RU2818186C2 - Polypropylene polymer composition with high rigidity properties - Google Patents

Abstract

FIELD: manufacturing technology; molding.

SUBSTANCE: group of inventions relates to a polypropylene polymer composition for producing molded articles, a method for production thereof and an article molded from the composition in the form of a container. Polypropylene polymer composition for producing molded articles contains a first polypropylene polymer in combination with a second polypropylene polymer, wherein the melt flow rate of the first polypropylene polymer ranges from 0.1 g/10 min to 3 g/10 min and the content of xylene soluble substances ranges from 1.0% by weight to 7% by weight, wherein the melt flow rate of the second polypropylene polymer ranges from 5 g/10 min to 100 g/10 min and the content of xylene-soluble substances ranges from 1 wt.% to 7 wt.%. First polypropylene polymer is present in the polymer composition in amount of 30% to 66% by weight and the first polypropylene polymer and the second polypropylene polymer both contain polypropylene polymers catalysed by a non-phthalate Ziegler–Natta catalyst. Bending modulus of polypropylene polymer composition ranges from 1,500 MPa to 2,500 MPa, content of xylene-soluble substances in the polypropylene polymer composition ranges from 2.5% to 7% by weight, wherein the first polypropylene polymer is a homopolymer, second polypropylene polymer is a polypropylene homopolymer or a copolymer of polypropylene and ethylene, having an ethylene content of less than or equal to 1.5% by weight, where the melt flow rate is measured in accordance with ASTM D 1238, at 230 °C with load of 2.16 kg and the flexural modulus is determined in accordance with ASTM D790-10 method A at 1.3 mm/min using a sample of type 1 according to ASTM 3641, cast in accordance with ASTM D4101.

EFFECT: providing a polymer composition having relatively high stiffness and mechanical viscosity properties without detriment to catalytic activity and with a wide distribution by molecular weight, which improves processability of the composition.

23 cl, 1 dwg, 1 tbl, 15 ex

Description

Related applications

This application is based on and claims benefit from U.S. Provisional Patent Application No. 62/830,007, filed April 5, 2019, the contents of which are incorporated herein by reference.

Prerequisites for creating the invention

One of the important properties of many polymer materials is rigidity. Stiffness is a material characteristic. It can be measured by determining the flexural modulus of the material. Flexural modulus refers to a material's ability to bend, or in other words its resistance to bending, when a force is applied perpendicular to the molded polymer plate.

Polymers with increased rigidity provide a number of advantages when molding products. Polymers with high rigidity, for example, do not substantially deform when exposed to external forces. Thus, polymers with high rigidity can be used to create free-standing products, as well as products that need to maintain their shape. The higher the rigidity of the polymer, the thinner the walls of a product, for example, a container, can be, while maintaining its properties and shape.

Previous attempts have been made to increase the stiffness of polypropylene polymers. For example, the rigidity of polypropylene polymers was increased by increasing the crystallinity of the material. This provided the required increase in rigidity. However, problems arose.

For example, increasing the crystallinity of a polypropylene polymer can reduce mechanical viscosity and lead to brittleness of the final product. In addition, processing highly crystalline polypropylene can be somewhat difficult. Increasing the crystallinity of a polypropylene polymer, for example, can reduce the range of effective polymer melt conditions, complicating the formation of products.

In addition, the production of highly crystalline polypropylene can be quite expensive. Increasing the degree of crystallinity of the polymer, for example, can reduce the efficiency of the catalyst used to produce the polymer. For example, Ziegler-Natta catalysts decrease in catalytic activity as the crystallinity of the polymer increases. Consequently, more catalysts are needed to produce the polymer, which significantly increases the cost of producing the polymer.

In view of the above, there is a need for a polypropylene polymer composition having relatively high properties of rigidity and mechanical viscosity. There is also a need for a method of producing a polypropylene polymer composition with high rigidity without compromising catalytic activity.

Summary of the invention

In general, the present invention relates to polypropylene polymer compositions having relatively high stiffness properties. The polymer composition of the present invention can be obtained without compromising catalytic activity and with a wide molecular weight distribution. A wide distribution of molecular weights improves the processability of the composition.

In one embodiment, the present invention relates to a polypropylene polymer composition comprising a first polypropylene polymer in combination with a second polypropylene polymer. The melt flow rate of the first polypropylene polymer is greater than about 0.1 g/10 min and less than about 3 g/10 min. The xylene solubles content of the first polypropylene polymer is greater than about 1%, such as greater than about 2.5%, such as greater than about 3%, such as greater than about 3.5%, and substantially less than about 8%, such as less than about 7% by weight. In one aspect, the xylene solubles content is greater than about 5% by weight, such as greater than about 6% by weight. In another aspect, the xylene solubles content is less than about 4% by weight. The polydispersity index of the first polypropylene polymer may be substantially greater than about 4 and less than about 10.

The melt flow rate of the second polypropylene polymer added to the first polypropylene polymer may be greater than about 5 g/10 min and less than about 100 g/10 min. The xylene solubles content of the second polypropylene polymer is greater than about 1%, such as greater than about 2.5%, such as greater than about 3%, such as greater than about 4%, and substantially less than about 8%, such as less than about 7%, by weight. The polydispersity index of the second polypropylene polymer may be greater than about 4 and less than about 5.5.

In one aspect, the xylene soluble content of one of the polypropylene polymers is greater than about 5% by weight, such as greater than about 6% by weight, and the xylene soluble content of the other polypropylene polymer is less than about 4% by weight.

The first polypropylene polymer may be present in the polypropylene polymer composition in a weight ratio to the second polypropylene polymer of from about 5:95 to about 80:20, such as from about 30:70 to about 67:33. In one particular embodiment, the first polypropylene polymer has a low melt flow rate is present in the composition in an amount less than the second polypropylene polymer. For example, in one embodiment, the weight ratio of the first polypropylene polymer to the second polypropylene polymer may be from about 5:95 to about 45:55. The melt flow rate of the overall polypropylene polymer composition may be substantially greater than about 0.5 g/10 min. for example, more than about 0.7 g/10 min, for example, more than about 1 g/10 min, and substantially less than about 30 g/10 min, for example, less than about 25 g/10 min, for example, less than about 20 g/10 min. In one embodiment, for example, the melt flow rate may be from about 0.5 g/10 min to about 3 g/10 min. In an alternative embodiment, the melt flow rate may be from about 5 g/10 min to about 20 g/10 min.

The total xylene solubles content of the polypropylene polymer composition may be substantially greater than about 3%, such as greater than about 3.5%, such as greater than about 4%, and substantially less than about 8%, such as less than about 7%, such as less than about 6 .8% by weight. The overall polydispersity index of the polypropylene polymer composition may be greater than about 5 and less than about 10.

As described above, the polypropylene resin composition according to the present invention has a relatively high rigidity. For example, a polypropylene polymer composition may have a flexural modulus (ASTM Test D790) according to the following equation:

2072 H XS ^-0.18

wherein "XS" represents the xylene solubles content of the polypropylene resin composition, and the xylene solubles content of the polypropylene resin composition may be from about 2.5% to about 8% by weight.

For example, the flexural modulus of the polypropylene polymer composition of the present invention may be greater than about 1500 MPa, such as greater than about 1550 MPa, such as greater than about 1600 MPa, such as greater than about 1650 MPa, such as greater than about 1700 MPa, and substantially less than about 2500 MPa . In addition to excellent stiffness properties, the polypropylene polymer composition may also exhibit an Izod impact strength of greater than about 40 J/m, such as greater than about 45 J/m, such as greater than about 55 J/m, and substantially less than about 90 J/m.

In one embodiment, the first polypropylene polymer and the second polypropylene polymer may comprise polypropylene homopolymers. In an alternative embodiment, at least one of the polypropylene polymers may be a copolymer, such as a copolymer containing ethylene units.

The polypropylene polymer composition of the present invention, in one embodiment, can be formed in a process in which the propylene polymer is polymerized in the presence of a phthalate-free Ziegler-Natta catalyst. The catalytic activity of the Ziegler-Natta catalyst may be greater than about 50 kg/g to produce a polypropylene polymer composition. Polypropylene polymers can be produced in a gas-phase or liquid-phase reactor. In one embodiment, each of the first and second polypropylene polymers is formed separately and then combined. In an alternative embodiment, the first polypropylene polymer and the second polypropylene polymer may be formed sequentially in a series of reactors.

