least one of R5-R9, and R6 is 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. In another embodiment, at least one of R1-R4, at least one of R5-R9, and R6 is 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. 10 ~R 14 At least one of is 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.

[0065] In one embodiment, any consecutive R groups from R1 to R4, and / or any consecutive R groups from R5 to R9, and / or R 10 ~R 14 Any consecutive R groups may be linked to form an intercyclic or endocyclic structure. The intercyclic / endocyclic structure may or may not be aromatic. In one embodiment, the intercyclic / endocyclic structure is a C5 or C6 membered ring.

[0066] In one embodiment, at least one of R1 through 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. 14 At least one of R1 to R4, and / or R5 to R9, and / or R 10 ~R 14 may be linked to form an intercyclic or endocyclic structure. The intercyclic and / or endocyclic structures may or may not be aromatic.

[0067] In one embodiment, R1 to R4, and / or R5 to R9, and / or R 10 ~R 14 Any successive R groups may be members of a C5 or C6 membered ring.

[0068] In one embodiment, structure (I) includes R1, R3, and R4 as hydrogen. R2 is selected from substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, and combinations thereof. R5 to R 14 are the same or different, and R5 to R 14 are each selected from hydrogen, 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, halogens, and combinations thereof.

[0069] In one embodiment, R2 is selected from a C1-C8 alkyl group, a C3-C6 cycloalkyl group, or a substituted C3-C6 cycloalkyl group. R2 can 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, and a cyclohexyl group.

[0070] In one embodiment, structure (I) includes R2 that is methyl, and R5-R 14is hydrogen. In one embodiment, structure (I) includes R2 which is ethyl, and R5 through R 14 is hydrogen. In one embodiment, structure (I) includes R2 that is t-butyl, and R5 through R 14 is hydrogen. In one embodiment, structure (I) includes R2 that is ethoxycarbonyl, and R5 through R 14 Each of is hydrogen.

[0071] In one embodiment, structure (I) includes R2, R3, and R4, each as hydrogen, and R1 is selected from substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, and combinations thereof. 14 are the same or different and each is selected from hydrogen, 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, halogens, and combinations thereof.

[0072] In one embodiment, structure (I) includes R1 which is methyl, and R5-R 14 Each of is hydrogen.

[0073] In one embodiment, structure (I) includes R2 and R4 that are hydrogen, and R1 and R3 are the same or different. Each of R1 and R3 is selected from substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, and combinations thereof. R5 to R 14 are the same or different, and R5 to R 14 are each 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, halogens, and combinations thereof.

[0074] In one embodiment, structure (I) comprises R1 and R3, which may be the same or different. Each of R1 and R3 is selected from a C1-C8 alkyl group, a C3-C6 cycloalkyl group, or a substituted C3-C6 cycloalkyl group. R5-R 14 are the same or different, and R5 to R 14 are each selected from hydrogen, a C1-C8 alkyl group, and halogen. Non-limiting examples of suitable 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 suitable C3-C6 cycloalkyl groups include cyclopentyl and cyclohexyl groups. In a further embodiment, R5-R 14 At least one of them is a C1 to C8 alkyl group or halogen.

[0075] In one embodiment, structure (I) comprises R1 being a methyl group and R3 being a t-butyl group. R2, R4, and R5 through R 14 Each of is hydrogen.

[0076] 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.

[0077] In one embodiment, structure (I) includes R1 and R3 that are isopropyl groups. R2, R4, and R5 through R 14 Each of is hydrogen.

[0078] In one embodiment, structure (I) comprises R, R, and R 10 R2, R4, R6 to R9, and R 11 ~R 14 Each of is hydrogen.

[0079] In one embodiment, structure (I) comprises R, R, and R 12R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of is hydrogen.

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

[0081] In one embodiment, structure (I) is R, R, R, R, R 10 , R 12 , and R 14 R2, R4, R6, R8, R 11 , and R 13 Each of is hydrogen.

[0082] In one embodiment, structure (I) includes R1 as a methyl group and R3 is a t-butyl group. 10 , R 12 , and R 14 Each of R2, R4, R6, R8, R 11 , and R 13 Each of is hydrogen.

