Polypropylene copolymer composition having subzero impact resistance

Abstract

Disclosed is a polypropylene polymer composition that can be formulated to have excellent clarity properties combined with excellent impact resistance at sub-zero temperatures. The polypropylene polymer composition is a heterophasic composition containing a first-phase polymer combined with a second-phase polymer. The first-phase polymer is a polypropylene and alpha-olefin copolymer, while the second-phase polymer is also a polypropylene and alpha-olefin random copolymer. The second-phase polymer contains a relatively large amount of ethylene. It has been found that increasing the amount of ethylene in the second-phase polymer dramatically improves impact resistance at sub-zero temperatures.

Description

[Technical Field]

[0001] (Related Applications) This application is based on and claims priority to U.S. Provisional Patent Application No. 62 / 829,932, filed April 5, 2019, which is incorporated herein by reference. [Background technology]

[0002] Transparency and impact resistance are highly desirable properties 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 of great benefit to the user. In many situations, for example, it is highly advantageous to be able to see the contents of a package or container through the wall of the package or container. On the other hand, high impact resistance makes a container durable.

[0003] One type of polymer that can be made highly transparent is semicrystalline polypropylene homopolymer. Polypropylene homopolymers are generally very translucent due to their high crystallinity and large spherulites. The transparency of polypropylene polymers can be improved by incorporating ethylene or another alpha-olefin into the polymer chain to produce a polypropylene random copolymer. Nucleating and / or clarifying agents can also be incorporated into the polymer to further reduce the crystal size and increase clarity. Summary of the Invention [Problem to be solved by the invention]

[0004] Although polypropylene random copolymers have excellent transparency properties, the polymers tend to have relatively low impact resistance, especially in sub-zero environments. Therefore, for refrigerator or freezer storage containers and / or long-term storage containers, greater impact resistance is required. However, attempts to improve the impact resistance of polypropylene polymers may result in a decrease in other properties of the polymer.

[0005] In the past, polypropylene impact copolymers have been designed that include a homopolymer matrix blended with a rubber-like propylene-alpha-olefin copolymer phase. The copolymer phase is intended to enhance impact resistance, such as at low temperatures. The propylene-alpha-olefin copolymer may be primarily amorphous, thus possessing elastomeric properties that form a rubber phase within the polymer composition. The incorporation of the propylene-alpha-olefin copolymer improves impact resistance, but at the expense of clarity.

[0006] To improve the transparency of heterophasic polypropylene compositions containing a rubber phase, those skilled in the art have attempted to reduce the size of the rubber phase. For example, adding ethylene to the matrix polymer and minimizing the ethylene content in the rubber phase can be used to improve compatibility between the matrix phase and the rubber phase. However, past attempts have not adequately provided polymer compositions having the desired blend of transparency and impact strength. More specifically, past attempts have not produced polypropylene polymer compositions with sufficient impact resistance at sub-zero temperatures.

[0007] Generally, the present disclosure relates to polypropylene polymer compositions with an improved balance of properties. Polypropylene polymer compositions made according to the present disclosure can be formulated to have, for example, excellent clarity properties along with excellent sub-zero impact strength. In one embodiment, the polypropylene polymer composition comprises a polypropylene polymer in combination with a relatively high alpha-olefin-containing alpha-olefin copolymer. The alpha-olefin content (e.g., ethylene) of each polymer phase can be controlled within desired limits. Additionally, the relative amounts of each polymer phase can be selected to maximize specific properties. In one embodiment, all of the polymers blended together are made using a Ziegler-Natta catalyst system, which allows for close control of different parameters and variables during polymer processing.

[0008] In one embodiment, for example, the present disclosure relates to a polypropylene composition comprising a first polymer phase combined or blended with a second polymer phase. The first polymer phase comprises a polypropylene polymer, such as a polypropylene random copolymer. The polypropylene random copolymer may contain an alpha-olefin, such as ethylene or butylene, in an amount up to about 4% by weight, e.g., about 1% to about 4% by weight. The polypropylene random copolymer may have a xylene-soluble fraction of less than about 10%, e.g., less than about 8% by weight. The polypropylene random copolymer is generally present in the polymer composition in an amount greater than about 50% by weight, e.g., greater than about 60% by weight, e.g., greater than about 65% by weight. The first polymer phase generally has a melt flow rate of about 20 g / 10 min to about 50 g / 10 min.

[0009] The second polymer phase blended with the first polymer phase generally comprises propylene and an alpha-olefin copolymer, such as a propylene-ethylene copolymer, containing a relatively large amount of an alpha-olefin, such as ethylene. It has been discovered that increasing the amount of ethylene in an elastomeric or rubbery copolymer can dramatically and unexpectedly improve the impact resistance of the polymer composition at subzero temperatures, e.g., temperatures below 0°C, e.g., -20°C. The amount of ethylene contained in the copolymer can be characterized by the amount of ethylene in the xylene-soluble portion and the amount of ethylene in the xylene-insoluble portion of the polypropylene composition. For example, the polypropylene composition (both the first and second polymer phases) can have a total xylene-soluble content of about 12% to about 25% by weight. The xylene-soluble portion can contain ethylene in an amount of about 55% to about 70% by weight, e.g., about 60% to about 70% by weight. Ethylene may be present in the xylene-insoluble portion in an amount of about 15% to about 40% by weight, e.g., about 20% to about 38% by weight. In this regard, the propylene-ethylene copolymer in the second polymer phase generally contains ethylene in an amount greater than about 75% by weight, e.g., greater than about 80% by weight, and generally less than about 95% by weight, e.g., less than about 92% by weight. In one embodiment, ethylene is present in the second polymer phase in an amount of about 75% to about 85% by weight, e.g., about 77% to about 83% by weight.

[0010] The heterophasic polypropylene composition has an excellent balance of physical properties. For example, when tested at -20°C, the polypropylene composition may have a Gardner impact strength of greater than about 200 inch-pounds, e.g., greater than about 250 inch-pounds, e.g., greater than about 300 inch-pounds, e.g., greater than about 350 inch-pounds, and typically less than about 500 inch-pounds. In addition, the polypropylene composition may have a flexural modulus of less than about 1000 MPa, e.g., less than about 800 MPa, and typically greater than about 500 MPa, e.g., greater than about 650 MPa. In addition, the polypropylene composition may have a haze at 1 mm of less than about 45%. For example, the haze may be from about 5% to about 45%. In addition, the polypropylene composition may have a relatively high clarity. For example, the clarity of the composition may be greater than about 90%, e.g., greater than about 92%.