The polypropylene polymer composition of the present invention can be used to produce all different types of molded articles. In one embodiment, the polymer composition can be used to produce all different types of molded articles using any suitable thermoforming or casting method. For example, the products may be manufactured by extrusion blow molding, injection molding, rotomoulding, extrusion, and the like. The polypropylene polymer composition can also be used to form a biaxially oriented polypropylene film. Products that can be manufactured in accordance with the present disclosure include storage or packaging containers, such as food containers.

Other features and aspects of the present disclosure are described in more detail below.

Brief description of graphic materials

A complete and sufficient description of the present invention is set forth more specifically in the remainder of the specification, including reference to the accompanying figures.

In fig. Figure 1 provides a graphical representation of the results obtained in the example below.

Repetition of reference numerals throughout the present specification and drawings is intended to represent the same or similar features or elements of the present invention.

Test Definitions and Procedures

As used herein, the term “polypropylene homopolymer” refers to a homopolymer containing propylene monomer units.

As used herein, the term “propylene-ethylene copolymer” means a copolymer containing propylene monomer with a predominant weight percentage relative to ethylene monomer as a secondary constituent. A "propylene-ethylene copolymer" (also sometimes called polypropylene random copolymer, PPR, PP-R, RCP, or RACO) is a polymer having individual repeating ethylene monomer units present in a random or random distribution throughout the polymer chain.

Melt flow rate (MFR) as used herein is measured in accordance with the test method set forth in ASTM D 1238 at 230°C with a 2.16 kg load for propylene-based polymers.

Xylene solubles (XS) are defined as the percentage by weight of resin that remains in solution after dissolving a sample of propylene random copolymer resin in hot xylene and cooling the solution to 25°C. This method is also referred to as the gravimetric XS method according to ASTM D5492-06 using a 90 minute settling time and is also referred to herein as the "wet method". The XS content can also be measured according to the Viscotek method as follows: Dissolve 0.4 g of polymer in 20 ml of xylenes with stirring at 130° C. for 60 minutes. Subsequently, the solution is cooled to 25°C, and after 60 minutes the insoluble polymer fraction is filtered off. The resulting filtrate is analyzed by flow injection analysis of polymers using a Viscotek ViscoGEL H-100-3078 column with a THF mobile phase flowing at a rate of 1.0 ml/min. The column is coupled to a Viscotek Model 302 three-detector array equipped with a light scattering detector, viscometer and refractometer operating at 45°C. The instrument was calibrated using Viscotek PolyCAL™ polystyrene standards. A polypropylene (PP) homopolymer, such as Dow brand 5D98 biaxially oriented polypropylene (BOPP), is used as a reference material to ensure that the Viscotek instrument and sample preparation procedures produce reproducible results when using a polypropylene homopolymer, such as 5D98, as a reference material to check the effectiveness of the method. The value for a reference polypropylene homopolymer such as 5D98 is initially obtained from testing using the ASTM method above.

The ASTM D5492-06 method mentioned above can be adapted to determine the xylene soluble portion. The general procedure consists of weighing a 2 g sample and dissolving the sample in 200 ml of o-xylene in a 400 ml flask with a 24/40 joint. The flask is connected to a water-cooled condenser and the contents are stirred and heated under nitrogen (N ₂ ) until condensation appears, and then maintained at reflux for a further 30 minutes. The solution is then cooled in a water bath maintained at 25°C for 90 minutes to allow the xylene-insoluble fraction to crystallize. After the solution has cooled and the insoluble fraction has precipitated out of the solution, separation of the xylene soluble portion (XS) from the xylene insoluble portion (XI) is achieved by filtration through 25 micron filter paper. One hundred milliliters of the filtrate is collected in a pre-weighed aluminum bowl and o-xylene is evaporated from the said 100 ml of filtrate under a stream of nitrogen. After the solvent has evaporated, the tray and contents are placed in a vacuum oven at 100°C for 30 minutes or until dry. The tray is then allowed to cool to room temperature and weighed. The content of the xylene-soluble part is calculated using the formula: XS (wt.%) = [(m ₃ − m ₂ ) * 2/m ₁ ] * 100, where m ₁ is the initial mass of the sample used, m ₂ is the mass of the empty aluminum pan, and m ₃ is the mass of the pallet and the remainder (here and throughout the description, the “asterisk” symbol (*) means the product of the given terms or meanings).

Ethylene content is measured by Fourier Transform Infrared (FTIR) spectroscopy, and the results of these measurements are correlated with ethylene content values determined by ¹³ C NMR as the primary method. The relationship and agreement between measurements made using these two methods are described, for example, in J. R. Paxson, J. C. Randall, “Quantitative Measurement of Ethylene Incorporation into Propylene Copolymers by Carbon-13 Nuclear Magnetic Resonance and Infrared Spectroscopy,” Analytical Chemistry, Vol. . 50, No. 13, Nov. 1978, 1777-1780.

The flexural modulus is determined according to Method A of ASTM D790-10 at 1.3 mm/min using an ASTM 3641 Type 1 specimen cast in accordance with ASTM D4101.

The polydispersity coefficient is measured using small amplitude oscillatory shift (SAOS). The test is carried out using the ARES G2 (TA Instruments), which is a dynamic voltage monitoring spectrometer from TA Instruments, using the method in accordance with Zeichner GR, Patel PD (1981) "A comprehensive Study of Polypropylene Melt Rheology" Proc. Of the ^2nd World Congress of Chemical Eng., Montreal, Canada. An ETC oven is used to control the temperature to 180°C ± 0.1°C. Nitrogen is used to purge the interior of the oven to prevent oxygen and moisture from degrading the sample. The sample holder is a parallel plate with a diameter of 25 mm. The diameter of the sample, injection molded at 230°C, was 25 mm and the thickness was 2 mm. Frequency sweep is used to obtain the dynamic elastic modulus (G') and mechanical loss modulus (G'') at 190°C in a nitrogen atmosphere. The intersection of G' and G'' at 190°C (Gc) is used to calculate polydispersity (PDS) using the following equation:

MDS = 10 ⁵ /Gc

The test method is also essentially described in US Patent No. 9,045,570, which uses a different sample size and cone plate rheometry.

Izod impact strength is measured in accordance with ASTM D 256 and D4101.

Detailed description

It should be understood by one of ordinary skill in the art that this text is only a description of embodiments and is not intended to limit the broader aspects of the present description.

In general, the present description relates to a polypropylene composition having a unique combination of physical properties. For example, in one embodiment, the polymer composition may be formulated to have relatively high stiffness properties combined with excellent mechanical viscosity properties. In addition, the polymer composition can be formulated to have good flow characteristics. Thus, the polymer composition is particularly well suited for the production of thermoformed products and molded articles, such as injection molded articles. For example, in one embodiment, the polymer composition can be used to mold containers. Due to the properties of rigidity and mechanical viscosity of the polymer composition, containers and other products with internal volume can be molded with minimal wall thickness. Thus, polymer products can be efficiently produced using a minimal amount of the polymer composition.

It is a particular advantage that the polypropylene polymer composition of the present invention can be manufactured with high stiffness properties as well as a wide molecular weight distribution and using a catalyst system that maintains high catalytic activity during the polymerization process. For example, during the polymerization of the polymers of the present disclosure, a non-phthalate Ziegler-Natta catalyst may be used that maintains an activity greater than about 50 kg/g, such as greater than about 55 kg/g, such as greater than about 60 kg/g, during production of the polymer composition.

In general, the polypropylene polymer composition of the present invention includes a mixture of polymers. In particular, the polymer composition includes a first polypropylene polymer in combination with a second polypropylene polymer. The first polypropylene polymer essentially has a relatively low melt flow rate compared to the second polypropylene polymer. Surprisingly, it has been discovered that relatively small amounts of low melt flow rate polymer in combination with a second polypropylene polymer are needed to obtain a polymer composition having the desired high stiffness properties. In fact, the low melt flow rate polypropylene polymer may be present in the composition in amounts less than 50% by weight, such as amounts less than 40% by weight, such as amounts less than 30% by weight, such as amounts less than 20% by weight, and still provide an overall polymer composition having excellent stiffness characteristics. These results are significant and unexpected.

In addition, as described above, the polypropylene polymer composition can be obtained with a relatively broad molecular weight distribution. A wide distribution of molecular weights significantly improves the technological characteristics of the composition.