[0083] In one embodiment, the substituted phenylene aromatic diester is 14 and having a structure selected from the group consisting of Structures (II) through (V), including alternatives of each of the following, which are detailed in U.S. Pat. No. 8,536,372, which is incorporated herein by reference.

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

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

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

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

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

[0089] In one embodiment, structure (I) comprises R1 being a methyl group and R3 being a t-butyl group. 11 , and R12 Each of R2, R4, R5, R8, R9, R 10 , R 13 , and R 14 Each of is hydrogen.

[0090] In one embodiment, structure (I) comprises R1 being a methyl group and R3 being a t-butyl group. 11 , and R 13 Each of R2, R4, R5, R7, R9, R 10 , R 12 , and R 14 Each of is hydrogen.

[0091] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. 14 Each of is a fluorine atom.

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

[0093] In one embodiment, structure (I) includes R1 being a methyl group and R3 being a t-butyl group. 12 Each of R2, R4, R5, R6, R8, R9, and R 10 , R 11 , R 13 , and R 14 Each of is hydrogen.

[0094] In one embodiment, R1 is a methyl group and R3 is a t-butyl group. 12 Each of R2, R4, R5, R6, R8, R9, and R 10 , R 11 , R 13 , and R 14Each of is hydrogen.

[0095] In one embodiment, structure (I) includes R1 being a methyl group and R3 being a t-butyl group. 12 Each of R2, R4, R5, R6, R8, R9, and R 10 , R 11 , R 13 , and R 14 Each of is hydrogen.

[0096] In one embodiment, structure (I) includes R1 being a methyl group, and R3 being a 2,4,4-trimethylpentan-2-yl group. 14 Each of is hydrogen.

[0097] 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 is hydrogen.

[0098] In one embodiment, structure (I) includes R1 and R4, each of which is a methyl group. R2, R3, R5-R9, and R 10 ~R 14 Each of is hydrogen.

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

[0100] 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 is hydrogen.

[0101] In one embodiment, another precursor catalyst composition is provided. The precursor catalyst composition includes a combination of a magnesium portion, a titanium portion, and a mixed internal electron donor. As used herein, a "mixed internal electron donor" is (i) a substituted phenylene aromatic diester, (ii) an electron donor component that donates a pair of electrons to one or more metals present in the resulting precursor catalyst composition, and (iii) optionally other components. In one embodiment, the electron donor component is a diether, a benzoate, and combinations thereof. The precursor catalyst composition having a mixed internal electron donor can be produced by the precursor catalyst production procedures disclosed in the previously issued patents and publications identified herein.

[0102] For example, a suitable catalyst composition includes a precatalyst composition, a cocatalyst, and two or more different external electron donors or mixed external electron donors (M-EEDs). 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, an "external electron donor" is a component or composition comprising a mixture of components added independently of the precatalyst formation to modify catalyst performance. As used herein, an "activity limiting agent" is a composition that reduces catalyst activity as the polymerization temperature in the presence of the catalyst increases above a threshold temperature (e.g., above about 85°C). A "selectivity control agent" is a composition that improves the stereoregularity of the polymer, where improved stereoregularity is generally understood to mean an increase in stereoregularity or a decrease in xylene solubles, or both. It is understood that the above definitions are not mutually exclusive, and that a single compound may be classified, for example, as both an activity limiting agent and a selectivity controlling agent.

[0103] In one embodiment, the external electron donor is an alkoxysilane. Alkoxysilanes have the general formula: SiR m (OR') 4-m (I) wherein R is independently at each occurrence hydrogen or a hydrocarbyl or amino group optionally substituted with one or more substituents containing one or more Group 14, 15, 16, or 17 heteroatoms, and R' contains up to 20 atoms excluding hydrogen and halogens, and R' is C 1~4 In one embodiment, R is an alkyl group, and m is 0, 1, 2, or 3. In one embodiment, R is 6~12 Arylalkyl or aralkyl, C 3~12 Cycloalkyl, C 3~12 Branched alkyl, or C 3~12 A cyclic or acyclic amino group, R' is C 1~4 alkyl, and m is 1 or 2.