[0011] Generally, the polypropylene composition may have a melt flow rate of greater than about 3 g / 10 min, for example greater than about 5 g / 10 min, for example greater than about 10 g / 10 min, and generally less than about 50 g / 10 min. In one embodiment, the melt flow rate may be from about 15 g / 10 min to about 25 g / 10 min. The ratio of the melt flow rate of the first polymer phase to the melt flow rate of the polypropylene composition is generally 1 or greater. The second polymer phase is generally contained in the polypropylene composition in an amount of from about 15 wt% to about 50 wt%. In one embodiment, the composition may further include a clarifier to improve transparency.

[0012] The polymer compositions of the present disclosure can be used to make many different types of products. In one embodiment, the polymer compositions can be used to form a variety of different molded articles, such as injection molded articles. In one embodiment, the polymer compositions can be used to form containers, such as storage containers. The storage containers may be configured to hold, for example, food products or may be used to form long-term storage containers, such as warehouses, attics, garages, etc. The polymer compositions of the present disclosure are particularly suitable for storage containers and other packaging materials for freezer applications or applications where the containers are exposed to sub-zero temperatures.

[0013] Other features and aspects of the present disclosure are discussed in more detail below. [Brief explanation of the drawings]

[0014] A full and enabling disclosure of the present disclosure is more particularly set forth in the remainder of the specification, including reference to the accompanying drawings, in which: [Figure 1] FIG. 1 is a perspective view of one embodiment of a container made in accordance with the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0015] Repeat use of reference characters in the present specification and drawings is intended to represent same or analogous features or elements of the invention. Definitions and Test Procedures

[0016] As used herein, the term "propylene-ethylene copolymer" refers to a copolymer containing a majority weight percent of propylene monomer with ethylene monomer as a secondary constituent. A "propylene-ethylene copolymer" (also called polypropylene random copolymer, PPR, PP-R, RCP, or RACO) is a polymer with individual repeat units of ethylene monomer present in a random or statistical distribution within the polymer chain.

[0017] As used herein, melt flow rate (MFR) is measured according to ASTM D1238 test method using a propylene-based polymer weighing 2.16 kg at 230°C.

[0018] Xylene solubles (XS) are defined as the weight percent of resin remaining in solution after dissolving a sample of polypropylene random copolymer resin in hot xylene and allowing the solution to cool to 25°C. This is also referred to as the gravimetric XS method according to ASTM D5492-06, which uses a 90-minute precipitation time, and is also referred to herein as the "wet method." XS can also be measured according to the Viscotek method as follows: 0.4 g of polymer is dissolved in 20 mL of xylene with stirring 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 connected 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 by verifying method performance using 5D98 as a control. 5D98 values ​​are originally derived from testing using the ASTM method identified above.

[0019] The ASTM D5492-06 method, mentioned above, may 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 joint. 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 to 25°C in a temperature-controlled water bath for 90 minutes to crystallize the xylene-insoluble fraction. Once the solution has cooled and the insoluble fraction has precipitated 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, place the aluminum pan and contents in a vacuum oven at 100°C for 30 minutes or until dry. The aluminum pan is then allowed to cool to room temperature and weighed. The xylene soluble portion is calculated as XS (wt%) = [(m3 - m2) * 2 / m1] * 100, where m1 is the initial weight of the sample used, m2 is the weight of the empty aluminum pan, and m3 is the weight of the pan and residue (asterisk, * , here and elsewhere in this disclosure indicate that the identified term or value is multiplied).

[0020] The ethylene content of the xylene soluble (XS) and xylene insoluble (XI) fractions is 13C-NMR. Samples are prepared by adding approximately 2.7 g of a 50 / 50 mixture of tetrachloroethane-d2 / orthochlorobenzene 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 confirm homogeneity. Data are collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe. Data are acquired using 500 transients per data file, a 6-second pulse repetition delay, a 90-degree flip angle, and reverse-gated decoupling at a sample temperature of 120 °C. All measurements are performed in locked mode with the sample unspun. The sample is allowed to thermally equilibrate for 10 minutes before data collection. The ethylene content was calculated based on the triad distribution. The triad chemical shift assignments are shown in Table 1. PPP=(F+A-0.5D) / 2 PPE=D EPE=C EEE=(E-0.5G) / 2 PEE=G PEP=H The ethylene content is based on the following calculation: Mole number P = sum of triads with P at the center Mole number E = sum of triads with E at the center [Table 1]

[0021] The Koenig B value, a measure of randomness or blockiness in a copolymer, is calculated by the formula: Koenig B = [EP] / (2[P][E]), where [EP] is the total mole fraction of EP dimers (EP + PE) (Spectroscopy of Polymers, 2nd edition, Jack L. Koenig, 1999, Elsevier; pp. 17-18).

[0022] Flexural modulus is determined according to ASTM D790-10 Method A at 1.3 mm / min using Type 1 specimens according to ASTM 3641 molded according to ASTM D4101.

[0023] Mw / Mn (also referred to as "MWD") and Mz / Mw are measured by gel permeation chromatography (GPC) according to the GPC analytical method for polypropylene. Polymers are analyzed on a PL-220 series high-temperature gel permeation chromatography (GPC) unit equipped with a refractometer detector and four PLgel Mixed A (20 μm) columns (Polymer Laboratory Inc.). The oven temperature is set at 150 °C, and the autosampler hot and heated zone temperatures are 135 °C and 130 °C, respectively. 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 is 1.0 mL / min, and the injection volume is 200 μL. A 2 mg / mL sample concentration is prepared by dissolving the sample in N2-purged, preheated TCB (containing 200 ppm BHT) at 160°C with gentle stirring for 2.5 hours.

[0024] The GPC column set was calibrated by running 20 narrow molecular weight distribution polystyrene standards. The molecular weights (MW) of the standards ranged from 580 to 8,400,000 g / mol, and the standards were included in six "cocktail" mixtures. Each standard mixture had at least several tens of intervals between individual molecular weights. The polystyrene standards were prepared at 0.005 g in 20 mL of solvent for MWs of 1,000,000 g / mol or greater, and 0.001 g in 20 mL of solvent for MWs less than 1,000,000 g / mol. The polystyrene standards were dissolved at 150 °C for 30 min under stirring. The narrow standard mixture was run first and to reduce the highest molecular weight components to minimize degradation effects. A logarithmic molecular weight calibration was generated using a fourth-order polynomial fit as a function of elution volume. The equivalent polypropylene molecular weight can be calculated using the Mark-Houwink coefficients reported for polypropylene (Th. G. Scholte, N.L. J. Meijerink, H.M. Schoffeleers, and A.M. 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:

number

[0025] IZOD impact strength is measured according to ASTM D256.

[0026] The Gardner impact test is measured according to ASTM D5420.

