WO2020231526A1

WO2020231526A1 - Polypropylene-based compositions

Info

Publication number: WO2020231526A1
Application number: PCT/US2020/024563
Authority: WO
Inventors: George J. Pehlert; Sarah K. NEWBY
Original assignee: Exxonmobil Chemical Patents Inc.
Priority date: 2019-05-15
Filing date: 2020-03-25
Publication date: 2020-11-19

Abstract

The present disclosure provides polyolefin compositions, such as polypropylenes, and methods for producing the composition and articles therefrom. The polyolefin compositions contain one or more long chain branched (LCB) polypropylenes and one or more linear polypropylenes. The polyolefin composition contains 10 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 90 wt% of the linear polypropylene, by weight of the polyolefin composition. The LCB polypropylene has a melt strength of 10 cN to 100 cN and a branching index (g'vis) of less than 0.95 and the linear polypropylene has a melt strength of 10 cN to 100 cN and a branching index (g'vis) of 0.95 or greater. The polyolefin composition has a melt strength of greater than 10 cN to 100 cN and a melt flow rate from 0.8 g/lO min to 20 g/lO min.

Description

POLYPROPYLENE-BASED COMPOSITIONS

INVENTORS: George J. Pehlert and Sarah K. Newby CROSS-REFERENCE OF RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 62/848,144, filed May 15, 2019, and EP 19191234.4 filed August 12, 2019, the disclosures of which are incorporated herein by reference.

FIELD

[0002] The present disclosure provides compositions containing polyolefin compositions, such as polypropylene-based materials, and methods of forming polyolefin compositions and articles from the polyolefin compositions.

BACKGROUND

[0003] In producing polymeric films, especially blown films, polymers with good processability are desired to achieve commercial throughput rates, while maintaining sufficient toughness. Further, desirable physical properties for the final film product include stiffness, roughness, or tear strength. High density polyethylene (HDPE) and polypropylene (PP) are two possible blending partners for polyethylene (PE) film to increase the stiffness. However, there are limited cases for selecting PP as a blending partner, because PP and PE have different crystallinity phases and types, and there is little to no co-crystallinity between PP and PE. Lean blending PP with PE can increase PE film stiffness while decreasing the PE film toughness at same time.

[0004] On the other hand, PP contains many advantages versus HDPE, such as much lower density, higher stiffness, and higher heat resistance. If PP can be used in a majority PE formulation to improve the film stiffness while still maintaining toughness properties, it would provide value for industrial and food package down-gauging of the PP/PE film structure. However, some properties, such as melt strength and strain hardening, of PP are not preserved through exposure to compounding and/or heat processing.

[0005] Therefore, there is a need for improved polyolefin compositions having relatively high melt strength and strain hardening, while maintaining toughness and stiffness, and methods for producing the polyolefin compositions and forming articles from the polyolefin compositions. [0006] Publications of interest include WO 2018/147944, EP 2 386 601 Al, US 9,376,549 and US 9,522,984.

SUMMARY

[0007] The present disclosure provides polyolefin compositions, such as compositions including polypropylenes, and methods for producing the polyolefin compositions, as well as forming films and other articles from the polyolefin compositions. The polyolefin compositions contain mixtures of two or more broad molecular weight distribution (BMWD) polypropylenes. For example, the polyolefin compositions contain one or more long chain branched (LCB) BMWD polypropylenes and one or more linear BMWD polypropylenes. Methods for forming articles from the polyolefin compositions can include foaming, thermoforming, sheet extrusion, blown film, injection molding, and/or other processes.

[0008] In any embodiment, a polyolefin composition contains (or comprises, or consists of, or consists essentially of) 10 wt% to 90 wt%, by weight of the polyolefin composition, of one or more LCB polypropylenes and 10 wt% to 90 wt%, by weight of the polyolefin composition, of one or more linear polypropylenes. The LCB polypropylene has a melt strength of 10 cN to 100 cN and a branching index (g'vis) of less than 0.95 and the linear polypropylene has a melt strength of 10 cN to 100 cN and a branching index t g’ _{vis )} of 0.95 or greater. The polyolefin composition has a melt strength of greater than 10 cN to 100 cN and a melt flow rate from 0.8 g/10 min to 20 g/10 min.

[0009] In any embodiment, a polyolefin composition contains (or comprises, or consists of, or consists essentially of) 10 wt% to 30 wt%, by weight of the polyolefin composition, of one or more LCB polypropylenes and 70 wt% to 90 wt%, by weight of the polyolefin composition, of one or more linear polypropylenes. The LCB polypropylene has a melt strength of 10 cN to 30 cN and a branching index t g' _vis J of 0.86 to 0.92 and the linear polypropylene has a melt strength of 25 cN to 50 cN and a branching index t g' _vis J of 0.98 to 1. The polyolefin composition has a melt strength of greater than 22 cN to 40 cN and a melt flow rate from 1.3 g/10 min to 5 g/10 min.

[0010] In any embodiment, a method of forming articles from a polyolefin composition includes (or comprises, or consists of, or consists essentially of) combining 10 wt% to 90 wt%, by weight of the polyolefin composition, of one or more LCB polypropylenes and 10 wt% to 90 wt%, by weight of the polyolefin composition, of one or more linear polypropylenes to produce the polyolefin composition. The LCB polypropylene has a melt strength of 10 cN to 100 cN and a branching index (g'_ViS) of less than 0.95, and the linear polypropylene has a melt strength of 10 cN to 100 cN and a branching index (g i_s) of 0.95 or greater. The polyolefin composition has a melt strength of

greater than 20 cN to 80 cN and a melt flow rate from 0.8 g/10 min to 20 g/10 min.

[0011] In any embodiment, a method of forming articles from a polyolefin composition comprising a mixture of two or more polypropylenes includes (or comprises, or consists of, or consists essentially of) combining one or more LCB polypropylenes and one or more linear polypropylenes, where a greater concentration of the LCB polypropylene in the polyolefin composition relative to the concentration of the linear polypropylene provides a stiff article having a high flexural modulus of greater than 250 MPa to 1,500 MPa, or a greater concentration of the linear polypropylene in the polyolefin composition relative to the concentration of the LCB polypropylene, provides a flexible article having a low flexural modulus of 50 MPa to 250 MPa.