[0104] 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); and any combination thereof.

[0105] In one embodiment, the selectivity control agent component can be a mixture of two or more alkoxysilanes. In further embodiments, the mixture can be dicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane and tetraethoxysilane, or dicyclopentyldimethoxysilane and n-propyltriethoxysilane. In one embodiment, the mixed external electron donor can include a benzoate, a succinate, and / or a diol ester. In one embodiment, the mixed external electron donor includes 2,2,6,6-tetramethylpiperidine as the SCA. In another embodiment, the mixed external electron donor includes a diether as both the SCA and the ALA.

[0106] The mixed external electron donor system can also include an activity limiting agent (ALA). ALA inhibits or otherwise prevents reactor failures, ensuring the continuation of the polymerization process. Typically, the activity of Ziegler-Natta catalysts increases as the reactor temperature increases. Ziegler-Natta catalysts also typically maintain high activity near the melting point temperature of the produced polymer. Heat generated by exothermic polymerization reactions can cause polymer particles to form agglomerates, ultimately disrupting the continuation of the polymer production process. ALA reduces catalyst activity at elevated temperatures, thereby preventing reactor failures and reducing (or preventing) particle agglomeration, ensuring the continuation of the polymerization process.

[0107] The activity limiting agent can be a carboxylic acid ester, a diether, a poly(alkene glycol), a diol ester, and combinations thereof. The carboxylic acid ester can be an aliphatic or aromatic, mono- or polycarboxylic acid ester. Non-limiting examples of suitable monocarboxylic acid esters include ethyl 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, amyl n-toluate, ethyl cyclohexanoate, and propyl pivalate.

[0108] The aliphatic carboxylic acid ester may be a C6 aliphatic acid ester, may be a mono- or poly(two or more) ester, may be linear or branched, may be saturated or unsaturated, and may be any combination thereof. 30 The aliphatic acid esters may also be substituted with substituents containing one or more Group 14, 15, or 16 heteroatoms. 30 Non-limiting examples of aliphatic acid esters include aliphatic C 6~30 Ci of monocarboxylic acids ~2 0 alkyl ester, aliphatic C 8~20 Monocarboxylic acid C 1~20 Alkyl ester, aliphatic C 4~20 C of monocarboxylic and dicarboxylic acids 1~4 Allyl mono- and diesters, aliphatic C 8~20 C of monocarboxylic and dicarboxylic acids 1~4 Alkyl esters, and C 2~100 (Poly)glycol or C 2~100 (Poly)glycol ether C 6~20 In a further embodiment, C6-C 30The fatty 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 In a further embodiment, the glyceryl tri-esters of fatty carboxylic acids may be C6-C8 glyceryl tri-esters of fatty carboxylic acids, and mixtures thereof. 20 The aliphatic ester is isopropyl myristate or di-n-butyl sebacate.

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

[0110] [ka] wherein R1-R4 are independently alkyl, aryl, or aralkyl groups having up to 20 carbon atoms, optionally containing heteroatoms of Group 14, 15, 16, or 17; and R i and R2 may be a hydrogen atom. The dialkyl ether may be linear or branched and may contain one or more of the following groups: an 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] wherein R and R' can be the same or different, and R and / or R' comprises one or more of the following groups: hydrogen, linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups, optionally containing heteroatoms. One or more ring structures can be formed through one or both of the 2- and 3-carbon atoms.

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

[0114] [ka] wherein 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, and substituted or unsubstituted hydrocarbyl having 1 to 20 carbon atoms. The R1-R6 groups may optionally contain one or more heteroatoms replacing carbon, hydrogen, or both, where the heteroatoms are selected from nitrogen, oxygen, sulfur, silicon, phosphorus, and halogen. R7 and R8 may be the same or different and may be attached to any of the 2-, 3-, 4-, 5-, and 6-position carbon atoms of either phenyl ring.