In addition, the xylene soluble content of the first and second polypropylene polymers is selectively controlled to maintain high catalytic activity during polymer production while maximizing stiffness. For example, the resulting polymer composition may exhibit a flexural modulus according to the following equation:

2072 H XS ^-0.18

where "XS" represents the xylene solubles content of the polypropylene polymer composition. The xylene solubles content of the polypropylene resin composition may be, for example, from about 2.5% to about 8% by weight.

For example, in one embodiment, the polypropylene polymer composition of the present invention may have a flexural modulus of greater than about 1500 MPa, such as greater than about 1550 MPa, such as greater than about 1600 MPa, such as greater than about 1650 MPa, such as greater than about 1700 MPa, such as greater than about 1750 MPa, and substantially less than about 2500 MPa, such as less than about 2000 MPa. For example, in one embodiment, the polypropylene polymer composition may have a flexural modulus of greater than about 1525 MPa and less than about 2000 MPa, including all 25 MPa increments in between.

In addition to excellent stiffness properties, the polypropylene resin composition of the present invention also has excellent mechanical toughness properties. For example, the polypropylene polymer composition herein may have an Izod impact strength greater than about 40 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. The Izod impact strength is substantially less than about 90 J/m, such as less than about 80 J/m.

As described above, the polypropylene polymer composition according to the present description includes a first polypropylene polymer mixed with a second polypropylene polymer. The first polypropylene polymer has an inherently low melt flow rate and greatly enhances the stiffness properties of the resulting composition. The melt flow rate of the first polypropylene polymer, for example, may be less than about 3 g/10 min, such as less than about 1 g/10 min, such as less than about 0.8 g/10 min, such as less than about 0.5 g/10 min , and substantially greater than about 0.01 g/10 min, such as greater than about 0.1 g/10 min. Although the melt flow rate of the first polypropylene polymer is low, the xylene solubles content is greater than about 2.5% by weight, such as greater than about 3% by weight, such as greater than about 3.5% by weight, such as greater than about 4 % by weight, such as greater than about 4.5% by weight, and substantially less than about 8% by weight, such as less than about 7% by weight. The first polypropylene polymer may be formed using a Ziegler-Natta catalyst and may have a relatively broad molecular weight distribution. In one embodiment, the polydispersity index of the first polypropylene polymer is greater than about 4 and substantially less than about 10, such as less than about 8.5, such as less than about 7, such as less than about 5.5.

The second polypropylene polymer combined with the first polypropylene polymer has a substantially higher melt flow rate. For example, the melt flow rate of the second polypropylene polymer is substantially greater than about 5 g/10 min, such as greater than about 7 g/10 min, such as greater than about 9 g/10 min. The melt flow rate is substantially less than about 100 g/10 min, such as less than about 40 g/10 min, such as less than about 30 g/10 min, such as less than about 25 g/10 min. The content of xylene-soluble substances in the second polypropylene polymer is similar to the content of xylene-soluble substances in the first polypropylene polymer. For example, the xylene solubles content of the second polypropylene polymer is substantially greater than about 1% by weight, such as greater than about 2% by weight, such as greater than about 2.5% by weight, such as greater than about 3% by weight, such as greater than about 4 % by weight. In some embodiments, the xylene solubles content of the second polypropylene polymer may be greater than about 5% by weight, such as greater than about 6% by weight, such as greater than about 6.5% by weight. The xylene solubles content of the second polypropylene polymer is substantially less than about 10% by weight, such as less than about 9% by weight, such as less than about 8% by weight, such as less than about 7.5% by weight.

The second polypropylene polymer can also be formed using a Ziegler-Natta catalyst, which maintains high catalytic activity during polymerization. The second polypropylene polymer may have a relatively broad molecular weight distribution and may have a polydispersity index greater than about 4 and substantially less than about 10, such as less than about 8.5, such as less than about 7, such as less than about 5.5.

The first polypropylene polymer and the second polypropylene polymer, in one embodiment, may be homopolymers of polypropylene. In an alternative embodiment, one of the polypropylene polymers may be a copolymer. For example, the first polypropylene polymer may be a homopolymer and the second polypropylene polymer may be a copolymer. In an alternative embodiment, the first polypropylene polymer may be a copolymer and the second polypropylene polymer may be a homopolymer. In yet another embodiment, both the first and second polypropylene polymers are copolymers. In such an embodiment, one or both of the polypropylene polymers may include small amounts of a comonomer, such as ethylene. For example, ethylene may be present in amounts less than about 1.5% by weight, such as in amounts less than 1% by weight. The copolymer may be a random copolymer, such as a mini-random copolymer.

In accordance with the present invention, a first polypropylene polymer is mixed with a second polypropylene polymer to form a polypropylene polymer composition. The weight ratio between the first polypropylene polymer and the second polypropylene polymer in the final composition is substantially from about 5:95 to about 80:20, such as from about 30:70 to about 67:33. In one embodiment, the first polypropylene polymer or the polypropylene polymer with low melt flow rate may be present in an amount less than the second polypropylene polymer, but still have the required stiffness characteristics. For example, based on the weight of the two polypropylene polymers used, the first polypropylene polymer may be present in an amount of less than about 50% by weight, such as in an amount of less than about 45% by weight, such as in an amount of less than about 40% by weight, such as in an amount of less than about 35 % by weight, such as in an amount less than about 30% by weight, such as in an amount less than about 25% by weight, such as in an amount less than about 20% by weight, and substantially in an amount greater than about 5% by weight, such as in an amount greater than about 10% by weight, such as in an amount greater than about 15% by weight, such as in an amount greater than about 20% by weight. In one aspect, the first polypropylene polymer is present in the polymer composition in an amount of from about 30% to about 66% by weight, such as from about 30% to about 50% by weight, such as from about 30% to about 45% by weight.

The resulting polypropylene polymer composition not only has good rigidity properties, but is also well suited for thermoforming and molding processes such as injection molding to produce various products, especially due to its wide molecular weight distribution. For example, the melt flow rate of the composition may be greater than about 0.5 g/10 min, such as greater than about 0.7 g/10 min, such as greater than about 1 g/10 min, such as greater than about 2 g/10 min, such as greater than about 3 g/10 min, for example more than about 5 g/10 min, for example more than about 8 g/10 min, for example more than about 10 g/10 min, for example more than about 12 g/10 min, for example more than about 15 g/10 min. The melt flow rate is substantially less than about 30 g/10 min, such as less than about 25 g/10 min, such as less than about 20 g/10 min. In one embodiment, the melt flow rate of the polypropylene composition can be relatively low and can range from about 0.5 g/10 min to about 3 g/10 min. In an alternative embodiment, the melt flow rate may be higher and may generally range from about 5 g/10 min to about 20 g/10 min. The melt flow rate can be controlled by adjusting the relative amounts of different polymers to obtain a polymer composition having the desired physical properties in combination with the desired flow properties.

The total xylene solubles content of the polypropylene polymer composition is substantially greater than about 2% by weight, such as greater than about 2.5% by weight, such as greater than about 3% by weight, such as greater than about 3.5% by weight. The total xylene solubles content is substantially less than about 10% by weight, such as less than about 8% by weight, such as less than about 7% by weight, such as less than about 6.8% by weight. The polydispersity index of the polymer composition is substantially greater than about 4, such as greater than about 5, such as greater than about 6, and substantially less than about 10, such as less than about 9, such as less than about 8.

In addition to the first polypropylene polymer and the second polypropylene polymer, the polypropylene polymer composition herein may contain various other additives and ingredients.

For example, the polypropylene composition may contain site initiators, mold release agents, glidants, anti-blocking agents, UV stabilizers, heat stabilizer (eg, DSTDP), colorants/shades, and the like. In one embodiment, the polymer composition may contain an antioxidant, such as a hindered phenolic antioxidant. The polymer composition may also contain an acid scavenger. Each of the additives may be present in the polymer composition in an amount substantially less than about 3% by weight, such as in an amount less than about 2% by weight, such as in an amount less than about 1% by weight, such as in an amount less than about 0.5% by weight , and essentially in an amount greater than about 0.001% by weight.

For example, in one embodiment, the polymer composition may optionally contain a nucleating agent, such as an alpha nucleating agent. The nucleating agent may be present in an amount substantially greater than about 0.001% by weight and substantially less than about 1% by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.3% by weight.