[0012] In any embodiment, a method of forming a film includes (or comprises, or consists of, or consists essentially of) extruding a polyolefin composition through one or more die openings to form the film. For example, the method can include extruding a molten polyolefin composition containing 10 wt% to 90 wt%, by weight of the polyolefin composition, of one or more LCB polypropylenes and 10 wt% to 90 wt%, by weight of the polyolefin composition, of one or more linear polypropylenes through the die opening to form the film, and cooling the film at a distance away from the die opening to produce a finished film.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] So that the manner in which the above recited features of the disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to implementations, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical implementations of this disclosure and are therefore not to be considered limiting of scope, for the disclosure may admit to other equally effective implementations.

[0014] FIG. 1 depicts a graph illustrating MFR values of the polyolefin compositions relative to different concentrations of the linear polypropylene.

[0015] FIG. 2 depicts a graph illustrating melt strength values of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes.

[0016] FIG. 3 depicts a graph illustrating molecular weight distribution of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes.

[0017] FIG. 4 depicts a graph illustrating long chain branching of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes.

[0018] FIG. 5 depicts a graph illustrating polydispersity index (PDI) of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes.

[0019] FIG. 6 depicts a graph illustrating extensional viscosity of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes.

[0020] FIG. 7 depicts another graph illustrating extensional viscosity of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes [0021] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the Figures. It is contemplated that elements and features of one implementation may be beneficially incorporated in other implementations without further recitation.

DETAILED DESCRIPTION

[0022] The present disclosure provides polyolefin compositions that contain one or more long chain branched (LCB) polypropylenes and one or more linear polypropylenes. The LCB polypropylene and the linear polypropylene are each independently a broad molecular weight distribution (BMWD) polypropylene. Multiple types of articles can be produced from the polyolefin composition depending on the concentration ratios of the LCB polypropylene and the linear polypropylene, as well as the specific type of application used to produce the article. For example, a stiff article or product having a relatively high flexural modulus (e.g., greater than 20 MPa) can be produced by increasing the concentration of the LCB polypropylene. Alternatively, a flexible article or product having a low flexural modulus (e.g., 20 MPa or less) can be produced by increasing the concentration of the linear polypropylene. The articles can be produced by foaming, thermoforming, sheet extrusion, blown film, injection molding, and/or other processes.

[0023] In one or more embodiments, inclusion of the linear polypropylene to the LCB polypropylene to produce the polyolefin composition improves and/or maintains the melt strength of the LCB polypropylene during and after thermal processing cycles and allows for tailoring of melt strength and strain hardening for elongational flow applications. In other embodiments, addition of the LCB polypropylene to the linear polypropylene to produce the polyolefin composition improves the strain hardening of the linear polypropylene allowing for tailoring of melt strength and strain hardening in applications where the primary resin of choice is the linear polypropylene for elongational flow applications.

[0024] In any embodiment, the polyolefin composition contains from 5 wt%, 10 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or 55 wt% to 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of the LCB polypropylene, by weight of the polyolefin composition. For example, the polyolefin composition contains from 5 wt% to 95 wt%, 10 wt% to 90 wt%, 20 wt% to 90 wt%, 25 wt% to 90 wt%, 30 wt% to 90 wt%, 35 wt% to 90 wt%, 40 wt% to 90 wt%, 50 wt% to 90 wt%, 60 wt% to 90 wt%, 70 wt% to 90 wt%, 75 wt% to 90 wt%, 80 wt% to 90 wt%, 85 wt% to 90 wt%, 10 wt% to 80 wt%, 20 wt% to 80 wt%, 25 wt% to 80 wt%, 30 wt% to 80 wt%, 35 wt% to 80 wt%, 40 wt% to 80 wt%, 50 wt% to 80 wt%, 10 wt% to 60 wt%, 20 wt% to 60 wt%, 25 wt% to 60 wt%, 30 wt% to 60 wt%, 35 wt% to 60 wt%, 40 wt% to 60 wt%, 50 wt% to 60 wt%, 10 wt% to 50 wt%, 20 wt% to 50 wt%, 25 wt% to 50 wt%, 30 wt% to 50 wt%, 35 wt% to 50 wt%, 40 wt% to 50 wt%, 10 wt% to 30 wt%, 20 wt% to 30 wt%, 25 wt% to 30 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, or 10 wt% to 15 wt% of the LCB polypropylene, by weight of the polyolefin composition.

[0025] In any embodiment, the polyolefin composition contains from 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, or 25 wt% to 28 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of the linear polypropylene, by weight of the polyolefin composition. For example, the polyolefin composition contains 5 wt% to 95 wt%, 5 wt% to 90 wt%, 10 wt% to 90 wt%, 20 wt% to 90 wt%, 25 wt% to 90 wt%, 30 wt% to 90 wt%, 40 wt% to 90 wt%, 50 wt% to 90 wt%, 60 wt% to 90 wt%, 70 wt% to 90 wt%, 75 wt% to 90 wt%, 80 wt% to 90 wt%, 5 wt% to 70 wt%, 10 wt% to 70 wt%, 15 wt% to 70 wt%, 20 wt% to 70 wt%, 25 wt% to 70 wt%, 30 wt% to 70 wt%, 40 wt% to 70 wt%, 50 wt% to 70 wt%, 60 wt% to 70 wt%, 5 wt% to 60 wt%, 10 wt% to 60 wt%, 15 wt% to 60 wt%, 20 wt% to 60 wt%, 25 wt% to 60 wt%, 30 wt% to 60 wt%, 40 wt% to 60 wt%, 50 wt% to 60 wt%, 5 wt% to 50 wt%, 10 wt% to 50 wt%, 15 wt% to 50 wt%, 20 wt% to 50 wt%, 25 wt% to 50 wt%, 30 wt% to 50 wt%, 40 wt% to 50 wt%, 10 wt% to 40 wt%, 5 wt% to 30 wt%, 10 wt% to 30 wt%, 15 wt% to 30 wt%, 20 wt% to 30 wt%, 25 wt% to 30 wt%, 5 wt% to 20 wt%, 10 wt% to 20 wt%, or 15 wt% to 20 wt% of the linear polypropylene, by weight of the polyolefin composition.

[0026] In one or more examples, the polyolefin composition contains from 10 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 90 wt% of the linear polypropylene, by weight of the polyolefin composition. In some examples, the polyolefin composition contains 40 wt% to 90 wt% of the LCB polypropylene and 10 wt % to 60 wt % of the linear polypropylene, by weight of the polyolefin composition. In other examples, the polyolefin composition contains 70 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 30 wt% of the linear polypropylene, by weight of the polyolefin composition. In other examples, the polyolefin composition contains 80 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 20 wt% of the linear polypropylene, by weight of the polyolefin composition.