[0115] The individual external electron donor components can be added separately to the reactor, or two or more can be premixed together and then added as a mixture to the reactor. More than one selectivity control agent or activity limiting agent can be used in the mixture. In one embodiment, the mixture comprises: dicyclopentyldimethoxysilane and isopropyl myristate; diisopropyldimethoxysilane and isopropyl myristate; dicyclopentyldimethoxysilane and poly(ethylene glycol) laurate; dicyclopentyldimethoxysilane and isopropyl myristate and poly(ethylene glycol) dioleate; methylcyclohexyldimethoxysilane and isopropyl myristate; n-propyltrimethoxysilane and isopropyl myristate; dimethyldimethoxysilane and methylcyclohexyldimethoxysilane and isopropyl myristate; dicyclopentyldimethoxysilane and n-propyltriethoxysilane and isopropyl myristate; Diisopropyldimethoxysilane, n-propyltriethoxysilane, and isopropyl myristate; and dicyclopentyldimethoxysilane, tetraethoxysilane, and isopropyl myristate; dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, n-propyltriethoxysilane, and isopropyl myristate; and combinations thereof.

[0116] The catalyst composition includes a cocatalyst. The cocatalyst for use with the Ziegler-Natta precatalyst composition can be an aluminum-containing composition. Non-limiting examples of suitable aluminum-containing compositions include organoaluminum compounds, such as trialkylaluminum; dialkylaluminum hydrides; alkylaluminum dihydrides; dialkylaluminum halides; alkylaluminum dihalides; dialkylaluminum alkoxides; and alkylaluminum dialkoxide compounds containing 1 to 10 or 1 to 6 carbon atoms in each alkyl or alkoxide group. In one embodiment, the cocatalyst is a C alkylaluminum dialkoxide, such as triethylaluminum (TEA). 1~4A trialkylaluminum compound. The catalyst composition comprises a molar ratio of aluminum (Al) to (SCA(s) + ALA(s)) 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 one embodiment, the molar ratio of Al to (SCA(s) + ALA(s)) is 0.5 to 4.0:1. The molar ratio of total SCA to ALA 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 the present disclosure can be used in many different applications. As noted above, the nucleated / clarified propylene-butene copolymers have excellent stiffness properties and excellent transparency.

[0118] In one embodiment, the propylene-butene copolymer of the present disclosure can be incorporated into a composition for forming an injection-molded article, such as a container. When used in injection molding, the polymer can have a melt flow rate of greater than about 4 g / 10 min, such as greater than about 10 g / 10 min, such as greater than about 20 g / 10 min, such as greater than about 30 g / 10 min, or greater than about 35 g / 10 min. The container can have a bottom defining a hollow interior and an upper portion including a flange sealing the bottom. In addition to containers, generally, any injection-moldable article can be manufactured according to the present disclosure, which requires a degree of rigidity combined with good optics. For example, the propylene-butene copolymer of the present disclosure is particularly well suited for the manufacture of packaging, including all different types of food packaging.

[0119] In addition to injection-molded articles, the propylene-butene copolymers of the present disclosure can also be used in extrusion blow molding and thermoforming applications. When used in blow molding or thermoforming, the polymers can have a melt flow rate of less than about 5 g / 10 min, such as less than about 4.5 g / 10 min, such as less than about 4 g / 10 min, such as less than about 3.5 g / 10 min. The polymers can have a melt flow rate of greater than about 0.2 g / 10 min, such as greater than about 1 g / 10 min. When formulated at relatively low melt flow rates, the copolymers exhibit excellent melt strength, allowing for the formation of a variety of different blow-molded articles with relatively uniform wall thicknesses. For example, propylene-butene copolymers can be used to manufacture all kinds of plastic bottles, such as for containing beverages. As noted above, the polymers can be formed using non-phthalate catalysts, making them well-suited for food contact applications.

[0120] In yet another embodiment, the propylene-butene copolymers of the present disclosure can be used in thermoforming applications. For example, the polymers can be used to manufacture thermoformed containers, including beverage cups. For example, beverage cups manufactured according to the present disclosure can exhibit lower haze and higher stiffness compared to cups made using ethylene random copolymers.