In one embodiment, an inorganic nucleating agent such as talc can be used. Other nucleating agents include sodium benzoate or a polymeric nucleating agent such as a partial metal salt of turpentine acid.

In another embodiment, the nucleating agent may be selected from the group of phosphorus-based nucleating agents, such as the metal salts of phosphoric acid esters represented by the following formula.

where "R1" represents oxygen, sulfur or a hydrocarbon group containing from 1 to 10 carbon atoms; "R2" and "R3" represent hydrogen or a hydrocarbon or a hydrocarbon group containing from 1 to 10 carbon atoms; "R2" and "R3" may be the same or different from each other, two of R2, two of R3 or R2 and R3 may be bonded to each other to form a ring, "M" represents a monovalent or trivalent metal atom; "n" is an integer between 1 and 3, and "m" is 0 or 1, provided n > m.

REPLACED SHEET (RULE 26)
Preferable examples of alpha nucleating agents represented by the above formula include sodium 2,2'-methylene bis(4,6-di-tert-butylphenyl)phosphate, sodium 2,2'-ethylidene bis(4,6- di-tert-butylphenyl)-phosphate, lithium-2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate, lithium-2,2'-ethylidene-bis(4,6-di-tert -butylphenyl)phosphate, sodium 2,2'-ethylidene-bis(4-isopropyl-6-tert-butylphenyl)phosphate, lithium 2,2'-methylene-bis(4-methyl-6-tert-butylphenyl)phosphate , lithium 2,2'-methylene-bis(4-ethyl-6-tert-butylphenyl)phosphate, calcium bis[2,2'-thiobis(4-methyl-6-tert-butylphenyl)-phosphate], calcium -bis[2,2'-thiobis(4-ethyl-6-tert-butylphenyl)-phosphate], calcium-bis[2,2'-thiobis(4,6-di-tert-butylphenyl)phosphate], magnesium- bis[2,2'-thiobis(4,6-di-tert-butylphenyl)phosphate], magnesium bis[2,2'-thiobis(4-tert-octylphenyl)phosphate], sodium 2,2'-butylidene -bis(4,6-dimethylphenyl)phosphate, sodium 2,2'-butylidene-bis(4,6-di-tert-butylphenyl)-phosphate, sodium 2,2'-tert-octylmethylene-bis(4, 6-dimethylphenyl)-phosphate, sodium 2,2'-tert-octylmethylene-bis(4,6-di-tert-butylphenyl)-phosphate, calcium bis[2,2'-methylene-bis(4,6- di-tert-butylphenyl)-phosphate], magnesium bis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)-phosphate], barium bis[2,2'-methylene-bis( 4,6-di-tert-butylphenyl)-phosphate], sodium 2,2'-methylene-bis(4-methyl-6-tert-butylphenyl)-phosphate, sodium 2,2'-methylene-bis(4 -ethyl-6-tert-butylphenyl)phosphate, sodium (4,4'-dimethyl-5,6'-di-tert-butyl-2,2'-biphenyl)phosphate, calcium bis-[(4,4'-dimethyl-6,6'-di-tert-butyl-2,2'-biphenyl)phosphate], sodium 2,2'-ethylidene-bis(4-m-butyl-6-tert-butylphenyl)phosphate, sodium -2,2'-methylene-bis-(4,6-dimethylphenyl)-phosphate, sodium-2,2'-methylene-bis(4,6-di-tert-ethylphenyl)phosphate, potassium-2,2'- ethylidene bis(4,6-di-tert-butylphenyl)-phosphate, calcium bis[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)-phosphate], magnesium bis[2, 2'-ethylidene-bis(4,6-di-tert-butylphenyl)-phosphate], barium bis[2,2'-ethylidene-bis-(4,6-di-tert-butylphenyl)-phosphate], aluminum -hydroxy-bis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate], aluminum-tris[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl) -phosphate].

The second group of phosphorus-based nucleating agents includes, for example, aluminum-hydroxy-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]- dioxa-foshocin-6-oxidato] and mixtures thereof with Li-myristate or Li-stearate.

Of the phosphorus-based nucleating agents, the most preferred option is sodium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate, or aluminum hydroxy-bis[2,2'-methylene-bis(4 ,6-di-tert-butylphenyl)-phosphate], or aluminum-hydroxy-bis-[2,4,8,10-tetrakis(1,1-dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g ]-dioxa-foshocin-6-oxidato], or mixtures thereof with Li-myristate or Li-stearate.

In addition, sorbitol-based nucleating agents such as optionally substituted dibenzylidene sorbitol (e.g., 1,3:2,4 dibenzylidene sorbitol, 1,3:2,4 Di(methylbenzylidene) sorbitol, 1,3:2 can be used as nucleating agents ,4 Di(ethylbenzylidene) sorbitol, 1.3 : 2.4 Bis(3,4-dimethylbenzylidene) sorbitol, etc.) or pine rosin.

Other suitable alpha-nucleating agents are polymeric nucleating agents selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers. The formation of active crystallization sites with such polymeric nucleating agents is either carried out by a special reactor in which the catalyst is pre-polymerized with monomers, such as, for example, vinylcyclohexane (VCH), or by mixing a propylene polymer with a vinyl(cyclo)alkane polymer.

Nucleating agents such as ADK NA-11 (sodium methylene bis(4,6-di-tert-butylphenyl)phosphate) and ADK NA-21 (aluminum containing hydroxy-bis[2,4,8,10-tetrakis( 1,1-Dimethylethyl)-6-hydroxy-12H-dibenzo-[d,g]-dioxa-phoshwin-6-oxidato]) is commercially available from Asahi Denka Kokai and is an agent that can be added to a polyolefin composition. Millad NX8000 (nonitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene)], Millad 3988 (3,4-dimethylbenzylidene sorbitol), Millad 3905 and Millad 3940 , offered commercially by Milliken & Company, are other examples of nucleating agents that can be used.

Additional commercially available alpha nucleating agents that can be used for the formulation include, for example, Irgaclear XT 386 (N-[3,5-bis(2,2-dimethylpropionylamino)phenyl]-2,2-dimethylpropionamide) from Ciba Specialty Chemicals, Hyperform HPN-68L and Hyperform HPN-20E from Milliken & Company.

According to an embodiment, the at least one alpha nucleating agent consists of a polymeric nucleating agent selected from the group consisting of vinylcycloalkane polymers and vinylalkane polymers, preferably polyvinylcyclohexanes (poly-VCH).

According to a further embodiment, the at least one alpha nucleating agent is selected from the group consisting of aluminum-hydroxy-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)-6-hydroxy- 12H-dibenzo-[d,g]-dioxaphoshocin-6-oxidato] (e.g. ADK NA-21, NA-21 E, NA-21 F), sodium-2,2'-methylene-bis(4,6- di-tert-butylphenyl)phosphate (ADK NA-11), aluminum hydroxy-bis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)-phosphate] and sorbitol-based nucleating agents (e.g. , Millad 3988, Millad 3905 and Millad 3940).

In one embodiment, the polypropylene composition may further comprise a brightening agent. A brightening agent can be added to further improve the clarity properties of the composition. For example, the brightening agent may contain a compound to form a gel-like network in the composition.

In one embodiment, the brightening agent may contain a sorbitol compound, such as a sorbitol acetal derivative. For example, in one embodiment, the brightening agent may contain dibenzylsorbitol.

With respect to sorbitol acetal derivatives that can be used as an additive in some embodiments, the sorbitol acetal derivative is shown in Formula (I):

where R1-R5 contain the same or different functional groups selected from hydrogen and C1-C3 alkyl.

In some embodiments, R1-R5 is 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-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).

Other embodiments of brightening agents that may 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.

In one embodiment, the brightening agent may also contain a bisamide, such as benzenetrisamide. The brightening agents described above can be used alone or in combination.

When brightening agents are present in the polymer composition, one or more brightening agents are added substantially in an amount greater than about 200 ppm, such as in an amount greater than about 1800 ppm, such as in an amount greater than about 2000 ppm, such as in an amount greater than about 2200 ppm. The one or more brightening agents are typically present in an amount of 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, such as less than about 5000 ppm. The amount of brightening agent present in the composition may depend on various factors, including the type of brightening agent used.