[0027] In other embodiments, the polyolefin composition contains 10 wt% to 60 wt% of the LCB polypropylene and 40 wt% to 90 wt% of the linear polypropylene, by weight of the polyolefin composition. In some examples, the polyolefin composition contains 10 wt% to 30 wt% of the LCB polypropylene and 70 wt% to 90 wt% of the linear polypropylene, by weight of the polyolefin composition. In other examples, the polyolefin composition contains 10 wt% to 20 wt% of the LCB polypropylene and 80 wt% to 90 wt% of the linear polypropylene, by weight of the polyolefin composition.

[0028] In any embodiment, the polyolefin composition has a melt strength of 10 cN, or greater than 10 cN, greater than 15 cN, or greater than 20 cN. The polyolefin composition has a melt strength of 10 cN, 12 cN, 15 cN, 18 cN, 20 cN, 22 cN, 25 cN, 30 cN, 35 cN, or 38 cN to 40 cN, 45 cN, 50 cN, 60 cN, 70 cN, 80 cN, 90 cN, 100 cN, 120 cN, 150 cN, or greater. For example, the polyolefin composition has a melt strength of greater than 10 cN to 150 cN, greater than 10 cN to 120 cN, greater than 10 cN to 100 cN, greater than 10 cN to 80 cN, greater than 10 cN to 65 cN, greater than 10 cN to 50 cN, greater than 10 cN to 40 cN, greater than 10 cN to 30 cN, 20 cN to 150 cN, 20 cN to 120 cN, 20 cN to 100 cN, 20 cN to 80 cN, 20 cN to 65 cN, 20 cN to 50 cN, 20 cN to 40 cN, 20 cN to 30 cN, greater than 20 cN to 150 cN, greater than 20 cN to 120 cN, greater than 20 cN to 100 cN, greater than 20 cN to 80 cN, greater than 20 cN to 65 cN, greater than 20 cN to 50 cN, greater than 20 cN to 40 cN, greater than 20 cN to 30 cN, 22 cN to 150 cN, 22 cN to 120 cN, 22 cN to 100 cN, 22 cN to 80 cN, 22 cN to 65 cN, 22 cN to 50 cN, 22 cN to 40 cN, 22 cN to 30 cN, 25 cN to 150 cN, 25 cN to 120 cN, 25 cN to 100 cN, 25 cN to 80 cN, 25 cN to 65 cN, 25 cN to 50 cN, 25 cN to 40 cN, 25 cN to 30 cN, 30 cN to 150 cN, 30 cN to 120 cN, 30 cN to 100 cN, 30 cN to 80 cN, 30 cN to 65 cN, 30 cN to 50 cN, or 30 cN to 40 cN.

[0029] In any embodiment, the polyolefin composition has a melt flow rate (MFR) of 0.5 g/10 min, 0.8 g/10 min, 1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.5 g/10 min, 1.8 g/10 min, or 2 g/10 min to 2.5 g/10 min, 3 g/10 min, 3.5 g/10 min, 4 g/10 min, 5 g/10 min, 8 g/10 min, 10 g/10 min, 12 g/10 min, 15 g/10 min, 18 g/10 min, 20 g/10 min, or greater, as determined according to ASTM D1238 Condition L. For example, the polyolefin composition has an MFR of 0.5 g/10 min to 20 g/10 min, 0.8 g/10 min to 20 g/10 min, 1 g/10 min to 20 g/10 min, 1.3 g/10 min to 20 g/10 min, 1.5 g/10 min to 20 g/10 min, 1.8 g/10 min to 20 g/10 min, 2 g/10 min to 20 g/10 min, 2.5 g/10 min to 20 g/10 min, 3 g/10 min to 20 g/10 min, 3.5 g/10 min to 20 g/10 min, 0.5 g/10 min to 10 g/10 min, 0.8 g/10 min to 10 g/10 min, 1 g/10 min to 10 g/10 min, 1.3 g/10 min to 10 g/10 min, 1.5 g/10 min to 10 g/10 min, 1.8 g/10 min to 10 g/10 min, 2 g/10 min to 10 g/10 min, 2.5 g/10 min to 10 g/10 min, 3 g/10 min to 10 g/10 min, 3.5 g/10 min to 10 g/10 min, 0.5 g/10 min to 5 g/10 min, 0.8 g/10 min to 5 g/10 min, 1 g/10 min to 5 g/10 min, 1.3 g/10 min to 5 g/10 min, 1.5 g/10 min to 5 g/10 min, 1.8 g/10 min to 5 g/10 min, 2 g/10 min to 5 g/10 min, 2.5 g/10 min to 5 g/10 min, 3 g/10 min to 5 g/10 min, 3.5 g/10 min to 5 g/10 min, 0.5 g/10 min to 3.5 g/10 min, 0.8 g/10 min to 3.5 g/10 min, 1 g/10 min to 3.5 g/10 min, 1.3 g/10 min to 3.5 g/10 min, 1.5 g/10 min to 3.5 g/10 min, 1.8 g/10 min to 3.5 g/10 min, 2 g/10 min to 3.5 g/10 min, 2.5 g/10 min to 3.5 g/10 min, or 3 g/10 min to 3.5 g/10 min, as determined according to ASTM D1238 Condition L.

[0030] In one or more embodiments, the polyolefin composition or a product or article containing the polyolefin composition can be relatively stiff (e.g., stiff article) due to a greater concentration of the LCB polypropylene in the polyolefin composition relative to the concentration of the linear polypropylene, and therefore the polyolefin composition has a relatively high flexural modulus (e.g., greater than 250 MPa). In other embodiments, the polyolefin composition or a product or article containing the polyolefin composition can be relatively flexible (e.g., flexible article) due to a greater concentration of the linear polypropylene in the polyolefin composition relative to the concentration of the LCB polypropylene, and therefore the polyolefin composition has a relatively low flexural modulus (e.g., 250 MPa or less).