[0121] The propylene-butene copolymer of the present disclosure can be combined with various other ingredients and raw materials when formulating a polymer composition for making the molded articles described above. For example, in one embodiment, the polymer composition can contain an antioxidant and an acid scavenger, and in some applications, it may also preferably contain other additives such as nucleating agents, mold release agents, antistatic agents, slip agents, antiblocking agents, processing aids, UV stabilizers, and colorants (pigments). The antioxidant may be a hindered phenol, which may be used in conjunction with a phosphite stabilizer. Acid scavengers that can be used include metal stearates such as calcium stearate, hydrotalcite, or mixtures thereof. Each additive can be present in the composition in an amount of about 0.01% by weight to about 2% by weight, such as about 0.1% by weight to about 1% by weight.

[0122] In one embodiment, the copolymer composition can further contain a nucleating agent. The nucleating agent can be added to further improve the clarity of the composition. In one aspect, the nucleating agent can be a clarifying agent, which can include compounds capable of generating a gelling network within the composition.

[0123] In one embodiment, the nucleating agent may include a sorbitol compound, such as a sorbitol acetal derivative. In one embodiment, by way of example, the nucleating agent may include dibenzyl sorbitol.

[0124] With respect to sorbitol acetal derivatives that can be used as additives in some embodiments, the sorbitol acetal derivatives are shown in formula (I):

[0125] [ka] wherein R1 to R5 comprise the same or different moieties selected from hydrogen and C1 to C3 alkyl.

[0126] In some embodiments, R1 through R5 are hydrogen, such that the sorbitol acetal derivative is 2,4-dibenzylidene sorbitol ("DBS"). In some embodiments, R1, R4, and R5 are hydrogen, and R2 and R3 are methyl groups, such that the sorbitol acetal derivative is 1,3:2,4-di-p-methyldibenzylidene-D-sorbitol ("MDBS"). In some embodiments, R1 through R4 are methyl groups, and R5 is hydrogen, such that 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, such that the sorbitol acetal derivative is 1,2,3-trideoxy-4,6:5,7-bis-O-(4-propylphenylmethylene)nonitol ("TBPMN").

[0127] Other embodiments of nucleating agents that may be used include the following: 1,3:2,4-dibenzylidene sorbitol; 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 an example.

[0128] In one embodiment, the nucleating agent may also include a bisamide, such as benzenetrisamide.The above nucleating agents may be used alone or in combination.

[0129] The one or more nucleating agents may be present in the polymer composition in an amount greater than about 100 ppm, such as greater than about 300 ppm, such as greater than about 1000 ppm, such as greater than about 2000 ppm, and generally less than about 20,000 ppm, such as less than about 10,000 ppm, such as less than about 4000 ppm.

[0130] When the one or more nucleating agents are fining agents, the fining agents may be added in an amount greater than about 1,500 ppm, such as greater than about 1,800 ppm, such as greater than about 2,000 ppm, such as greater than about 2,200 ppm. The one or more fining agents are generally present in an amount less than about 20,000 ppm, such as less than about 15,000 ppm, such as less than about 10,000 ppm, such as less than about 8,000 ppm, for example less than about 5,000 ppm.

[0131] As described above, the polymer composition containing the propylene-butene copolymer of the present disclosure has excellent low haze properties, which can be improved when one or more nucleating agents are added to the polymer. For example, when measured at a thickness of 0.7 mm, the propylene-butene copolymer or the polymer composition containing the propylene-butene copolymer can have a haze of less than about 12%, such as less than about 10%, for example, less than about 8%. Molded articles such as bottles, containers, films, and cups made from the polymer can have a haze of less than about 10%, for example, less than about 7.5%, for example, less than about 7%, for example, less than about 6.5%, for example, less than about 6%, for example, less than about 5.5%. The haze is generally greater than about 1%.

[0132] V. Working Examples Example Setting No. 1 Following the procedures outlined above, propylene-butene random copolymer samples were produced and their properties were tested. The properties and experimental results are summarized in the table below.

[0133] Propylene-butene random copolymers were produced using a stereospecific, sixth-generation Ziegler-Natta magnesium-supported / titanium-based catalyst. The catalyst contained a non-phthalate internal donor, producing polymers with broader molecular weight distributions than polymers made 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 available from W.R. Grace and Company under the trade name CONSISTA. All copolymers were produced using triethylaluminum as the external electron donor and cocatalyst.