[0027] Haze and clarity are measured according to ASTM Test D1003 Procedure A and D1746 using a BYK Gardner Haze-Gard Plus 4725 using injection molded plaques having a thickness of 1 mm.

[0028] Tan δ is measured by DMA testing using a TA instrument Q800 with a dual cantilever fixture. Test specimens are cut from flexural modulus specimens with dimensions of 12.7 mm x 3.2 mm x 60 mm. The samples are first equilibrated at -150°C, left isothermal for 5 minutes, and then heated to 100°C at a heating rate of 3°C / min.

[0029] The term β / α refers to the ratio of the molecular weight of the copolymer of the discontinuous phase to the molecular weight of the propylene-based polymer of the continuous phase, where β and α are the intrinsic viscosity values ​​of the copolymer-based and propylene-based polymer fractions, respectively, when measured in decalin at 135° C. (ASTM D1601). For purposes of this disclosure, the value of β / α is calculated from the MFR of the matrix polymer, and the MFR of the overall impact copolymer and Fc before visbreaking are as follows:

number

[0030] Rubber particle size was measured using a Hitachi Tabletop Microscope TM3030Plus, a scanning electron microscope (SEM) device. Samples were first cut along the flow direction from the center of an IZOD test bar (ASTM D4101), then cryomicrotomed at -20°C, stained with RuO4, and cryomicrotomed again at -20°C. SEM images were observed in backscattering (BSE) mode, with highly stained areas (EPR rubber) representing the lighter phase and weakly stained areas representing the darker phase. Particle size was captured and analyzed using Image-Pro® Premier software. D50 was calculated in terms of the particle size at 50% cumulative volume fraction.

[0031] Detailed Description Those skilled in the art will appreciate that this discussion is a description of exemplary embodiments only and is not intended to limit the broader aspects of the present disclosure.

[0032] Generally, the present disclosure relates to polyolefin polymer compositions having a unique blend of physical properties. For example, in one embodiment, the polymer compositions can be formulated to have excellent transparency characteristics as well as excellent impact resistance. In addition, the polymer compositions can be formulated to have good flow properties. As such, the polymer compositions are particularly suitable for forming injection-molded articles. In one embodiment, for example, the polymer compositions can be used to form containers, particularly storage containers that allow products or items placed within the container to be viewed through the walls of the container or packaging. The polypropylene compositions of the present disclosure are particularly suitable for producing freezer packaging materials and containers.

[0033] Generally, the polypropylene composition of the present disclosure comprises a heterophasic composition. Specifically, the polypropylene composition comprises a first polymer phase blended with a second polymer phase. Both polymer phases are formed from polypropylene copolymers containing controlled amounts of alpha-olefins, such as ethylene or butylene. For example, in one embodiment, the first polymer phase comprises a polypropylene random copolymer containing up to about 4% by weight of ethylene. The first polymer phase generally exists in the polymer composition in greater amounts than the second polymer phase, thereby forming the matrix polymer. Meanwhile, the second polymer phase comprises a polypropylene copolymer having elastomeric or rubber-like properties. According to the present disclosure, the second polymer phase contains more ethylene than propylene. It has been discovered that substantially increasing the amount of ethylene in the second polymer phase can dramatically improve the impact resistance of the polymer composition at sub-zero temperatures. The unexpectedly improved toughness properties at lower temperatures, combined with excellent clarity properties, make the polypropylene composition particularly suitable for producing containers used in low-temperature environments.

[0034] For example, when tested according to the Gardner Impact Resistance Test, the polymer composition may exhibit a Gardner Impact Resistance at -20°C of greater than about 200 inch-pounds, such as greater than about 225 inch-pounds, for example greater than about 250 inch-pounds, such as greater than about 275 inch-pounds, for example greater than about 300 inch-pounds, for example greater than about 325 inch-pounds, and generally less than about 500 inch-pounds.

[0035] As mentioned above, in addition to the excellent impact strength properties, the polymer composition of the present disclosure can also have very good transparency properties.For example, the polymer composition can have a haze of less than about 45% at 1 mm, for example, less than about 40%, for example, less than about 35%, or even less than about 30%.The haze at 1 mm is generally greater than about 10%.

[0036] In addition to relatively low haze, the polypropylene compositions of the present disclosure may exhibit excellent clarity characteristics. For example, the polymer compositions may exhibit clarity of greater than about 80%, such as greater than about 85%, such as greater than about 90%, for example greater than about 92%.

[0037] The flexibility of the polymer composition can vary depending on various factors, including the relative amounts of the first and second polymer phases and the amount of comonomer in the first and second phases. Generally, the polymer composition of the general disclosure can have a flexural modulus of less than about 1000 MPa, for example, less than about 850 MPa, for example, less than about 800 MPa, for example, less than about 750 MPa. Generally, the flexural modulus is greater than about 500 MPa, for example, greater than about 550 MPa, for example, greater than about 600 MPa.

[0038] The term β / α refers to the ratio of the molecular weight of the copolymer to the molecular weight of the matrix polymer or polymers of the first polymer phase. The molecular weight of each polymer is proportional to its intrinsic viscosity. Intrinsic viscosity indicates the viscosity of a solution of a polymer in a given solvent at a given temperature. The polymer composition of the present disclosure may have a β / α ratio greater than about 1, e.g., 1.1 or greater. For example, the β / α ratio may be greater than about 1.2, e.g., greater than about 1.3. Generally, the β / α ratio is less than about 2, e.g., less than about 1.8, e.g., less than about 1.6.

[0039] The polymer composition formulated according to the present disclosure can also have excellent flow properties while maintaining relatively high impact strength. For example, the polymer composition of the present disclosure can have a melt flow rate of greater than about 3 g / 10 min, for example, greater than about 15 g / 10 min, for example, greater than about 17 g / 10 min, for example, greater than about 18 g / 10 min. The melt flow rate is generally less than about 80 g / 10 min, for example, less than about 70 g / 10 min, for example, less than about 50 g / 10 min, less than about 35 g / 10 min, for example, less than about 30 g / 10 min. Due to the above flow properties, the polymer composition is particularly suitable for use in injection molding applications.

[0040] As described above, the polypropylene composition of the present disclosure generally comprises a first-phase polymer in combination with a second-phase polymer. The first-phase polymer comprises a polypropylene polymer, such as a random copolymer of polypropylene. The random copolymer can be, for example, a copolymer of propylene and an alpha-olefin, such as ethylene or butylene. The polypropylene random copolymer forms the matrix polymer in the polypropylene composition and can contain up to about 4 wt. % of the alpha-olefin, e.g., less than about 3.8 wt. %, e.g., less than about 3.5 wt. %, and generally greater than about 0.5 wt. %, e.g., greater than about 1 wt. %, e.g., greater than about 1.5 wt. %, e.g., greater than about 2 wt. The first-phase polymer generally has a xylene solubles content of less than about 12 wt. %, e.g., less than about 10 wt. %, e.g., less than about 8 wt. %, e.g., less than about 7 wt. The xylene solubles content is generally greater than about 0.5 wt. %, e.g., greater than about 3 wt. %.