[0031] In any embodiment, the polyolefin composition has an extensional viscosity greater than an extensional viscosity of the linear polypropylene and less than an extensional viscosity of the LCB polypropylene, whereas all of the extensional viscosities are measured at the same temperature, such as at 190°C. In one or more examples, the polyolefin composition can have an extensional viscosity of 10 kPa-s, 15 kPa-s, 25 kPa-s, 50 kPa-s, 65 kPa-s, 80 kPa-s, or 100 kPa-s to 120 kPa-s, 150 kPa-s, 200 kPa-s, 250 kPa-s, 300 kPa-s, 400 kPa-s, 500 kPa-s, 600 kPa-s, 700 kPa-s, 850 kPa-s, or 1,000 kPa-s, as measure at 190°C. For example, the polyolefin composition can have an extensional viscosity of 10 kPa-s to 1,000 kPa-s, 15 kPa-s to 700 kPa-s, 25 kPa-s to 700 kPa-s, 50 kPa-s to 700 kPa-s, 100 kPa-s to 700 kPa-s, 150 kPa-s to 700 kPa-s, 200 kPa-s to 700 kPa-s, 300 kPa-s to 700 kPa-s, 500 kPa-s to 700 kPa-s, 15 kPa-s to 500 kPa-s, 25 kPa-s to 500 kPa-s, 50 kPa-s to 500 kPa-s, 100 kPa-s to 500 kPa-s, 150 kPa-s to 500 kPa-s, 200 kPa-s to 500 kPa-s, 300 kPa-s to 500 kPa-s, 15 kPa-s to 350 kPa-s, 25 kPa-s to 350 kPa-s, 50 kPa-s to 350 kPa-s, 100 kPa-s to 350 kPa-s, 150 kPa-s to 350 kPa-s, 200 kPa-s to 350 kPa-s, 300 kPa-s to 350 kPa-s, as measure at 190°C.

[0032] In one or more embodiments, the polyolefin composition has a high 1% secant flexural modulus, in each of the machine direction (MD) and the transverse direction (TD), independently, of greater than 250 MPa, such as from 260 MPa, 280 MPa, 300 MPa, 350 MPa, 400 MPa, 450 MPa, 500 MPa, 600 MPa, 700 MPa, 800 MPa, 900 MPa, 1,100 MPa, 1,200 MPa, 1,350 MPa, 1,500 MPa, or 1,700 MPa to 1,800 MPa, 2,000 MPa, 2,100 MPa, 2,250 MPa, 2,300 MPa, 2,500 MPa, 2,750 MPa, or 3,000 MPa, as determined for a film containing the polyolefin composition and having a thickness of 90 pm. For example, the polyolefin composition has a high 1% secant flexural modulus, in each of the machine direction (MD) and the transverse direction (TD), independently, of greater than 250 MPa to 3,000 MPa, greater than 250 MPa to

2.500 MPa, greater than 250 MPa to 2,300 MPa, greater than 250 MPa to 2,250 MPa, greater than 250 MPa to 2,000 MPa, greater than 250 MPa to 1,800 MPa, greater than 250 MPa to

1.500 MPa, greater than 250 MPa to 1,200 MPa, greater than 250 MPa to 1,000 MPa, greater than 250 MPa to 800 MPa, greater than 250 MPa to 500 MPa, 500 MPa to 3,000 MPa, 500 MPa to 2,500 MPa, 500 MPa to 2,300 MPa, 500 MPa to 2,250 MPa, 500 MPa to 2,000 MPa, 500

MPa to 1,800 MPa, 500 MPa to 1,500 MPa, 500 MPa to 1,200 MPa, 500 MPa to 1,000 MPa,

500 MPa to 800 MPa, 1,000 MPa to 3,000 MPa, 1,000 MPa to 2,500 MPa, 1,000 MPa to 2,300

MPa, 1,000 MPa to 2,250 MPa, 1,000 MPa to 2,000 MPa, 1,000 MPa to 1,800 MPa, 1,000 MPa to 1,500 MPa, 1,000 MPa to 1,200 MPa, 1,500 MPa to 3,000 MPa, 1,500 MPa to 2,500 MPa,

1,500 MPa to 2,300 MPa, 1,500 MPa to 2,250 MPa, 1,500 MPa to 2,000 MPa, 1,500 MPa to

1,800 MPa, 1,700 MPa to 3,000 MPa, 1,700 MPa to 2,500 MPa, 1,700 MPa to 2,300 MPa,

1,700 MPa to 2,250 MPa, or 1,700 MPa to 2,000 MPa, as determined for a film of the polyolefin composition having a thickness of 90 pm. In other examples, the polyolefin composition has a high 1% secant flexural modulus, in each of the machine direction (MD) and the transverse direction (TD), independently, 260 MPa to 1,500 MPa, 280 MPa to 1,500 MPa, 300 MPa to 1,500 MPa, 300 MPa to 1,200 MPa, 300 MPa to 1,000 MPa, 300 MPa to 800 MPa, 300 MPa to 600 MPa, 300 MPa to 500 MPa, 400 MPa to 1,200 MPa, 400 MPa to 1,000 MPa, 400 MPa to 800 MPa, or 400 MPa to 600 MPa, as determined for a film of the polyolefin composition having a thickness of 90 pm.

[0033] In other embodiments, the polyolefin composition has a low 1% secant flexural modulus, in each of the machine direction (MD) and the transverse direction (TD), independently, of 250 MPa or less, such as from 10 MPa, 30 MPa, 50 MPa, 80 MPa, or 100 MPa to 120 MPa, 150 MPa, 180 MPa, 200 MPa, 220 MPa, 230 MPa, 240 MPa, 245 MPa, or 250 MPa, as determined for a film containing the polyolefin composition and having a thickness of 90 pm. For example, the polyolefin composition has a low 1% secant flexural modulus, in each of the machine direction (MD) and the transverse direction (TD), independently, of 10 MPa to 250 MPa, 30 MPa to 250 MPa, 50 MPa to 250 MPa, 80 MPa to 250 MPa, 100 MPa to 250 MPa, 120 MPa to 250 MPa, 150 MPa to 250 MPa, 180 MPa to 250 MPa, 200 MPa to 250 MPa, 220 MPa to 250 MPa, 230 MPa to 250 MPa, 240 MPa to 250 MPa, 10 MPa to 240 MPa, 30 MPa to 240 MPa, 50 MPa to 240 MPa, 80 MPa to 240 MPa, 100 MPa to 240 MPa, 120 MPa to 240 MPa, 150 MPa to 240 MPa, 180 MPa to 240 MPa, 200 MPa to 240 MPa, 220 MPa to 240 MPa, 230 MPa to 240 MPa, 10 MPa to 200 MPa, 30 MPa to 200 MPa, 50 MPa to 200 MPa, 80 MPa to 200 MPa, 100 MPa to 200 MPa, 120 MPa to 200 MPa, 150 MPa to 200 MPa, 180 MPa to 200 MPa, 10 MPa to 150 MPa, 30 MPa to 150 MPa, 50 MPa to 150 MPa, 80 MPa to 150 MPa, 100 MPa to 150 MPa, or 120 MPa to 150 MPa, as determined for a film containing the polyolefin composition and having a thickness of 90 pm. The 1% secant flexural modulus is determined by the ExxonMobil PLFL- 242.001 standard, as provided below in the Examples section.