[0134] Various different random copolymers were produced and combined with nucleating agents, except for Samples 1, 6, 10, and 14, which did not contain any nucleating agent. Two different nucleating agents were used: (1) TPBMN (clarifier) ​​and (2) HYPERFORM HPN-600ei (nucleating agent), available from Milliken Chemical. Samples 2, 7, 11, and 15 contained HYPERFORM HPN-600ei at a concentration of 400 ppm. Samples 3, 8, 12, and 16 contained 2000 ppm TPBMN, and Samples 4, 5, 9, 13, and 17 contained 4000 ppm TPBMN. Each sample also contained a hindered phenol antioxidant, a phosphite antioxidant, and an acid scavenger (hydrotalcite).

[0135] The following results were obtained:

[0136] [Table 2]

[0137] [Table 3]

[0138] Example setting number 2 Following the procedures outlined above, propylene-butene random copolymer samples were produced and their properties were tested. The properties and experimental results are summarized in the table below.

[0139] Propylene-butene random copolymers were produced using a stereospecific, sixth-generation Ziegler-Natta magnesium-supported / titanium-based catalyst. The catalyst contained a non-phthalate internal donor, producing polymers with broader molecular weight distributions than polymers made 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 available from W.R. Grace and Company under the trade name CONSISTA. All copolymers were produced using triethylaluminum as the external electron donor and cocatalyst.

[0140] Propylene-ethylene random copolymers were also produced. In the table below, for example, Samples 20 to 28 and Samples 32 to 36 are directed to propylene-butene random copolymers, while Samples 18, 19, 29 to 31, and 37 to 40 are directed 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 to 31, 39, and 40 were produced using a phthalate-based catalyst. Some of the produced polymers 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 composition is then injection molded into containers or blow molded into bottles. The following results were obtained:

[0141] [Table 4-1]

[0142] [Table 4-2]

[0143] Samples 19 and 22 above were also tested for haze on injection molded articles one year after manufacture and compared to a commercially available grade of propylene-ethylene random copolymer having the following properties:

[0144] [Table 5]

[0145] The following results were obtained:

[0146] [Table 6]

[0147] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art without departing from the spirit and scope of the present invention, which is particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged in whole or in part. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention as further set forth in such appended claims. The present invention includes the following aspects. [1] A propylene-butene copolymer, propylene as the primary monomer; a butene content of about 1% to about 12% by weight; about 1.0 wt. % to about 8.0 wt. % of a xylene soluble fraction; a molecular weight distribution (Mw / Mn) greater than about 3.5; a substituted phenylene aromatic diester; propylene-butene copolymers, including [2] 2. The propylene-butene copolymer according to claim 1, wherein the butene content is from about 2% to about 8% by weight, such as from about 2% to about 6% by weight. [3] 3. The propylene-butene copolymer of claim 2, wherein the copolymer has a heat deflection temperature greater than about 75°C. [4] 4. The propylene-butene copolymer according to any one of claims 1 to 3, wherein the copolymer has a melting temperature of about 147°C to about 155°C. [5] 5. The propylene-butene copolymer according to any one of 1 to 4, wherein the xylene soluble content is from about 2% to about 7% by weight. [6] 6. The propylene-butene copolymer according to any one of 1 to 5, wherein the copolymer has a melt flow rate of about 0.2 g / 10 min to about 8 g / 10 min. [7] 4. The propylene-butene copolymer according to any one of 1 to 3, wherein the copolymer has a melt flow rate of about 8 g / 10 min to about 220 g / 10 min. [8] 8. The propylene-butene copolymer of any one of claims 1 to 7, wherein the copolymer has a flexural modulus of greater than about 1200 MPa, such as greater than about 1300 MPa, for example greater than about 1400 MPa, typically less than about 2000 MPa. [9] 9. The propylene-butene copolymer of any one of 1 to 8, wherein the polymer is Ziegler-Natta catalyzed using a non-phthalate catalyst.