[0041] As described in more detail below, the first phase polymer can comprise a Ziegler-Natta catalyzed polymer and can have a relatively broad molecular weight distribution (Mw / Mn) of 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 typically less than about 9, e.g., less than about 8.5, e.g., less than about 8. The weight average molecular weight (determined by GPC) of the first phase polymer is typically greater than about 100,000, e.g., greater than about 120,000.

[0042] In one embodiment, the polypropylene random copolymer constituting the first phase polymer has a relatively high melt flow rate. For example, the first phase polymer can have a melt flow rate of greater than about 15 g / 10 min, e.g., greater than about 18 g / 10 min, e.g., greater than about 20 g / 10 min, greater than about 22 g / 10 min, e.g., greater than about 25 g / 10 min. The melt flow rate of the first phase polymer is generally less than about 80 g / 10 min, e.g., less than about 50 g / 10 min.

[0043] The second-phase polymer is a copolymer of propylene and an alpha-olefin. In addition, the second-phase polymer has elastomeric or rubber-like properties. Therefore, the second-phase polymer can dramatically improve the impact resistance of the polymer composition.

[0044] According to the present disclosure, the second-phase polymer contains a relatively large amount of alpha-olefin relative to the amount of propylene contained in the second polymer phase. For example, in one embodiment, the second-phase polymer contains an amount of ethylene that is greater than the amount of propylene present. It has been discovered that increasing the ethylene content of the second polymer phase unexpectedly and dramatically improves the impact resistance of the polymer composition at sub-zero temperatures.

[0045] The amount of ethylene contained in the second polymer phase can be characterized or quantified by assaying the amount of ethylene in the xylene solubles and xylene insolubles. For example, the polypropylene composition of the present disclosure may generally have a total xylene solubles content of greater than about 12 wt%, for example, greater than about 15 wt%, for example, greater than about 18 wt%, for example, greater than about 20 wt%, and generally less than about 40 wt%, for example, less than about 30 wt%, for example, less than about 25 wt%, for example, less than about 21 wt%. Thus, the polypropylene composition comprises a xylene soluble portion and a xylene insoluble portion. According to the present disclosure, ethylene may be contained in the xylene soluble portion in an amount greater than about 55 wt%, for example, greater than about 58 wt%, for example, greater than about 60 wt%, and generally less than about 70 wt%, for example, less than about 68 wt%. On the other hand, the amount of ethylene contained in the xylene-insoluble portion may generally be greater than about 15% by weight, for example greater than about 18% by weight, for example greater than about 20% by weight, and generally less than about 50% by weight, for example less than about 40% by weight, for example less than about 38% by weight.

[0046] Based on the above ranges, ethylene is considered to be present in the second polymer phase in an amount greater than about 75 wt%, for example greater than about 80 wt%, for example greater than about 85 wt%, and generally less than about 95 wt%, for example less than about 90 wt%.

[0047] The second phase polymer can have a weight average molecular weight of at least about 130,000, such as at least about 140,000, such as at least about 150,000, and generally less than about 500,000.

[0048] The first-phase polymer generally forms a matrix, and the second-phase polymer forms particles within the matrix. In the past, various efforts have been made to reduce the size of second-phase polymer particles. However, in the polymer compositions of the present disclosure, the second-phase polymer particles have a relatively large size. It has been unexpectedly discovered that excellent physical properties, including clarity and haze, can be obtained while still having relatively large second-phase polymer particles. For example, the second-phase polymer particles can have an average particle size (D50) greater than about 1 micrometer, e.g., greater than about 1.1 micrometers, and generally less than about 8 micrometers, e.g., less than about 6 micrometers, e.g., less than about 4 micrometers. For example, the average particle size can be greater than about 1.5 micrometers, e.g., greater than about 2 micrometers, e.g., greater than about 2.5 micrometers, e.g., greater than 3 micrometers. For example, in one embodiment, the average particle size can be from about 1 micrometer to about 5 micrometers. In one embodiment, greater than 50% of the particles contained in the second-phase polymer, based on volume fraction, can be greater than about 2 micrometers, e.g., greater than about 3 micrometers. For example, in one embodiment, 50% of the particles have a particle size by volume fraction of about 3 micrometers to about 5 micrometers.

[0049] The relative amounts of the different phases included in the polymer composition can vary depending on various factors and the desired results. Generally, the second polymer phase can be included in the polypropylene composition in an amount greater than about 15 wt%, for example, greater than about 20 wt%, for example, greater than about 25 wt%, for example, greater than about 30 wt%, for example, greater than about 35 wt%, and generally less than about 60 wt%, for example, less than about 50 wt%, for example, less than about 40 wt%, for example, less than about 35 wt%. For example, the second phase polymer can be present in the composition in an amount greater than about 15 wt% and less than about 60 wt%, including all 1 wt% increments therebetween.

[0050] In addition to the first-phase polymer and the second-phase polymer, the polypropylene composition of the present disclosure can contain various other additives and ingredients. For example, the polypropylene composition can contain nucleating agents, mold release agents, slip agents, antiblocking agents, UV stabilizers, heat stabilizers (e.g., DSTDP), colorants / dyes, etc. In one embodiment, the polymer composition can contain an antioxidant, such as a hindered phenolic antioxidant. The polymer composition can also contain an acid scavenger. Each of the additives can generally be present in the polymer composition in an amount less than about 3 wt %, such as less than about 2 wt %, such as less than about 1 wt %, such as less than about 0.5 wt %, and generally greater than about 0.001 wt %.

[0051] In one embodiment, the polypropylene composition may further comprise a clarifier. The clarifier may be added to further improve the transparency properties of the composition. The clarifier may include, for example, a compound capable of forming a gelling network within the composition.

[0052] In one embodiment, the clarification agent may include a sorbitol compound, such as a sorbitol acetal derivative. In one embodiment, for example, the clarification agent may include benzyl sorbitol.

[0053] With respect to sorbitol acetal derivatives that can be used as additives in some embodiments, the sorbitol acetal derivatives have the formula (I): [ka] wherein R1 to R5 comprise the same or different moieties selected from hydrogen and C1 to C3 alkyl.

[0054] 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-dimethylobenzylidene) 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").