The first polypropylene polymer and the second polypropylene polymer can be produced using various polymerization methods and techniques. In one embodiment, both polymers are formed from propylene monomer in the presence of a Ziegler-Natta catalyst. For example, polymerization of olefins can occur in the presence of a catalyst system that includes a catalyst, an internal electron donor, a cocatalyst, and optionally an external electron donor and/or an activity limiting agent. The polymerization method used to obtain the two polymers can be carried out using known techniques. For example, the polymers can be formed in a gas-phase reactor or in a liquid-phase reactor. In particular, the polymers can be formed in a gas phase reactor using a fluidized bed or stirred bed reactor, or in slurry phase using an inert hydrocarbon solvent or diluent or liquid monomer. For example, the first polypropylene polymer and the second polypropylene polymer may be formed in a gas phase reactor. In an alternative embodiment, both the first polypropylene polymer and the second polypropylene polymer may be formed in a liquid phase reactor. In a further embodiment, one of the first polypropylene polymer and the second polypropylene polymer is formed in a gas phase reactor, and the other of the first polypropylene polymer and the second polypropylene polymer is formed in a liquid phase reactor. For example, the first polypropylene polymer may be formed in a liquid phase reactor and the second polypropylene polymer may be formed in a gas phase reactor.

In one embodiment, the first polypropylene polymer and the second polypropylene polymer are produced through two different polymerization processes and then combined together. In an alternative embodiment, the first polypropylene polymer and the second polypropylene polymer can be produced sequentially in a process that includes a series of reactors. For example, one of the polypropylene polymers may be produced in the first reactor and then transferred to a second reactor where another polypropylene polymer is produced.

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, electron donors that do not contain phthalates are selected.

In one embodiment, the catalyst includes a procatalyst composition that contains a titanium functional group, such as titanium chloride, a magnesium functional group, such as magnesium chloride, and at least one internal electron donor.

The procatalyst precursor may include (i) magnesium, (ii) a transition metal compound of an element from Groups IV-VII of the periodic table of elements, (iii) a halide, oxyhalide 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.

In one embodiment, the procatalyst precursor contains magnesium as the only metal component. Non-limiting examples include anhydrous magnesium chloride and/or an alcohol adduct thereof, magnesium alkoxide or aryloxide, mixed magnesium alkoxy halide and/or carboxylated magnesium dialkoxide or aryloxide.

In one embodiment, the procatalyst precursor is an alcohol adduct of anhydrous magnesium chloride. The anhydrous magnesium chloride adduct is essentially defined as MgCl ₂ -nROH, where n is in the range of 1.5-6.0, preferably 2.5-4.0 and most preferably 2.8-3.5 moles of total alcohol. ROH is a C ₁ -C ₄ alcohol, a linear or branched alcohol, or an alcohol mixture. Preferably, ROH is ethanol or a mixture of ethanol and a higher alcohol. If 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.

In one embodiment, a substantially spherical MgCl ₂ -nEtOH adduct can be formed by a spray crystallization process. In one embodiment, the spherical MgCl ₂ precursor has an average particle size (Malvern d ₅₀ ) of about 15-150 μm, preferably 20-100 μm, and most preferably 35-85 μm.

In one embodiment, the procatalyst precursor contains a transition metal compound and a magnesium metal compound. The transition metal compound has the general formula TrX _x where Tr is a transition metal, X is a halogen or C _1-10 hydrocarbyl group, and x is the number of such X groups in the compound in combination with the magnesium metal compound. Tr may be a Group IV, V or VI metal. In one embodiment, Tr is a Group IV metal, such as titanium. X may be a chloride, bromide, C _1-4 alkoxide or phenoxide, or a mixture thereof. In one embodiment, X is a chloride.

The precursor composition can be obtained by chlorinating the above mixed magnesium compounds, titanium compounds or mixtures thereof.

In one embodiment, the precursor composition is a mixed magnesium/titanium compound of the formula Mg _d Ti(OR ^e ) _f X _g where R ^e is an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, or COR' where R represents an aliphatic or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms; all OR ^e groups may be the same or different; X independently represents chlorine, bromine or iodine; D ranges from 0.5 to 56; or 2-4, or 3; F is from 2 to 116 or from 5 to 15; and g is from 0.5 to 116 or from 1 to 3.

In accordance with the present invention, the above-described procatalyst precursor is combined with at least one internal electron donor. The internal electron donor may be a substituted phenylene aromatic diester.

In one embodiment, the first internal electron donor contains a substituted phenylene aromatic diester with the following structure (I):

where R ₁ -R ₁₄ can be the same or different. Each of the groups R ₁ -R ₁₄ is selected from hydrogen, a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, a heteroatom, and combinations thereof At least one of R ₁ -R ₁₄ is not hydrogen.

In one embodiment, the substituted phenylene aromatic diester can be any substituted phenylene aromatic diester as described in US Patent Application No. 61/141,959, filed December 31, 2008, the contents of which are incorporated herein by reference in their entirety.

In one embodiment, the substituted phenylene aromatic diester may be any substituted phenylene aromatic diester described in WO12088028, filed December 20, 2011, the entire contents of which are incorporated herein by reference.

In one embodiment, at least one (or two, or three, or four) R group(s) of R ₁ -R ₄ is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group a group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, a heteroatom and combinations thereof.

In one embodiment, at least one (or some or all) R group(s) of R ₅ -R ₁₄ is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, a heteroatom and combinations thereof. In another embodiment, at least one of the R ₅ -R ₉ groups and at least one of the R ₁₀ -R ₁₄ groups is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, a heteroatom and combinations thereof.

In one embodiment, at least one of the R ₁ -R ₄ groups and at least one of the R ₅ -R ₁₄ groups is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, a heteroatom and combinations thereof. In another embodiment, at least one of the R ₁ -R ₄ groups, at least one of the R ₅ -R ₉ groups and at least one of the R ₁₀ -R ₁₄ groups is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, a heteroatom and combinations thereof.

In one embodiment, any consecutive R groups in R ₁ -R ₄ , and/or any consecutive R groups in R ₅ -R ₉ , and/or any consecutive R groups in R ₁₀ -R ₁₄ can be linked together to form intermolecular cyclic or intramolecular cyclic structure. Such inter- or intramolecular cyclic structure may or may not be aromatic. In one embodiment, the inter- or intramolecular cyclic structure is a C ₅ - or C ₆ -membered ring.

In one embodiment, at least one of the R ₁ -R ₄ groups is selected from a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and combinations thereof. At least one of R ₅ -R ₁₄ may optionally represent a halogen atom or an alkoxy group having from 1 to 20 carbon atoms. The groups R ₁ -R ₄ and/or R ₅ -R ₉ and/or R ₁₀ -R ₁₄ may optionally be linked to each other to form an intermolecular cyclic or intramolecular cyclic structure. Such intermolecular cyclic structure and/or intramolecular cyclic structure may or may not be aromatic.

In one embodiment, any successive R groups in R ₁ -R ₄ , and/or in R ₅ -R ₉ , and/or in R ₁₀ -R ₁₄ may be included in a C ₅ -C ₆ membered ring.

In one embodiment, structure (I) includes the groups R ₁ , R ₃ and R ₄ , which represent hydrogen. R ₂ is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, and combinations thereof. The R ₅ -R ₁₄ groups may be the same or different, and each of the R ₅ -R ₁₄ groups is selected from hydrogen, a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group , having from 1 to 20 carbon atoms, halogen and their combinations.

In one embodiment, the R ₂ group is selected from a C ₁ -C ₈ alkyl group, a C ₃ -C ₆ cycloalkyl group, or a substituted C ₃ -C ₆ cycloalkyl group. R ₂ may represent a methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, isobutyl group, sec-butyl group, 2,4,4-trimethylpentan-2-yl group, cyclopentyl group and cyclohexyl group .

In one embodiment, structure (I) includes an R ₂ group, which represents methyl, and each of the R ₅ -R ₁₄ groups represents hydrogen.

In one embodiment, structure (I) includes an R ₂ group, which represents ethyl, and each of the R ₅ -R ₁₄ groups represents hydrogen.

In one embodiment, structure (I) includes an R ₂ group that represents tert-butyl and each of the R ₅ -R ₁₄ groups represents hydrogen.

In one embodiment, structure (I) includes an R ₂ group that is ethoxycarbonyl and each of the R ₅ -R ₁₄ groups is hydrogen.

In one embodiment, structure (I) includes the groups R ₂ , R ₃ and R ₄ , each of which is hydrogen, and the group R ₁ is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group, having from 1 to 20 carbon atoms, and their combinations. The groups R ₅ -R ₁₄ may be the same or different, and each of them is selected from hydrogen, a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, halogen and their combinations.