[10] 10. The propylene-butene copolymer of any one of claims 1 to 9, wherein the polymer has a xylene soluble fraction / butene content ratio of from about 0.3 to about 3.0, such as from about 0.3 to about 2.0, or such as from 0.5 to about 1.0.

[11] 11. A polymer composition containing a propylene-butene copolymer according to any one of claims 1 to 10, wherein the propylene-butene copolymer is present in the polymer composition in an amount greater than about 70 wt%, such as greater than about 80 wt%, such as greater than about 90 wt%, such as greater than about 95 wt%.

[12] 12. The polymer composition of claim 11, wherein the composition further comprises a nucleating agent.

[13] 13. The polymer composition of claim 12, wherein the nucleating agent comprises nonitol.

[14] 14. The polymer composition of any one of claims 11 to 13, wherein the polymer composition exhibits a haze at 0.7 mm of about 8% or less, such as about 6% or less.

[15] 15. An article made from the polymer composition of any one of claims 1 to 14, wherein the article is an injection molded article, a blow molded article, a thermoformed article, a film, or a fiber.

[16] 1. An article, including a blow molded article, a thermoformed article, a film, or a fiber, made from a polymer composition comprising a propylene-butene copolymer, wherein the propylene-butene copolymer is propylene as the primary monomer; a butene content of about 1% to about 12% by weight; about 1.0 wt. % to about 8.0 wt. % of a xylene soluble fraction; a molecular weight distribution (Mw / Mn) greater than about 3.5; antioxidants and antacids; Including, goods.

[17] 17. The article according to 16, comprising a cup, bottle, or container.

[18] 17. The article according to 16, including packaging.

[19] 17. The article of claim 16, wherein the butene content of the copolymer is from about 2% to about 8% by weight, such as from about 2% to about 6% by weight.

[20] 20. The article of claim 19, wherein the copolymer has a deflection temperature under load greater than about 75°C.

[21] 21. The article of any one of paragraphs 19 or 20, wherein the copolymer has a melting temperature of from about 145°C to about 155°C, such as from 147°C to about 155°C.

[22] 22. The article of any one of claims 16 to 21, wherein the xylene soluble content is from about 2% to about 7% by weight.

[23] 23. The article of any one of claims 16 to 22, wherein the copolymer has a melt flow rate of from about 0.2 g / 10 min to about 4 g / 10 min.

[24] 24. The article of any one of claims 16 to 23, wherein the polymer has a xylene soluble fraction / butene content ratio of about 0.3 to about 3.0, such as about 0.3 to about 2.0.

[25] 25. The article of any one of claims 16 to 24, wherein the propylene-butene copolymer is present in the polymer composition in an amount greater than about 70 wt%, such as greater than about 80 wt%, such as greater than about 90 wt%, such as greater than about 95 wt%.

[26] 26. The article of any one of claims 16 to 25, wherein the composition further comprises a nucleating agent.

[27] 27. The article of claim 26, wherein the nucleating agent comprises nonitol.

[28] 28. The article of any one of claims 16 to 27, wherein the polymer composition exhibits a haze at 0.7 mm of about 8% or less, such as about 6% or less.

Claims

1. 1. A propylene-butene copolymer composition comprising: propylene as the primary monomer; 1% to 12% by weight of butene monomer; 1.0 wt. % to 8.0 wt. % of a xylene soluble fraction; a molecular weight distribution (Mw / Mn) greater than 3.5; and the propylene-butene copolymer comprises the following structure (I): 【Chemistry 1】 wherein R1-R14 are the same or different and each of R1-R14 is selected from hydrogen, 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, and at least one of R1-R14 is not hydrogen; A propylene-butene copolymer composition catalyzed in the presence of a non-phthalate Ziegler-Natta catalyst comprising a substituted phenylene aromatic diester having the formula:

2. 2. The propylene-butene copolymer composition of claim 1, wherein the butene monomer is from 2% to 8% by weight.

3. 3. The propylene-butene copolymer composition of claim 2, wherein the copolymer has a heat deflection temperature greater than 75°C.

4. The propylene-butene copolymer composition of any one of claims 1 to 3, wherein the copolymer has a melting temperature of from 147°C to 155°C.