[0055] Other embodiments of fining agents that can be used include: 1,3:2,4-dibenzylidene sorbitol, 1,3:2,4-bis(p-methylbenzylidene) sorbitol, Di(p-methylbenzylidene)sorbitol Di(p-ethylbenzylidene)sorbitol Bis(5',6',7',8'-tetrahydro-2-naphthylidene)sorbitol.

[0056] In one embodiment, the clarifier may also include a bisamide, such as benzenetrisamide.The above clarifiers may be used alone or in combination.

[0057] When present in the polymer composition, one or more clarifiers are generally added in an amount greater than about 200 ppm, for example, greater than about 1,800 ppm, for example, greater than about 2,000 ppm, for example, greater than about 2,200 ppm. One or more clarifiers are generally present in an amount less than about 5,000 ppm, for example, less than about 4,000 ppm, for example, less than about 3,000 ppm, for example, less than about 2,000 ppm, and the amount of clarifier present in the composition can depend on various factors, including the type of clarifier used.

[0058] The first-phase polymer and the second-phase polymer can be produced using a variety of different polymerization methods and procedures. In one embodiment, a Ziegler-Natta catalyst is used to produce the polymer composition. For example, olefin polymerization can occur in the presence of a catalyst system including a catalyst, an internal electron donor, a cocatalyst, and, optionally, an external electron donor. An olefin of formula CH═CHR, where R is hydrogen or a hydrocarbon radical having 1 to 12 atoms, can be contacted with the catalyst system under conditions suitable to form the polymer product. Copolymerization can occur in a method-step process to produce the heterophasic compositions of the present disclosure. The polymerization process can be carried out in the gas phase using a fluidized or stirred-bed reactor, or in the slurry phase using an inert hydrocarbon solvent or diluent or liquid monomer, using known techniques.

[0059] In one embodiment, the first-phase polymer and the second-phase polymer can be produced in a two-stage process, including a first stage in which a continuous polymer phase propylene random copolymer is prepared, and a second stage in which a propylene copolymer is produced. The first-stage polymerization can be carried out in one or more bulk reactors or one or more gas-phase reactors. The second-stage polymerization can be carried out in one or more gas-phase reactors. The second-stage polymerization is typically carried out immediately after the first-stage polymerization. For example, the polymerization product recovered from the first polymerization stage can be directly transferred to the second polymerization stage. In this regard, the polymerization can be carried out according to a sequential polymerization process. A heterophasic copolymer composition is produced.

[0060] In one embodiment of the present disclosure, the polymerization is carried out in the presence of a stereoregular olefin polymerization catalyst. For example, the catalyst may be a Ziegler-Natta catalyst. For example, in one embodiment, a catalyst sold under the trade name CONSISTA, commercially available from W.R. Grace & Company, may be used. In one embodiment, a phthalate-free electron donor is selected.

[0061] In one embodiment, the catalyst comprises a procatalyst composition containing a titanium moiety, such as titanium chloride, a magnesium moiety, such as magnesium chloride, and at least one internal electron donor.

[0062] The procatalyst precursor can include (i) magnesium, (ii) a transition metal compound from Groups IV through VII of the periodic table, (iii) a halide ion, oxyhalide and / or alkoxide, and / or alkoxide of (i) or (i) and / or (ii), and (iv) a combination of (i), (ii), and (iii). Non-limiting examples of suitable procatalyst precursors include halides, oxyhalides, alkoxides of magnesium, manganese, titanium, vanadium, chromium, molybdenum, zirconium, hafnium, and combinations thereof.

[0063] 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.

[0064] 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 has a total alcohol mole range of 1.5 to 6.0, preferably 2.5 to 4.0, and most preferably 2.8 to 3.5. ROH is a C1-C4 alcohol, straight or branched chain, 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.

[0065] 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 )

[0066] 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 The hydrocarboxyl or hydrocarbyl group, x is the number of such X groups in the compound combined with the magnesium metal compound. Tr may be a Group IV metal, a Group V metal, or a Group VI metal. In one embodiment, Tr is preferably a Group IV metal, such as titanium. X is a chloride ion, a bromide ion, C 1~4 It may be an alkoxide or phenoxide, or a mixture thereof. In one embodiment, X is a chloride ion.

[0067] The precursor composition may be prepared by chlorination of the aforementioned mixed magnesium compounds, titanium compounds, or mixtures thereof.

[0068] In one embodiment, the precursor composition has the formula Mg d Ti(OR e ) f X g a mixed magnesium / titanium compound having the formula: 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 e The groups are the same or different, X is independently chlorine, bromine, or iodine, d is 0.5 to 56, or 2 to 4, or 3, f is 2 to 116 or 5 to 15, and g is 0.5 to 116 or 1 to 3.

[0069] According to the present disclosure, the procatalyst precursor described above is combined with at least one internal electron donor, which can include a substituted phenylene aromatic diester.

[0070] In one embodiment, the first internal electron donor has the following structure (I): [ka] wherein R1 to R2 are substituted phenylene aromatic diesters having the formula: 14 are the same or different. 14 are 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 alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof. 14 At least one of the is not hydrogen.

[0071] In one embodiment, the substituted phenylene aromatic diester may be any of the substituted phenylene aromatic diesters disclosed in U.S. Patent Application No. 61 / 141,959, filed December 31, 2008, the entire contents of which are incorporated herein by reference.

[0072] In one embodiment, the substituted phenylene aromatic diester may be any of the substituted phenylene aromatic diesters disclosed in International Publication No. WO 12088028, filed December 20, 2011, the entire contents of which are incorporated herein by reference.

[0073] In one embodiment, at least one (or two, or three, or four) R group(s) of R1-R4 is / are selected from substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof.

[0074] In one embodiment, R to R 14 In another embodiment, at least one (or some, or all) of the R group(s) is selected from the group consisting of substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, alkoxy 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, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof.

[0075] 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, alkoxy 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, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof. 10 ~R 14At least one of which is selected from substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof.

[0076] 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.

[0077] 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.

[0078] 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-C6 membered ring.

[0079] 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 14Each of is selected from hydrogen, substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, halogen, and combinations thereof.

[0080] 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.

[0081] In one embodiment, structure (I) includes R2 that is methyl, and R5 through R 14 Each of is hydrogen.

[0082] In one embodiment, structure (I) includes R2 that is ethyl, and R5 through R 14 Each of is hydrogen.

[0083] In one embodiment, structure (I) includes R2 that is t-butyl, and R5 through R 14 Each of is hydrogen.

[0084] In one embodiment, structure (I) includes R2 that is ethoxycarbonyl, and R5-R 14 Each of is hydrogen.

[0085] 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, alkoxy groups having 1 to 20 carbon atoms, halogens, and combinations thereof.

[0086] In one embodiment, structure (I) includes R1 which is methyl, and R5 through R 14 Each of is hydrogen.