In one embodiment, structure (I) includes an R ₁ group that represents methyl and each of the R ₅ -R ₁₄ groups represents hydrogen.

In one embodiment, structure (I) includes R ₂ and R ₄ groups, which are hydrogen, and the R ₁ and R ₃ groups may be the same or different. Each of the groups R ₁ and R ₃ is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, and combinations thereof. The R ₅ -R ₁₄ groups may be the same or different, and each of the R ₅ -R ₁₄ groups is selected from a substituted hydrocarbon group having from 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, halogen and their combinations.

In one embodiment, structure (I) includes R ₁ and R ₃ groups, which may be the same or different. Each of the groups R ₁ and R ₃ is selected from a C ₁ -C ₈ alkyl group, a C ₃ -C ₆ cycloalkyl group or a substituted C ₃ -C ₆ cycloalkyl group. The R ₅ -R ₁₄ groups may be the same or different, and each of the R ₅ -R ₁₄ groups is selected from hydrogen, a C ₁ -C ₈ alkyl group and halogen. Non-limiting examples of suitable C ₁ -C ₈ alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl,

tert-pentyl, n-hexyl and 2,4,4-trimethylpentan-2-yl groups. Non-limiting examples of suitable C ₃ -C ₆ cycloalkyl groups include cyclopentyl and cyclohexyl groups. In a further embodiment, at least one of the R ₅ -R ₁₄ groups is a C ₁ -C ₈ alkyl group or halogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₂ , R ₄ and R ₅ -R ₁₄ each represent hydrogen.

In one embodiment, structure (I) includes R ₁ and R ₃ groups, each of which is an isopropyl group. The groups R ₂ , R ₄ and R ₅ -R ₁₄ each represent hydrogen.

In one embodiment, structure (I) includes the groups R ₁ , R ₅ and R ₁₀ , each of which is a methyl group, and the group R ₃ , which is a tert-butyl group. The groups R ₂ , R ₄ , R ₆ -R ₉ and R ₁₁ -R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes the groups R ₁ , R ₇ and R ₁₂ , each of which is a methyl group, and the group R ₃ , which is a tert-butyl group. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ each represent an ethyl group. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes the groups R ₁ , R ₅ , R ₇ , R ₉ , R ₁₀ , R ₁₂ and R ₁₄ , each of which is a methyl group, and the group R ₃ , which is a tert -butyl group. The groups R ₂ , R ₄ , R ₆ , R ₈ , R ₁₁ and R ₁₃ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₅ , R ₇ , R ₉ , R ₁₀ , R ₁₂ and R ₁₄ are each an isopropyl group. The groups R ₂ , R ₄ , R ₆ , R ₈ , R ₁₁ and R ₁₃ are each hydrogen.

In one embodiment, the substituted phenylene aromatic diester has a structure (II) that includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₂ and R ₄ each represent hydrogen. The _R8 and _R9 groups fit into the _C6 -membered ring to form a 1-naphthoyl moiety. The R ₁₃ and R ₁₄ groups are included in the C ₆ -membered ring to form another 1-naphthoyl fragment. Structure (II) is shown below.

In one embodiment, the substituted phenylene aromatic diester has a structure (III) that includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₂ and R ₄ each represent hydrogen. The _R6 and _R7 groups fit into the _C6 -membered ring to form a 2-naphthoyl moiety. The R ₁₂ and R ₁₃ groups fit into the C ₆ -membered ring to form a 2-naphthoyl moiety. The structure of (III) is shown below.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ are each an ethoxy group. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ each represent a fluorine atom. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ each represent a chlorine atom. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ each represent a bromine atom. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ each represent an iodine atom. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups _R6 , _R7 , _R11 and _R12 each represent a chlorine atom. The groups R ₂ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₀ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups _R6 , _R8 , _R11 and _R13 each represent a chlorine atom. The groups R ₂ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₀ , R ₁₂ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₂ , R ₄ and R ₅ -R ₁₄ each represent a fluorine atom.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ are each a trifluoromethyl group. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ are each an ethoxycarbonyl group. The groups R ₂ , R ₄ , R ₅ , R _{6 ,} R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, the group R ₁ is a methyl group and the group R ₃ is a tert-butyl group. The groups R ₇ and R ₁₂ are each an ethoxy group. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a tert-butyl group. The groups R ₇ and R ₁₂ each represent a diethylamine group. The groups R ₂ , R ₄ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group, and an R ₃ group, which is a 2,4,4-trimethylpentan-2-yl group. The groups R ₂ , R ₄ and R ₅ -R ₁₄ each represent hydrogen.

In one embodiment, structure (I) includes R ₁ and R ₃ groups, each of which is a sec-butyl group. The groups R ₂ , R ₄ and R ₅ -R ₁₄ each represent hydrogen.

In one embodiment, the substituted phenylene aromatic diester has structure (IV), with the R ₁ and R ₂ groups included on a C ₆ membered ring to form a 1,2-naphthalene moiety. Each of the groups R ₅ -R ₁₄ represents hydrogen. The structure of (IV) is shown below.

In one embodiment, the substituted phenylene aromatic diester has structure (V), with R ₂ and R ₃ groups included on a C ₆ membered ring to form a 2,3-naphthalene moiety. Each of the groups R ₅ -R ₁₄ represents hydrogen. Structure (V) is shown below.

In one embodiment, structure (I) includes R ₁ and R ₄ groups, each of which is a methyl group. The groups R ₂ , R ₃ , R ₅ -R ₉ and R ₁₀ -R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes an R ₁ group, which is a methyl group. The R ₄ group is an isopropyl group. The groups R ₂ , R ₃ , R ₅ -R ₉ and R ₁₀ -R ₁₄ are each hydrogen.

In one embodiment, structure (I) includes the groups R ₁ , R ₃ and R ₄ , each of which is an isopropyl group. The groups R ₂ , R ₅ -R ₉ and R ₁₀ -R ₁₄ are each hydrogen.

In one embodiment, R ₁ and R ₄ are each selected from a methyl group, an ethyl group, and a vinyl group. Each of the groups R ₂ and R ₃ is selected from hydrogen, a secondary alkyl group or a tertiary alkyl group, wherein R ₂ and R ₃ are not hydrogen. In other words, if R2 is hydrogen, R3 is not hydrogen (and vice versa).

In one embodiment, a second internal electron donor may be used, containing an essentially polyether, which can be coordinated bidentately. In one embodiment, the second internal electron donor is a substituted 1,3-diester of structure VI:

where R ₁ and R ₂ are the same or different, methyl, C ₂ -C ₁₈ linear or branched alkyls, C ₃ -C ₁₈ cycloalkyl, C ₄ -C ₁₈ cycloalkyl-alkyl, C ₄ -C ₁₈ alkyl-cycloalkyl, phenyl, organosilicon, C ₇ -C ₁₈ arylalkyl or C ₇ -C ₁₈ alkylaryl radicals; and R ₁ or R ₂ may also represent a hydrogen atom.

In one embodiment, the second internal electron donor may comprise a 1,3-diester with a cyclic or polycyclic structure VII:

where R ₁ , R ₂ , R ₃ and R ₄ correspond to those described for R ₁ and R ₂ structures VI or can be combined to form one or more C ₅ -C ₇ fused aromatic or non-aromatic ring structures, optionally containing a heteroatom N, O or S. Specific examples of the second internal electron donor include 4,4-bis(methoxymethyl)-2,6-dimethylheptane, 9,9-bis(methoxymethyl)fluorene, or mixtures thereof.

The precursor is converted to a solid procatalyst by subsequent reaction (halogenation) with an inorganic halide compound, preferably a titanium halide compound, and the inclusion of internal electron donors.

One suitable method for halogenating a precursor is to react the precursor at an elevated temperature with a tetravalent titanium halide, optionally in the presence of a hydrocarbon or halohydrocarbon diluent. A preferred tetravalent titanium halide is titanium tetrachloride.