Long Chain Branched (LCB) Polypropylenes

[0034] The polyolefin compositions of the present disclosure include one or more broad molecular weight distribution (BMWD) polypropylenes which are or contain one or more long chain branched (LCB) polypropylenes.

[0035] The efficiency of the reaction between polypropylene and a thermally decomposing free-radical forming agent is enhanced by judicious selection of the process conditions including granule temperature, granule size, residence time, atmosphere (e.g., O2 deficient), or other conditions. Reaction efficiency improvements of as much as 20% were demonstrated, allowing for use of a relatively low amount of organic peroxide. This improvement in efficiency is beneficial from a materials handling and cost perspective since a lower concentration of the thermally decomposing free-radical forming agent is needed.

[0036] LCB polypropylenes can be formed by mixing a polypropylene with an organic peroxide. As used herein, "mixing" refers to intimately combining solid polypropylene and organic peroxide, which may be solid. In some embodiments, a homogenizer is used for such mixing. "Homogenizers" are mechanical devices that combine two or more distinct materials, one or all in solid form, by physical methods such as mixing, spinning, agitation, vibration, or some combination thereof. Common homogenizers can be generally divided between horizontal conveyors, in which a screw or screw-like mechanism conveys polymer granules and additive mixtures down the length of the homogenizer, and vertical or horizontal blenders which homogenizes polymer granules and additive mixtures by agitation or some other non-conveying means. In one or more examples, the homogenizer maintains the materials being mixed in solid and/or liquid form and does not create a molten material such as by heating a polymer to its melting point temperature.

[0037] In any case, blenders can be ribbon-type or paddle-type. Ribbon blenders control mixing and residence time with reverse-flow angle ribbon section(s) and paddle-blenders use reverse flow angle paddles. Though complete solid-solid homogenization is desirable, it has been found that pre-extruder homogenization is not needed to achieve acceptable solid-solid variation. For solid organic peroxides in granule or flake form, a blender is beneficial not only for the homogenization but to increase residence time of the peroxide/granule mixture in the temperature range that the long-chain branching reaction occurs prior to entering the melt section of the extruder, where the temperature is elevated to the point that the organic peroxide produces chain scissioning and has a half-life on the order of milliseconds. Some specific types of homogenizers that can be used include horizontal screw conveyer, horizontal ribbon blender, and horizontal single or twin shaft paddle blender. These may each be adjusted to change the rate of rotation, the number of paddles, the angle of the paddles and/or ribbons, the pitch of the ribbons or screw, and length of travel to effect the solid-liquid or solid-solid reaction.

[0038] Thus, in any embodiment, a process includes (or comprises, or consists of, or consists essentially of) combining a polymerization catalyst with propylene at a polymerization temperature to produce polypropylene granules having a first melt flow rate (MFR1). The temperature of the polypropylene granules is maintained at least at the polymerization temperature, which can be any desirable temperature depending on the type of catalyst and other process conditions, an example of which is a temperature of at least 50°C. The polypropylene granules are combined or otherwise mixed with an organic peroxide at a temperature of at least the polymerization temperature for a residence time of at least 40 seconds, or 50 seconds, or 60 seconds, or 70 seconds at a temperature below the melting point temperature of the polypropylene granules, such as from 50°C to 75°C, or 80°C, or 85°C, or 90°C, or 95°C, or 100°C, to form a LCB polypropylene having a second melt flow rate (MFR2), where MFR1 is greater than MFR2. The step of combining the polymerization catalyst and the propylene takes place in an environment such as a polymerization reactor that is maintained at a "polymerization temperature" as is described herein.

[0039] In one or more embodiments, the process includes (or comprises, or consists of, or consists essentially of) combining a polymerization catalyst with propylene at a polymerization temperature to produce polypropylene granules having an MFR1, where the temperature of the polypropylene granules is maintained at least at the polymerization temperature such as at least the polymerization temperature, such as at least 50°C. The polypropylene granules are conveyed or otherwise transported to a homogenizer while maintaining the temperature of the granules at a temperature of at least 50°C, or 60°C, or 70°C. The polypropylene granules are mixed or otherwise combined with an organic peroxide in the homogenizer for a residence time of at least 40 seconds, or 50 seconds, or 60 seconds, or 70 seconds at a temperature below the melting point temperature of the polypropylene granules to form a LCB polypropylene having an MFR2. In some examples, MFR1 is greater than MFR2.

[0040] The polypropylene granules described herein can be produced by any means of olefin polymerization, but are produced from a single catalyst and single stage polymerization process. By "single catalyst", what is meant is that the olefins are contacted with a catalyst derived from the same or similar preparation, thus having the same or similar homogeneous composition such as a single Ziegler-Natta type of catalyst, metallocene catalyst, or other catalyst. In one or more examples, the single catalyst is a Ziegler-Natta catalyst with one or more external electron donors in a slurry polymerization system, such as two external donors whose overall concentration can be varied, and/or they can be varied with respect to one another.

[0041] In any embodiment, the polymerization catalyst is a Ziegler-Natta catalyst that includes a solid titanium catalyst component containing titanium as well as magnesium, halogen, at least one non-aromatic "internal" electron donor, and at least one, two, or more "external" electron donors. The solid titanium catalyst component, also referred to as a Ziegler- Natta catalyst, can be prepared by contacting a magnesium compound, a titanium compound, and at least the internal electron donor. Examples of the titanium compound used in the preparation of the solid titanium catalyst component include tetravalent titanium compounds having the formula Ti(OR_n)X4-_n, where "R" is a hydrocarbyl radical, "X" is a halogen atom, and n is from 0 to 4. For purposes of this disclosure, a hydrocarbyl radical is defined to be Cl to C20 radicals, or Cl to CIO radicals, or C6 to C20 radicals, or C7 to C21 radicals that may be linear, branched, or cyclic where appropriate (aromatic or non- aromatic).

[0042] In some examples, the halogen-containing titanium compound is a titanium tetrahalide, such as titanium tetrachloride. In other examples, the magnesium compound to be used in the preparation of the solid titanium catalyst component includes a magnesium compound having reducibility and/or a magnesium compound having no reducibility. Suitable magnesium compounds having reducibility may, for example, be magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Suitable examples of such reducible magnesium compounds include dimethyl magnesium, diethyl-magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, magnesium ethyl chloride, magnesium propyl chloride, magnesium butyl chloride, magnesium hexyl chloride, magnesium amyl chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and/or butyl magnesium halides. In combination with the magnesium compound, the titanium- based Ziegler-Natta catalyst is said to be supported.