[0087] In one embodiment, structure (I) comprises 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, alkoxy groups having 1 to 20 carbon atoms, halogens, and combinations thereof.

[0088] 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 a halogen.

[0089] In one embodiment, structure (I) comprises R1, which is a methyl group, and R3, which is a t-butyl group. R2, R4, and R5 through R 14 Each of is hydrogen.

[0090] In one embodiment, structure (I) includes R1 and R3 that are isopropyl groups. R2, R4 and R5 through R 14 Each of is hydrogen.

[0091] In one embodiment, structure (I) comprises R, R, and R as methyl groups. 10 and R3 is a t-butyl group. 11 ~R 14 Each of is hydrogen.

[0092] In one embodiment, structure (I) comprises R, R, and R as methyl groups. 12 and R3 is a t-butyl group. 10 , R 11 , R 13 , and R 14 Each of is hydrogen.

[0093] 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.

[0094] In one embodiment, structure (I) is a methyl group having R, R, R, R, R 10 , R 12 , and R 14 and R3 is a t-butyl group. 11 , and R 13 Each of is hydrogen.

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

[0096] In one embodiment, the substituted phenylene aromatic diester has structure (II) with R1 being a methyl group, and R3 being a t-butyl group. Each of R2 and R4 is hydrogen. R8 and R9 are ring members of a C6-membered ring to form a 1-naphthoyl moiety. R 13 and R 14 is a ring member of a C6-membered ring and forms another 1-naphthoyl moiety. Structure (II) is provided below. [ka]

[0097] In one embodiment, the substituted phenylene aromatic diester has structure (III) with R1 being a methyl group, and R3 being a t-butyl group. Each of R2 and R4 is hydrogen. R6 and R7 are ring members of a C6-membered ring to form a 2-naphthoyl moiety. R 12 and R 13 is a ring member of a C6-membered ring to form a 2-naphthoyl moiety. Structure (III) is provided below. [ka]

[0098] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is 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.

[0099] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is a t-butyl group. 12Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 , and R 14 Each of is hydrogen.

[0100] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is 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.

[0101] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is 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.

[0102] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is 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.

[0103] In one embodiment, structure (I) includes R1 being a methyl group and R3 being a t-butyl group. 11 , and R 12 Each of R2, R4, R5, R8, R9, R 10 , R 13 , and R 14 Each of is hydrogen.

[0104] In one embodiment, structure (I) includes 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.

[0105] In one embodiment, structure (I) includes R1 which is a methyl group, and R3 is a t-butyl group. 14 is a fluorine atom.

[0106] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is 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.

[0107] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is 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.

[0108] In one embodiment, R1 is a methyl group and R3 is 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.

[0109] In one embodiment, structure (I) includes R1 that is a methyl group and R3 that is 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.

[0110] In one embodiment, structure (I) includes R1, which is a methyl group, and R3, which is a 2,4,4-trimethylpentan-2-yl group. 14 Each of is hydrogen.

[0111] In one embodiment, structure (I) includes R1 and R3, each of which is a sec-butyl group. 14 Each of is hydrogen.

[0112] In one embodiment, the substituted phenylene aromatic diester has structure (IV), where R1 and R2 are members of a C6-membered ring and form a 1,2-naphthalene moiety. 14 is hydrogen. Structure (IV) is provided below. [ka]

[0113] In one embodiment, the substituted phenylene aromatic diester has structure (V), where R2 and R3 are members of a C6-membered ring and form a 2,3-naphthalene moiety. 14 is hydrogen. Structure (V) is provided below. [ka]

[0114] 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.

[0115] 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.

[0116] In one embodiment, structure (I) comprises R1, R3, and R4, each of which is an i-propyl group. 10 ~R 14 Each of is hydrogen.

[0117] In one embodiment, each of R1 and R4 is selected from a methyl group, an ethyl group, and a vinyl group. Each of R2 and R3 is selected from a hydrogen, a secondary alkyl group, or a tertiary alkyl group, and R2 and R3 are not both hydrogen. In other words, if R2 is hydrogen, then R3 is not hydrogen (and vice versa).

[0118] In one embodiment, a second internal electron donor may be used, generally comprising a polyether capable of coordinating in a bidentate manner. In one embodiment, the second internal electron donor is a substituted 1,3-diether of structure VI. [ka] In the formula, R1 and R2 are the same or different and are each selected from the group consisting of methyl, C2 to C 18 Straight or branched chain alkyl, C3-C 18 Cycloalkyl, C4-C 18 Cycloalkyl-Alkyl, C4-C 18 Alkyl-cycloalkyl, phenyl, organosilicon, C7-C 18 Aryl alkyl or C7-C 18 It is an alkylaryl radical, and R1 or R2 may also be a hydrogen atom.

[0119] In one embodiment, the second internal electron donor may comprise a cyclic or polycyclic 1,3-diether having structure VII. [ka] wherein R1, R2, R3, and R4 are as described for R1 and R2 in Structure VI, or may combine to form one or more C5-C7 fused aromatic or non-aromatic ring structures, optionally containing N, O, or S heteroatoms. Specific examples of second internal electron donors include: Examples include 4,4-bis(methoxymethyl)-2,6-dimethylheptane, 9,9-bis(methoxymethyl)fluorene, or a mixture thereof.

[0120] The precursor is converted to a solid procatalyst by further reaction (halogenation) with an inorganic halide compound, preferably a titanium halide compound, to incorporate an internal electron donor.

[0121] One suitable method for halogenating the precursor is by reacting the precursor with a tetravalent titanium halide, optionally in the presence of a hydrocarbon or halogenated hydrocarbon diluent, at elevated temperature. A preferred tetravalent titanium halide is titanium tetrachloride.

[0122] The resulting procatalyst composition may generally contain titanium in an amount of about 0.5% to about 6% by weight, for example, about 1.5% to about 5% by weight, for example, about 2% to about 4% by weight. The solid catalyst may generally contain magnesium in an amount greater than about 5% by weight, for example, greater than about 8% by weight, for example, greater than about 10% by weight, for example, greater than about 12% by weight, for example, greater than about 14% by weight, for example, greater than about 16% by weight. Magnesium is contained in the catalyst in an amount less than about 25% by weight, for example, less than about 23% by weight, for example, less than about 20% by weight. The internal electron donor may be present in the catalyst composition in an amount less than about 30% by weight, for example, less than about 25% by weight, for example, less than about 22% by weight, for example, less than about 20% by weight, for example, less than about 19% by weight. The internal electron donor is generally present in an amount greater than about 5% by weight, for example, greater than about 9% by weight.