5. The propylene-butene copolymer composition according to any one of claims 1 to 4, wherein the xylene soluble fraction is from 2% to 7% by weight.

6. The propylene-butene copolymer composition of any one of claims 1 to 5, wherein the copolymer has a melt flow rate of from 0.2 g / 10 min to 8 g / 10 min.

7. The propylene-butene copolymer composition of any one of claims 1 to 3, wherein the copolymer has a melt flow rate of from 8 g / 10 min to 220 g / 10 min.

8. The propylene-butene copolymer composition of any one of claims 1 to 7, wherein the copolymer has a flexural modulus greater than 1200 MPa.

9. The propylene-butene copolymer composition of any one of claims 1 to 8, wherein the copolymer is Ziegler-Natta catalyzed with a non-phthalate catalyst.

10. The propylene-butene copolymer composition of any one of claims 1 to 9, wherein the copolymer has a xylene soluble fraction / butene monomer ratio of 0.3 to 3.

0.

11. A polymer composition containing the propylene-butene copolymer composition of any one of claims 1 to 10, wherein the propylene-butene copolymer is present in the polymer composition in an amount greater than 70 wt%.

12. The polymer composition of claim 11 , wherein the polymer composition further comprises a nucleating agent.

13. The polymer composition of claim 12 , wherein the nucleating agent comprises nonitol.

14. The polymer composition of any one of claims 11 to 13, wherein the polymer composition exhibits a haze of 8% or less at 0.7 mm.

15. An article made from the polymer composition of any one of claims 1 to 14, wherein the article is an injection molded article, a blow molded article, a thermoformed article, a film, or a fiber.

16. 1. An article, including a blow molded article, a thermoformed article, a film, or a fiber, made from a polymer composition comprising a propylene-butene copolymer composition, wherein the propylene-butene copolymer composition is propylene as the primary monomer; 1% to 12% by weight of butene monomer; 1.0 wt. % to 8.0 wt. % of a xylene soluble fraction; a molecular weight distribution (Mw / Mn) greater than 3.5; antioxidants and antacids; and the propylene-butene copolymer comprises the following structure (I): 【Chemistry 2】 wherein R1-R14 are the same or different and each of R1-R14 is selected from hydrogen, 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, and at least one of R1-R14 is not hydrogen; wherein the catalyst is a non-phthalate Ziegler-Natta catalyst comprising a substituted phenylene aromatic diester having the formula:

17. 17. The article of claim 16, comprising a cup, bottle, or container.

18. 17. The article of claim 16, comprising packaging.

19. 17. The article of claim 16, wherein the butene monomer of the propylene-butene copolymer composition is from 2% to 8% by weight.

20. 20. The article of claim 19, wherein the copolymer has a deflection temperature under load greater than 75°C.

21. 21. The article of claim 19 or claim 20, wherein the copolymer has a melting temperature of 145°C to 155°C.

22. The article of any one of claims 16 to 21, wherein the xylene soluble fraction is from 2% to 7% by weight.

23. The article of any one of claims 16 to 22, wherein the copolymer has a melt flow rate of from 0.2 g / 10 min to 4 g / 10 min.

24. The article of any one of claims 16 to 23, wherein the copolymer has a xylene soluble fraction / butene monomer ratio of 0.3 to 3.

0.

25. The article of any one of claims 16 to 24, wherein the propylene-butene copolymer is present in the polymer composition in an amount greater than 70 wt%.

26. The article of any one of claims 16 to 25, wherein the propylene-butene copolymer composition further comprises a nucleating agent.

27. 27. The article of claim 26, wherein the nucleating agent comprises nonitol.

28. The article of any one of claims 16 to 27, wherein the polymer composition exhibits a haze of 8% or less at 0.7 mm.

29. The propylene-butene copolymer composition of any one of claims 1 to 10, wherein the copolymer has a xylene soluble fraction / butene monomer ratio of 0.5 to 3.

0.

30. The article of any one of claims 16 to 23, wherein the copolymer has a xylene soluble fraction / butene monomer ratio of 0.5 to 3.0.

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