[0043] In any embodiment, the Ziegler-Natta catalysts are used in combination with a co catalyst. Compounds containing at least one aluminum-carbon bond in the molecule may be utilized as the co-catalysts, also referred to herein as an organoaluminum co-catalyst. Suitable organoaluminum compounds include organoaluminum compounds of the general formula R¹ _mAl(OR²)_nH_pX_q, where R¹ and R² are identical or different, and each represents a Cl to C15 hydrocarbyl radical, or Cl to C4 hydrocarbon radical; "X" represents a halogen atom; and "m" is 1, 2, or 3; "n" is 0, 1, or 2; "p" is 0, 1, 2, or 3; and "q" is 0, 1, or 2; and where m+n+p+q = 3. Other suitable organoaluminum compounds include complex alkylated compounds of metals of Group I of the Period Table (e.g., lithium, sodium, or potassium) and aluminum represented by the general formula M ¹ A1R , where M¹ is the Group I metal such as Li, Na, or K, and R¹ is as defined in formula (2). Suitable examples of the organoaluminum compounds include trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethylaluminum ethoxide and dibutyl aluminum ethoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide.

[0044] Electron donors are present with the metal components described above in forming the catalyst suitable for producing the polypropylenes described herein. Both "internal" and "external" electron donors are desirable for forming the catalyst suitable for making the polypropylene described herein. More particularly, the internal electron donor may be used in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl. Examples of suitable internal electron donors include amines, amides, ethers, esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, and salts of organic acids. In one or more examples, the one or more internal donors are non- aromatic. The non- aromatic internal electron donor may contain an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioethers, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof. In one or more examples, the non-aromatic internal electron donor(s) comprises a Cl to C20 diester of a substituted or unsubstituted C2 to CIO dicarboxylic acid.

[0045] In any embodiment, two or more external electron donors are used in combination with the Ziegler-Natta catalyst. The external electron donors may comprise an organic silicon compound of the general formula R¹ _nSi(OR²)4-_n, where R¹ and R² independently represent a hydrocarbyl radical and "n" is 1, 2, or 3. Examples of the suitable organic silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diiso-propyldiethoxysilane, t-butylmethyl- n-diethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o- tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p- tolyldimethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyl-dimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyl-trimethoxysilane, methyltrimethoxysilane, n-propyl-triethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, [gamma]- chloropropyltri-methoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, gamma-aminopropyltriethoxysilane, chlorotriethoxysilane, vinyltributoxysilane, cyclo-hexyltrimethoxysilane, cyclohexyltriethoxysilane, 2- norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethyl-phenoxysilane, methylallyloxy silane, vinyltris(beta-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltriethoxy silane, and/or dicyclopentyldimethoxysilane.

[0046] In one or more examples, the external electron donors are selected from any one or more of methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane cyclohexyltrimethoxysilane, tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltriethoxysilane, and/or dicyclopentyldimethoxysilane.

[0047] In any embodiment, the production of the polypropylene granules includes the use of two external electron donors, such as to simultaneously use two external electron donors. Suitable methods for using such external electron donors is disclosed in US 6,087,459, and US 6,686,433. The two external electron donors may be selected from any of the external electron donors described herein. But in a particular embodiment, the first external electron donor has the formula R¹2Si(OR²)2, where each R¹ is independently a Cl to CIO hydrocarbyl radical in which the carbon adjacent to the silicon atom is a secondary or a tertiary carbon atom, and where each R² is independently a Cl to CIO hydrocarbyl radical; and the second external electron donor has the formula R³ _nSi(OR⁴)4-_n, where each R³ and R⁴ is independently a Cl to CIO hydrocarbyl radical, and "n" is 1, 2, or 3; where the second external electron donor is different than the first external electron donor. The combined concentration of external electron donors can be present with the catalyst and monomer(s) in the polymerization reactor to from 10, or 20 ppm to 80, or 100, or 120 ppm.

[0048] The concentration of the catalyst system in the polymerization reactor(s) may be from 0.01 to 200 millimoles, or such as from 0.05 to 100 millimoles, calculated as a titanium atom, per liter of an inert hydrocarbon medium. The organoaluminum co-catalyst may be present in an amount sufficient to produce from 0.1 to 500 g, or such as from 0.3 to 300 g, of a polymer per gram of the titanium catalyst present, and may be present at from 0.1 to 100 moles, or from 0.5 to 50 moles, per mole of the titanium atom present in the catalyst component.

[0049] Examples of suitable means of polymerization include contacting the catalyst and olefins in a gas phase reactor, stirred tank reactor, loop reactor, or other reactors known in the art. The polymerization may take place in the gas phase, as a solution, or as a slurry. In any case, hydrogen may be present in the reactor to modulate the molecular weight of the polypropylene being produced. In any embodiment, the hydrogen, if combined with the single catalyst during the polymerization, is combined at a constant level. This means that the total concentration of hydrogen in the reactor is held constant during the production of the polypropylene.

[0050] The polymerization can be a "single stage" polymerization process, meaning that the olefins and catalyst, and optional hydrogen are contacted under the same or similar conditions throughout the production of the polypropylene granules, such as in a single reactor, or multiple reactors in parallel or series, held at a constant level of temperature, pressure, monomer concentration, and hydrogen concentration, where no parameter changes by more than ±5%, or ±10% in going from one reactor to the next. Thus, for example, a polymerization is single stage even if performed in two or more loop slurry reactors in parallel if the reactor conditions are held at a constant (±10%) level.

[0051] The phrases "slurry polymerization process" or "slurry polymerization reactor" refer to a process or reactor that handles polymer that is only partly dissolved or not dissolved at all in the medium, either monomer, solvent, or both, typically having at least 20 wt% polymer, by weight of the polymer, monomers and diluent, suspended or not dissolved. In a typical solution or slurry polymerization process, catalyst components, solvent, monomers and hydrogen (when used) are passed under pressure to one or more polymerization reactors. Catalyst components may be passed in the inventive processes to the polymerization reactor as a mixture in aliphatic hydrocarbon solvent, in oil, a mixture thereof, or as a dry powder. In one or more examples, the polymerization process is carried out using propylene as the only solvent.