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

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

As used herein, the term “cocatalyst” means a substance capable of converting a procatalyst into an active polymerization catalyst. The cocatalyst may contain hydrides, alkyls or aryls of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium and combinations thereof. In one embodiment, the cocatalyst is an aluminum hydrocarbyla cocatalyst represented by the formula R ₃ Al, where each R group represents an alkyl, cycloalkyl, aryl or hydrogen radical; at least one R is a hydrocarbon radical; two or three R radicals can be combined into a cyclic radical to form a heterocyclic structure; each R can be the same or different; and each R which is a hydrocarbyl radical has from 1 to 20 carbon atoms, and preferably from 1 to 10 carbon atoms. In a further embodiment, each alkyl radical may be straight or branched chain, and such hydrocarbyl radical may be a mixed radical, i.e. the radical may contain alkyl, aryl and/or cycloalkyl groups. Non-limiting examples of suitable radicals include 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.

Non-limiting examples of suitable hydrocarbylaluminum compounds include triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, propylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, tri-n-dodecylaluminum. In one embodiment, the preferred cocatalysts are selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride and di-n-hexylaluminum hydride, and the most preferred cocatalyst is triethylaluminum.

In one embodiment, the cocatalyst is an organoaluminum compound represented by the formula R _n AlX _3-n where n = 1 or 2, R is an alkyl, and X is a halide or alkoxide. Non-limiting examples of suitable compounds include methylaluminoxane, isobutylaluminumoxane, diethylaluminum ethoxide, diisobutylaluminum chloride, tetraethyldialuminoxane, tetraisobutyldialuminoxane, diethylaluminum chloride, ethylaluminum dichloride, methylaluminum dichloride and dimethylaluminum chloride.

In one embodiment, the catalyst composition includes an external electron donor. As used herein, the term “external electron donor” means a compound added independently of the formation of the procatalyst and containing at least one functional group that is capable of donating a pair of electrons to a metal atom. Without intending to be limited by any particular theory, it is believed that an external electron donor improves the stereoselectivity of the catalyst (ie, reduces the amount of xylene-soluble material in the formant polymer).

In one embodiment, the external electron donor may be selected from one or more of the following compounds: alkoxysilane, amine, ether, carboxylate, ketone, amide, carbamate, phosphine, phosphate, phosphite, sulfonate, sulfone, and/or sulfoxide.

In one embodiment, the external electron donor is an alkoxysilane. Alkoxysilane has the following general formula: SiR _m (OR') _4-m (I) wherein each of the R groups independently represents hydrogen, or a hydrocarbon group, or an amino group, optionally substituted with one or more substituents containing one or more heteroatoms from the group 14, 15, 16 or 17, wherein said group R' contains up to 20 atoms, excluding hydrogen and halogen; R' represents a C _1-4 alkyl group; and m is 0, 1, 2 or 3. In one embodiment, R is a C _6-12 aryl, alkyl or aralkyl, a C _3-12 cycloalkyl, a C _3-12 branched alkyl, or a C _3-12 cyclic or acyclic amino group, R' is C _1-4 alkyl, 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, tetraethylaminetriethoxysilane, , cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane and dimethyldimethoxysilane. In one embodiment, the silane-based composition is dicyclopentyldimethoxysilane (DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), diisopropyldimethoxysilane (DIPDMS), n-propyltmethoxysilane (NPTMS), diethylaminotriethoxysilane (DATES) or n-propyltriethoxysilane (PTES), and any combination thereof.

In one embodiment, the external donor may be a mixture of at least 2 alkoxysilanes. In a further embodiment, the mixture may contain dicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane and tetraethoxysilane, or dicyclopentyldimethoxysilane and n-propyltriethoxysilane.

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 diester.

In one embodiment, the catalyst composition includes an activity limiting agent (ALA). As used herein, the term “activity limiting agent” (ALA) refers to a material that reduces the activity of the catalyst at elevated temperature (ie, above about 85°C). ALA inhibits or otherwise prevents disruption of the polymerization reactor and ensures continuity of the polymerization process. Typically, as the reaction temperature increases, the activity of Ziegler-Natta catalysts increases. Ziegler-Natta catalysts also typically retain high activity near the softening point temperature of the resulting polymer. The heat generated by the exothermic polymerization reaction can cause agglomerates to form from the polymer particles and ultimately disrupt the continuity of the polymer production process. ALA reduces the activity of the catalyst at elevated temperatures, thereby preventing disturbances in the operation of the reactor, reduces (or prevents) particle agglomeration and ensures continuity of the polymerization process.

The activity limiting agent may be a carboxylic acid ester, a diester, a poly(alkene glycol), a poly(alkene glycol) ester, a diol ester, and combinations thereof. The carboxylic acid ether may be an aliphatic or aromatic ether of a mono- or polycarboxylic acid. 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.

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 consists of dicyclopentyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and poly(ethylene glycol) laurate, dicyclopentyldimethoxysilane and isopropyl myristate with poly(ethylene glycol) dioleate, methylcyclohexyl dimethoxysilane and isopropyl myristate, n-propyl trimethoxysilane and isopropyl myristate, dimethyl dimethoxysilane and methylcyclohexyldimethoxysilane with isopropyl myristate, dicyclopentyldimethoxysilane and n-propyltriethoxysilane with isopropyl myristate, dicyclopentyldimethoxysilane and tetraethoxysilane, isopropyl myristate, pentyl valerate and combinations thereof.

In one embodiment, the catalyst composition includes any of the above external electron donors in combination with any of the above activity limiting agents.

Each of the first polypropylene polymer and the second polypropylene polymer may be formed from a catalyst system as described above. Propylene polymers can be formed from the same non-phthalate Ziegler-Natta catalyst system or can be prepared from different non-phthalate Ziegler-Natta catalyst systems. It has been found that by using a catalyst system as described above, in combination with controlling the xylene solubles content of the propylene polymer, first and second polypropylene polymers can be produced with relatively high catalytic activity while simultaneously producing a polypropylene polymer composition having excellent stiffness properties. For example, the first and second polypropylene polymers can be produced from a catalyst system as described above in a process in which the catalytic activity is at least 50 kg/g, such as at least 55 kg/g, such as at least 60 kg/g. g, for example even more than about 65 kg/g. Catalytic activity is typically less than about 100 kg/g. In accordance with the present invention, two different polypropylene polymers are then combined to maximize stiffness properties without sacrificing mechanical viscosity. Generally, the polypropylene polymer composition can be produced in a more efficient manner than previously produced polypropylene polymers. Moreover, in addition to excellent stiffness and toughness properties, the polypropylene resin composition of the present invention also has excellent thermoformability and moldability properties and can be easily molded into various articles and products.

For example, the polypropylene resin composition according to the present invention is well suited for producing molded articles. For example, the polypropylene composition can be used for injection molding, blow molding, extrusion and rotomoulding.

The polypropylene polymer composition of the present disclosure can be used to make a wide variety of articles and products. Due to its high rigidity and excellent flow properties, for example, the polypropylene polymer composition can be used to produce all different types of articles and products. High rigidity allows the production of products with relatively thin walls without compromising the required shape retention properties. In addition, high stiffness and toughness enable products and articles manufactured in accordance with this specification to withstand impact forces from falling loads or other external phenomena.

The polypropylene polymer composition of the present disclosure, for example, allows all different types of thin wall containers to be manufactured and therefore reduces the volume of polymer required to manufacture the article. Containers that can be manufactured in accordance with the present disclosure include, for example, storage containers, packaging containers, food containers, and the like. Other containers may include cups and other containers for storing drinks or liquids.

The present invention can be better understood by reference to the following example.

Example

Various polypropylene polymer compositions have been manufactured in accordance with the present invention and tested for stiffness and toughness. The samples were compared with polypropylene polymers of the main reactor class.

Samples prepared in accordance with the present disclosure included a first polypropylene polymer combined with a second polypropylene polymer to form a polypropylene polymer composition. All resulting polypropylene polymers were polymerized using a non-phthalate Ziegler-Natta catalyst system as described above. Specifically, the catalyst used was W. R. Grace & Co.'s CONSISTA catalyst. The polymers were produced in a gas-phase reactor. In this example, only polypropylene homopolymers were prepared.

In particular, samples of polymer granules were made, from which samples were cast. Specimens were prepared in accordance with ASTM Test D4101 for the preparation of flexural modulus and Izod impact test specimens.

The melt flow rate and xylene-soluble substance content of each resulting polypropylene polymer were measured. The following results were obtained.