[0123] In one embodiment, the procatalyst composition is combined with a cocatalyst to form a catalyst system, which is a system that forms an olefin-based polymer when contacted with an olefin under polymerization conditions. The catalyst system may optionally include an external electron donor, an activity limiting agent, and / or various other components.

[0124] As used herein, a "cocatalyst" is a material capable of converting a procatalyst into an active polymerization catalyst. Cocatalysts may include hydrides, alkyls, or aryls of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium, and combinations thereof. In one embodiment, the cocatalyst is a hydrocarbyl aluminum cocatalyst represented by the formula RAl, where each R is an alkyl, cycloalkyl, aryl, or hydride radical; at least one R is a hydrocarbyl radical; two or three R radicals can be bonded to a cyclic radical forming a heterocyclic ring structure; each R can be the same or different; and each R, which is a hydrocarbyl radical, has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. In further embodiments, each alkyl radical can be straight-chain or branched-chain; and such hydrocarbyl radicals can be mixed radicals, i.e., the radicals can contain alkyl, aryl, and / or cycloalkyl groups. Non-limiting examples of suitable radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, n-nonyl, n-decyl, isodecyl, n-undecyl, n-dodecyl.

[0125] Non-limiting examples of suitable hydrocarbyl aluminum compounds are triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and tri-n-dodecylaluminum. In one embodiment, preferred cocatalysts are selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, and di-n-hexylaluminum hydride, with triethylaluminum being the most preferred cocatalyst.

[0126] In one embodiment, the co-catalyst has the formula R n AlX 3-n where n=1 or 2, R is alkyl, and X is a halide ion or alkoxide. Non-limiting examples of suitable compounds are methylaluminoxane, isobutylaluminoxane, diethylaluminum ethoxide, diisobutylaluminum chloride, tetraethyldialuminoxane, tetraisobutyldialuminoxane, diethylaluminum chloride, ethylaluminum dichloride, methylaluminum dichloride, and dimethylaluminum chloride.

[0127] In one embodiment, the catalyst composition includes an external electron donor. As used herein, an "external electron donor" is a compound added independently of the procatalyst formation and containing at least one functional group capable of donating a pair of electrons to a metal atom. Without being bound by theory, the external electron donor is believed to enhance the stereoselectivity of the catalyst (i.e., reduce xylene-soluble species in the formant polymer).

[0128] In one embodiment, the external electron donor may be selected from one or more of alkoxysilanes, amines, ethers, carboxylates, ketones, amides, carbamates, phosphines, phosphates, phosphites, sulfonates, sulfones, and / or sulfoxides.

[0129] In one embodiment, the external electron donor is an alkoxysilane. Alkoxysilanes have the general formula SiR m (OR') 4-m (I) wherein R, independently at each occurrence, is 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; R' contains up to 20 atoms other than hydrogen and halogen; and R' is C 1~4 alkyl group, and m is 0, 1, 2, or 3. In one embodiment, R is C 6~12 Aryl, alkyl or aralkyl, C 3~12 Cycloalkyl, C 3~12 Branched alkyl, or C 3~12 A cyclic or acyclic amino group, R' is C 1~4alkyl, and m is 1 or 2. 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), diisopropyldimethoxysilane (DIPDMS), n-propyltrimethoxysilane (NPTMS), diethylaminotriethoxysilane (DATES), or n-propyltriethoxysilane (PTES), and any combination thereof.

[0130] In one embodiment, the external donor can be a mixture of at least two alkoxysilanes. In further embodiments, the mixture can be dicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane and tetraethoxysilane, or dicyclopentyldimethoxysilane and n-propyltriethoxysilane.

[0131] In one embodiment, the external electron donor is selected from one or more of a benzoate and / or a diol ester. In another embodiment, the external electron donor is 2,2,6,6-tetramethylpiperidine. In yet another embodiment, the external electron donor is a diether.

[0132] In one embodiment, the catalyst composition includes an activity limiting agent (ALA). As used herein, an "activity limiting agent" ("ALA") is a substance that reduces catalyst activity at elevated temperatures (i.e., temperatures above about 85°C). The ALA inhibits or otherwise prevents polymerization reactor upset, ensuring the continuation of the polymerization process. Typically, the activity of a Ziegler-Natta catalyst increases as the reactor temperature increases. Ziegler-Natta catalysts also typically maintain high activity at temperatures near the melting point of the produced polymer. Heat generated by an exothermic polymerization reaction can cause polymer particle agglomerates to form, ultimately disrupting the polymer production process. The ALA reduces catalyst activity at elevated temperatures, thereby preventing reactor upset and reducing (or preventing) particle agglomeration, ensuring the continuation of the polymerization process.

[0133] The activity limiting agent may be a carboxylic acid ester, a diether, a poly(alkene glycol), a poly(alkene glycol) ester, a diol ester, or a combination thereof. The carboxylic acid ester may 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 acrylate, methyl methacrylate, ethyl acetate, ethyl p-chlorobenzoate, hexyl p-aminobenzoate, isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate, and propyl pivalate.

[0134] In one embodiment, the external electron donor and / or activity limiting agent may be added separately to the reactor. In another embodiment, the external electron donor and activity limiting agent may be premixed and then added to the reactor as a mixture. More than one external electron donor or more than one activity limiting agent may be used in the mixture. In one embodiment, the mixture may include dicyclopentyldimethoxysilane and isopropyl myristate, dicyclopentyldinethoxysilane and polyethylene glycol laurate, dicyclopentyldimethoxysilane and isopropyl myristate and polyethylene glycol dioleate, methylcyclohexyldimethoxysilane and isopropyl myristate, n-propyltrimethoxysilane and isopropyl myristate, dimethyldimethoxysilane and methylcyclohexyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and n-propyltriethoxysilane and isopropyl myristate, and dicyclopentyldimethoxysilane and tetraethoxysilane, isopropyl myristate, pentyl valerate, and combinations thereof.

[0135] In one embodiment, the catalyst composition comprises any of the aforementioned external electron donors in combination with any of the aforementioned activity limiting agents.

[0136] The above catalyst systems have been found to be particularly suitable for producing the heterophasic polymer compositions of the present disclosure.

[0137] The physical properties of the polypropylene compositions of the present disclosure, particularly the flow properties of the compositions, make them particularly suitable for the manufacture of molded articles. The polypropylene compositions can be used, for example, in injection molding, blow molding, and rotational molding applications.

[0138] The polypropylene polymer composition of the present disclosure can be used to make a number of different articles and products. The polymer composition's high transparency combined with excellent impact resistance makes it particularly suitable for manufacturing storage containers. The storage container may be, for example, food packaging. The impact-resistant properties of the polymer allow the storage container to be used, for example, to hold food items in a freezer. Referring to FIG. 1 , for example, one embodiment of a storage container made in accordance with the present disclosure is shown. As shown, the storage container 10 includes a container portion 14 defining a hollow interior for receiving one or more items. The container portion 14 may be mated with a lid 12. The lid 12 may include a channel and flange that interlocks with the rim of the container portion 14. According to the present disclosure, the contents of the container 10 can be viewed through the container wall.