[0052] In any case, the temperature of the reactor is controlled by the rate of catalyst addition (rate of polymerization), the temperature of the solvent/monomer feed stream and/or the use of heat transfer systems. For olefin polymerization, reactor temperatures can range from 50°C to 120°C or more, while pressures are generally higher than 300 psig, or from 300 psig to 1,000, or 1,200 psig. These process conditions favor in-situ catalyst activation since high temperature enhances the solubility of catalysts and activators in aliphatic hydrocarbon solvent. In any embodiment, the polymerization temperature, that is, the temperature at which the polymerization reaction is conducted such as the environment of a polymerization vessel or reactor, is at least 50°C, or 60°C, or 70°C, or from 50°C, or 60°C, or 70°C, or 80°C, or 90°C, or 100°C, or 120°C to 130°C, or 140°C, or 150°C, or 160°C, or 170°C. The vessel or reactor can be a loop reactor, or stirred tank reactor, a gas phase reactor, or other reactor as is known in the art.

[0053] The propylene and, if present, ethylene and/or other C4 to C12 a-olefin, are dissolved/dispersed in the solvent either prior to being passed to the polymerization reactor (or for gaseous monomers, the monomer may be passed to the reactor so that it will dissolve in the reaction mixture). Prior to mixing, the solvent and monomers are generally purified to remove potential catalyst poisons. The feedstock may be heated or cooled prior to delivery to the first reactor. Additional monomers and solvent may be added to the second reactor, and it may be heated or cooled. In some examples, the solvent is the propylene monomer itself.

[0054] The catalysts/activators can be passed to one polymerization reactor or split between two or more reactors. In solution or slurry polymerization, polymer produced is molten and remains dissolved or partially dissolved in the solvent under reactor conditions, forming a polymer solution. The catalyst may be passed to the reactor in solid form or as a slurry/suspension in a solvent. Alternatively, the catalyst suspension may be premixed with the solvent in the feed stream for the polymerization reaction. Catalyst can be activated in-line, or by an activator with which it is co-supported. In some instances premixing is desirable to provide some reaction time prior to the catalyst components entering the polymerization reactor, which may be in the presence or absence of the monomer to effect what is known as "pre polymerization," but this step is absent. The catalyst activity is 20,000 kg polymer per kg of catalyst or more, such as 50,000 kg polymer per kg of catalyst or more, or 100,000 kg polymer per kg of catalyst or more.

[0055] In any embodiment, the solution or slurry polymerization processes of this disclosure includes a stirred reactor system comprising one or more stirred polymerization reactors. Generally the reactors should be operated under conditions to achieve a thorough mixing of the reactants. In a dual reactor system, the reactors may operate at the same or different temperatures and fluidly connected in series, but can operate at the same temperature or within ±2°C, or ±4°C of one another as measured by an internal thermocouple within the polymerization medium or inside wall of each reactor, consistent with one another. The residence time in each reactor will depend on the design and the capacity of the reactor. In one or more examples, the two or more reactors otherwise operate under the same conditions. [0056] In any embodiment, the solution or slurry polymerization process is carried out in one or more loop-type of reactors, such as two loop-type of reactors fluidly connected in series. Such reactor systems include a single reactor and multiple reactors in series or parallel configuration, such as that disclosed in U.S. Pub. No. 2007/0022768. The solvent/monomer, such as propylene, flow in these reactors is typically maintained using pumps and/or pressure systems, and may operate continuously by having monomer and catalyst feed at one point and extracting the forming polymer from another point, such as downstream therefrom. The conditions of temperature, catalyst concentration, hydrogen concentration, and monomer concentration may be the same or different in each loop reactor and may be tailored as necessary to suit the desired end product.

[0057] In any embodiment, the solution polymerization process of this disclosure uses heat exchanger types of reactors where the polymerization. The reactors can be one or more shell and tube type of heat exchangers, or one or more spiral type of heat exchanger.

[0058] In any case, the polypropylene solution is then discharged from the reactor as an effluent stream and the polymerization reaction is quenched, typically with coordinating polar compounds, to prevent further polymerization. On leaving the reactor system the polymer solution is passed through a heat exchanger system on route to a devolatilization system and polymer finishing process. Under certain conditions of temperature and pressure, the polymer solution can phase separate into a polymer lean phase and a polymer rich phase. The polypropylene granules can be recovered from the effluent by coagulation with a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer can be recovered by stripping the solvent or other media with heat or steam. One or more conventional additives such as antioxidants can be incorporated in the polymer during the finishing procedure. Possible antioxidants include phenyl-beta-naphthylamine; di-tert-butylhydroquinone, triphenyl phosphate, heptylated diphenylamine, 2,2'-methylene-bis(4-methyl-6-tert-butyl)phenol, and 2,2,4-trimethyl-6-phenyl- 1 ,2-dihydroquinoline, and/or stabilizing agents such as tocopherols or lactones, or other agents as disclosed in PCT Pub. No. WO 2009/007265.

[0059] The "polypropylene granules" are the solid product of the polymerization reaction between the polymerization catalyst, such as a Ziegler-Natta catalyst and two external donors, and propylene, with optional comonomers such as ethylene, 1-butene, 1-hexene, and/or 1- octene. The resulting polypropylene granules can be homopolymers of propylene-derived units, or copolymers of propylene-derived units from 0.1 wt% to 4 wt% or 5 wt%, by weight of the polymer, of ethylene or C4 to C12 a-olefin derived units. The polypropylene granules, as produced as described, are then mixed with an organic peroxide to produce a LCB polypropylene. The "LCB polypropylene" is the polypropylene reaction product between the organic peroxide and the polypropylene granules prior to any melt blending step. The LCB polypropylenes described herein are expected to have the same comonomer content as the granules.

[0060] The "organic peroxide" is any organic compound comprising at least one— (O)COO— group and/or— O— O— group, and possesses a 1 hour half-life temperature (^lTm) of less than 100°C, or 85°C, or 75°C, or 65 °C as determined in an aromatic and/or halogenated aromatic solvent, and has a (¹Ti_/2) from 25°C, or 35°C, or 45°C to 65°C, or 75°C, or 85°C, or 100°C.

[0061] In any embodiment, the organic peroxide is selected from compounds having one or more structures selected from (a) and (b):

[0062] where each "R" group is independently selected from hydrogen, Cl or C5 to C24 or

C30 linear alkyls, Cl or C5 to C24 or C30 secondary alkyls, Cl or C5 to C24 or C30 tertiary alkyls, C7 to C34 alkylaryls, C7 to C34 arylalkyls, and substituted versions thereof. The organic peroxide is selected from the structures represented by formula (a). By "substituted" what is meant are hydrocarbon "R" groups having substituents such as halogens, carboxylates, hydroxyl groups, amines, mercaptans, and phosphorous containing groups. In a particular embodiment, each "R" group is independently selected from C8 to C20 or C24 linear, secondary, or tertiary alkyls, such as octyl, decyl, lauryl, myristyl, cetyl, arachidyl, behenyl, erucyl and ceryl groups and linear, secondary or tertiary versions thereof. Specific, non-limiting examples of suitable organic peroxides include di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dibutyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, didodecyl peroxydicarbonate, diicosyl peroxydicarbonate, and ditetracosyl peroxydicarbonate.