MFR1 XS1 MFR2 XS2 MFR First polypropylene polymer,% by weight PDI XS (%) Module M, MPa according to Izod, J/m Comparative
sample 1 2.1 3 - - 2.1 100 4.1 3 1617 44.0 Comparative
sample 2 0.3 6.7 - - 0.3 100 4.3 6.7 1436 87.0 Comparative
sample 3 3 5.4 3 100 5 5.4 1497 44.5 Sample 1 0.8 3.8 10 2.5 2.5 56% 4.7 3.3 1722 49.0 Sample 2 0.8 3.8 20 3.5 2.1 66% 4.9 3.8 1722 46.9 Sample 3 0.3 3.8 10 2.5 2.5 35% 5.6 3.6 1784 53.0 Sample 4 0.3 3.8 20 3.5 1.6 50% 6.1 3.8 1794 60.9 Sample 5 0.3 3.8 10 2.5 0.7 80% 4.2 3 1652 70.4 Sample 6 0.8 7 10 7 2.3 56% 5.4 6.8 1497 54.2 Sample 7 0.3 7 10 7 2.3 40% 5.8 6.8 1540 64.4 Sample 8 0.15 7 10 7 2.2 thirty% 6.6 6.8 1585 60.1 Sample 9 0.8 7 10 1.5 2.7 56% 5 5 1626 63.7 Sample 10 0.9 1.5 10 7 2.2 56% 5.1 4.3 1665 58.5 Sample 11 0.15 7 10 3.5 2 thirty% 7.5 4.7 1725 50.3 Sample 12 0.15 7 20 3.5 2 40% 8.1 4.7 1757 50.9

In fig. 1 graphically presents the above results. In particular, in FIG. Figure 1 compares the flexural modulus with the xylene solubles content of the polymers. As shown, the polymers made in accordance with the present invention had significantly better stiffness properties than comparative samples. In one aspect, samples prepared in accordance with the present disclosure may exhibit a flexural modulus in accordance with the following equation:

2072 H XS ^-0.18

and the content of xylene soluble substances ranged from 3% by weight to 6.8% by weight.

These and other modifications and variations of the present invention can be implemented by those of ordinary skill in the art without departing from the spirit and scope of the present invention, which are more specifically set forth in the accompanying claims. In addition, it should be understood that aspects of the various embodiments may be completely or partially interchangeable. Moreover, those skilled in the art will appreciate that the above description is provided by way of example only and is not intended to limit the invention, which is further described in the accompanying claims.

Claims (41)

1. Polypropylene polymer composition for the production of molded products, containing: a first polypropylene polymer in combination with a second polypropylene polymer, wherein the melt flow rate of the first polypropylene polymer is from 0.1 g/10 min to 3 g/10 min, and the xylene solubles content is from 1.0% by weight to 7 % by weight, wherein the melt flow rate of the second polypropylene polymer is from 5 g/10 min to 100 g/10 min, and the content of xylene soluble substances is from 1% by weight to 7% by weight; the first polypropylene polymer is present in the polymer composition in an amount of from 30% to 66% by weight; And the first polypropylene polymer and the second polypropylene polymer both contain polypropylene polymers catalyzed by a Ziegler-Natta non-phthalate catalyst; wherein the flexural modulus of elasticity of the polypropylene polymer composition ranges from 1500 MPa to 2500 MPa; the content of xylene-soluble substances in the polypropylene polymer composition ranges from 2.5% to 7% by weight; wherein the first polypropylene polymer is a homopolymer; wherein the second polypropylene polymer is a polypropylene homopolymer or a polypropylene-ethylene copolymer having an ethylene content of less than or equal to 1.5% by weight; wherein the melt flow rate is measured in accordance with ASTM D 1238, at 230°C with a load of 2.16 kg; And wherein the flexural modulus was determined in accordance with Method A of ASTM D790-10 at 1.3 mm/min using an ASTM 3641 Type 1 specimen cast in accordance with ASTM D4101. 2. The polypropylene polymer composition according to claim 1, in which the content of xylene-soluble substances in the first polypropylene polymer is from 2.5% by weight to 7% by weight, and the content of xylene-soluble substances in the second polypropylene polymer is from 2.5 % by weight to 7% by weight. 3. The polypropylene polymer composition according to claim 1, in which the xylene-soluble substance content of one of the polypropylene polymers is more than 5% by weight, and the xylene-soluble substance content of the other polypropylene polymer is less than 4% by weight. 4. The polypropylene polymer composition according to claim 1, in which the xylene-soluble substance content of one of the polypropylene polymers is more than 6% by weight, and the xylene-soluble substance content of the other polypropylene polymer is less than 4% by weight. 5. Polypropylene polymer composition according to claim 1, which contains a nucleating agent. 6. Polypropylene polymer composition according to claim 1, which does not contain a nucleating agent. 7. The polypropylene polymer composition according to any one of the preceding claims, wherein the melt flow rate of the polypropylene polymer composition is from 0.5 g/10 min to 30 g/10 min, and the content of xylene soluble substances is from 3% to 7% by weight. weight 8. Polypropylene polymer composition according to any of the preceding paragraphs, in which the polydispersity coefficient of the polypropylene polymer composition is from 5 to 10. 9. The polypropylene polymer composition according to any one of the preceding claims, wherein the polydispersity coefficient of the first polypropylene polymer is from 4 to 5.5, and the polydispersity coefficient of the second polypropylene polymer is from 4 to 5.5. 10. The polypropylene polymer composition according to any one of the preceding claims, wherein the weight ratio between the first polypropylene polymer and the second polypropylene polymer is from 5:95 to 80:20. 11. The polypropylene polymer composition according to any one of the preceding claims, wherein the melt flow rate of the polypropylene polymer composition is from 0.5 g/10 min to 3 g/10 min. 12. The polypropylene polymer composition according to claim 11, in which the content of xylene-soluble substances in the composition is from 3.5 to 7% by weight. 13. Polypropylene polymer composition according to claims. 1-10, in which the melt flow rate of the polypropylene polymer composition is from 5 g/10 min to 30 g/10 min. 14. The polypropylene polymer composition according to any one of the preceding claims, wherein the Izod impact strength of the polypropylene polymer composition is more than 40 J/m and less than 90 J/m. 15. A method for producing a polypropylene polymer composition for the production of molded products, which includes: polymerization of propylene monomer in the presence of a non-phthalate Ziegler-Natta catalyst to obtain a polypropylene polymer composition containing a first polypropylene polymer in combination with a second polypropylene polymer, wherein the melt flow rate of the first polypropylene polymer is from 0.1 g/10 min to 3 g/10 min, and the xylene solubles content is from 1.0% by weight to 7 % by weight, wherein the melt flow rate of the second polypropylene polymer is from 5 g/10 min to 100 g/10 min, and the content of xylene soluble substances is from 1% by weight to 7% by weight; wherein the first polypropylene polymer is present in the polymer composition in an amount of from 30% to 66% by weight; And wherein the flexural modulus of elasticity of the polypropylene polymer composition ranges from 1500 MPa to 2500 MPa; the content of xylene-soluble substances in the polypropylene polymer composition ranges from 2.5% to 7% by weight; wherein the first polypropylene polymer is a homopolymer; wherein the second polypropylene polymer is a polypropylene homopolymer or a copolymer of polypropylene and ethylene having an ethylene content of less than or equal to 1.5% by weight; wherein the melt flow rate is measured in accordance with ASTM D 1238, at 230°C with a load of 2.16 kg; And wherein the flexural modulus was determined in accordance with Method A of ASTM D790-10 at 1.3 mm/min using an ASTM 3641 Type 1 specimen cast in accordance with ASTM D4101. 16. The method of claim 15, wherein each of the first polypropylene polymer and the second polypropylene polymer is formed in a gas phase reactor. 17. The method of claim 15, wherein each of the first polypropylene polymer and the second polypropylene polymer are formed in a liquid phase reactor. 18. The method of claim 15, wherein one of the first polypropylene polymer and the second polypropylene polymer is formed in a gas phase reactor, and the other of the first polypropylene polymer and the second polypropylene polymer is formed in a liquid phase reactor. 19. The method of claim 18, wherein the first polypropylene polymer is formed in a liquid phase reactor and the second polypropylene polymer is formed in a gas phase reactor. 20. The method of claim 15, wherein each of the first polypropylene polymer and the second polypropylene polymer are formed in separate reactors and then combined. 21. The method of claim 15, wherein the first polypropylene polymer and the second polypropylene polymer are formed sequentially in a series of reactors. 22. A container formed from a polypropylene polymer composition according to any one of paragraphs. 1-14. 23. The container according to claim 22, which is a storage container or a packaging container.

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