[0139] In addition to food containers, various other storage containers can be made according to the present disclosure. For example, larger storage containers can be made using the polymer compositions of the present disclosure. For example, larger storage containers can be designed to store various items in attics, garages, or other storage facilities where temperature swings may occur.

[0140] The present disclosure may be better understood with reference to the following examples. [Example]

[0141] Two different heterophasic polypropylene copolymer samples were produced according to the present disclosure and tested for various properties, including impact strength and haze. A comparative example containing a lower amount of ethylene in the second-phase polymer was also produced. The heterophasic copolymers were generally produced using the process described above with the catalysts described above. Specifically, the copolymers were produced in a dual reactor configuration, where a matrix polymer was produced in a first gas-phase reactor, and then the contents of the first reactor were passed through a second gas-phase reactor. Ethylene was used as the comonomer. The ethylene content was controlled in the first-phase polymer and the second-phase polymer.

[0142] Polymer pellet samples were prepared and injection molded into test specimens. An additive package was added to the polymer, including 1000 ppm of tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)pentaerythritol; 1000 ppm of tris(2,4-ditert-butylphenyl)phosphite; 180 ppm of an acid scavenger (hydrotalcite); 2000 ppm of glycerol monostearate; and 4000 ppm of a clarifier. For example, test specimens were prepared according to ASTM test D4101 to prepare specimens for flex test and IZOD test.

[0143] The polymerization conditions for the three samples are as follows: A gas phase reactor was used to produce the polymer. [Table 3]

[0144] The following polypropylene compositions were produced: [Table 4]

[0145] The above compositions were tested for various properties with the following results: [Table 5]

[0146] Samples No. 2 and No. 3 above were made in accordance with the present disclosure and exhibited dramatically better impact resistance properties at temperatures of -20°C.

[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 invention, which is more particularly set forth in the appended claims. Additionally, 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.

Claims

1. a first polymer phase comprising a polypropylene random copolymer containing ethylene, said polypropylene random copolymer having a xylene solubles content of less than 10% by weight and a melt flow rate of 20 g / 10 min to 50 g / 10 min as measured according to ASTM 1238 at 230°C using a 2.16 kg weight; a second polymer phase combined with the first polymer phase, the second polymer phase comprising an ethylene-containing polypropylene random copolymer; A polypropylene composition comprising: The polypropylene composition has a melt flow rate of 3 g / 10 min or more, a ratio of the melt flow rate of the first polymer phase to the melt flow rate of the polypropylene composition is 1.2 or greater; the polypropylene composition having a xylene soluble portion and a xylene insoluble portion; the polypropylene composition having a total xylene solubles content of 12% to 25% by weight; the xylene soluble portion contains the ethylene in an amount of 55% to 70% by weight; the xylene-insoluble portion contains the ethylene in an amount of 15% to 40% by weight; the polypropylene composition has a Gardner impact strength of greater than 200 inch-pounds at −20° C. as measured in accordance with ASTM D5420; the polypropylene random copolymer in the first polymer phase is prepared using a first Ziegler-Natta catalyst; the polypropylene random copolymer in the second polymer phase is prepared using the first Ziegler-Natta catalyst or the second Ziegler-Natta catalyst; the second polymer phase is in the form of polymer particles dispersed within the first polymer phase, the polymer particles having an average particle size of 1.5 micrometers or greater; The polypropylene composition.

2. 10. The polypropylene composition of claim 1, wherein said composition further comprises a clarifier, and wherein said polypropylene composition has a haze at 1 mm of less than 45%.

3. 3. The polypropylene composition according to claim 1 or 2, wherein the polymer particles have an average particle size of 2 micrometers or greater.

4. 2. The polypropylene composition of claim 1, wherein the ethylene content in the xylene soluble portion of the polypropylene composition is from 60% to 70% by weight.

5. 2. The polypropylene composition of claim 1, wherein the ethylene content in the xylene insoluble portion of the polypropylene composition is from 20% to 38% by weight.

6. 10. The polypropylene composition of claim 1, wherein the composition has a flexural modulus of from 500 MPa to 1000 MPa.

7. 10. The polypropylene composition of claim 1, wherein said composition has a Gardner impact strength of from 300 inch-pounds to 500 inch-pounds at -20°C.

8. 10. The polypropylene composition of claim 1, wherein the polypropylene random copolymer in the first polymer phase contains ethylene in an amount of 1 wt% to 4 wt%.

9. 10. The polypropylene composition of claim 1, wherein the polypropylene random copolymer in the second polymer phase contains ethylene in an amount greater than 75 wt%.

10. 10. The polypropylene composition of claim 1, wherein the second polymer phase is present in the polypropylene composition in an amount of from 15% to 50% by weight.

11. 10. The polypropylene composition of claim 1, wherein the polypropylene composition has a total xylene solubles content of 15% to 21% by weight.

12. 10. The polypropylene composition of claim 1, wherein the polypropylene composition has a clarity of greater than 90% as determined using ASTM test D1746 on injection molded plaques having a thickness of 1 mm.

13. 10. The polypropylene composition of claim 1, wherein the polypropylene composition has a melt flow rate of 5 g / 10 min to 30 g / 10 min.

14. 2. The polypropylene composition of claim 1, wherein the ethylene-containing polypropylene random copolymer in the first polymer phase is produced using a Ziegler-Natta catalyst, and the ethylene-containing polypropylene random copolymer in the second polymer phase is also produced using a Ziegler-Natta catalyst.

15. 15. The polypropylene composition of claim 14, wherein the Ziegler-Natta catalyst used to produce the polypropylene polymer of the first polymer phase and the polypropylene random copolymer of the second polymer phase comprises an internal electron donor comprising a substituted phenylene aromatic diester.

16. 15. The polypropylene composition of claim 14, wherein the second polymer phase is formed in the presence of the first polymer phase.

17. 10. The polypropylene composition of claim 1, wherein the polypropylene composition exhibits at least three tan δ peaks at three different temperatures.

18. The polypropylene composition of claim 1 , wherein the composition further comprises an acid neutralizer and an antioxidant.

19. A molded article formed from the polypropylene composition of claim 1.

20. 20. The molded article of claim 19, wherein the molded article is an injection molded article.

21. A storage container formed from the polypropylene composition of claim 1.

22. 22. The storage container of claim 21, wherein the storage container is a food container.

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