[0063] In any embodiment, the melting point of the organic peroxide is from 30°C, or 40°C, or 45°C to 55°C, or 65°C, or 75°C. The solid, neat organic peroxide has a bulk density from 0.4 g/cm³, or 0.5 g/cm³ to 0.7 g/cm³, or 0.8 g/cm³. In any embodiment, the organic peroxide is in the form of solid granules, flakes, particles, powder, or other solid "granular" form. It may be used in its neat form or as a masterbatch with an inert polymer matrix, or solution with an inert solvent. The size and shape of the organic peroxide can be tailored by low temperature methods such as prilling or compaction, or other known means.

[0064] The methods for producing the LCB polypropylenes described herein are effected in any embodiment by melt blending the polypropylene granules with the organic peroxide, especially through shear forces and applied radiative heating during blending/extrusion, to a melt temperature of at least the melting point of the linear polypropylene, such as at least 140°C, or 150°C, or 160°C, or from 140°C, or 150°C, or 160°C to 180°C, or 200°C, or 220°C, or 240°C, or 260°C, or 280°C, or 300°C. Suitable means include a single or twin screw extruder or Brabender- or Banbury-type apparatus.

[0065] The LCB polypropylenes produced from the polymerization process are conveyed to a homogenizer. In any embodiment, cooling is absent from the conveying process, and the pellets, still heated from the polymerization reaction, are maintained at the same or even greater temperature. In particular, though there may be a cooling apparatus present with the capability of cooling the polypropylene granules, it is not used for such purpose and no external cooling is applied to the granules, and the granules are kept at the same or higher temperature as when they exit the polymerization reactor. In one or more examples, the mixing step takes place after the combining step without cooling the polypropylene granules. In any embodiment, the polypropylene granules are heated to a temperature from 50°C to 75 °C, or 80°C, or 85 °C, or 90°C, or 95°C, or 100°C prior to (and/or during) mixing with the organic peroxide, meaning that the granules are exposed to a temperature within the named range, such as the homogenizer or the like.

[0066] In any embodiment, the amount of organic peroxide that is combined, contacted or otherwise "mixed" with the polypropylene granules is from 0.4, or 0.5, or 0.6 wt% to 0.8, or 1.0, or 1.2, or 1.4, or 1.5 wt% by weight of the polypropylene granules and organic peroxide. The mixing occurs in the presence of an inert gas, for instance in the presence of a flow of nitrogen or argon gas. In any embodiment, the mixing occurs in a homogenizer at a rate of at least 50,000, or 60,000, or 80,000 lbs of polymer/hour.

[0067] Thus, the overall process may start with forming the polypropylene granules, which are the reactor grade, untreated polymer from the polymerization reaction, followed by mixing the pellets with organic peroxide to form the LCB polypropylene, followed by melt blending to form pellets containing the LCB polypropylene. The overall process, and/or individual steps, is carried out without the need for certain added steps and/or agents.

[0068] In particular, in any embodiment, bifunctional agents are absent during the mixing, or during any stage of the process. By "bifunctional agents" what is meant are agents having at least two reactive moieties capable of forming a chemical bond between two different polymer chains, such as carbon-carbon double bonds in divinylbenzene, isoprene, or polyisobutylene and other conjugated dienes. Other bifunctional agents are those with moieties such as hydroxyl, mercaptans, sulfide, and imide groups including 1 ,4-benzenediol and furfuryl sulfide. Also, in any embodiment, irradiation is absent, such as electron beam, ultra-violet radiation, gamma-radiation, and other such high energy radiation. In one or more examples, no solvent, such as acetone, toluene, propane, propylene, isobutane, or hexanes was present during the mixing or at any stage of the process.

[0069] It may be desirable to control the particle size of the polypropylene granules coming from the reactor. One method to accomplish this is by controlling the particle size of the catalyst itself. Thus in any embodiment, the average particle size of the catalyst can be reduced from an average diameter of 50 to 80 micrometers to an average diameter of less than 50, or 40 micrometers. In any embodiment, the average particle size of the polypropylene granules is reduced from an average diameter of at least 1,500 or 2,000 micrometers to an average diameter of less than 1,000, or 800 micrometers.

[0070] Finally, the use of a cooling apparatus or any type of cooling means is absent in the process, either any of the individual steps, or all of the steps. Thus, the combining and mixing steps occur at or above the polymerization temperature, where heating can be applied in the mixing step to increase the temperature further.

[0071] The LCB polypropylenes have a number of desirable features. In any embodiment, the LCB polypropylenes have a melt strength (pull-off-force) of 5 cN, 10 cN, 12 cN, 15 cN, or 18 cN to 20 cN, 25 cN, 30 cN, 40 cN, 50 cN, 60 cN, 70 cN, 80 cN, 90 cN, 100 cN, or 120 cN. For example, the LCB polypropylenes have a melt strength (pull-off-force) of 5 cN to 120 cN, 5 cN to 100 cN, 5 cN to 80 cN, 5 cN to 60 cN, 5 cN to 50 cN, 5 cN to 40 cN, 5 cN to 30 cN, 5 cN to 20 cN, 5 cN to 15 cN, 5 cN to 10 cN, 10 cN to 120 cN, 10 cN to 100 cN, 10 cN to 80 cN, 10 cN to 60 cN, 10 cN to 50 cN, 10 cN to 40 cN, 10 cN to 30 cN, 10 cN to 20 cN, 10 cN to 15 cN, 12 cN to 120 cN, 12 cN to 100 cN, 12 cN to 80 cN, 12 cN to 60 cN, 12 cN to 50 cN, 12 cN to 40 cN, 12 cN to 30 cN, 12 cN to 20 cN, or 12 cN to 15 cN.

[0072] The LCB polypropylenes also exhibit strain hardening as evidenced by an increase in the viscosity as the melt is drawn in a rheometer, as described below, to at least a viscosity of 10,000 Pa, or 20,000 Pa, or 40,000 Pa above the linear-viscoelastic (LVE) range at a rate from 1 sec ¹ to 10 sec ¹, or from 10,000 Pa, or 20,000 Pa, or 40,000 Pa to 100,000 Pa, or 200,000 Pa, or 500,000 Pa. In one or more examples, the LCB polypropylene exhibits such strain hardening values even when as little as 0.6 wt% to 1 wt% or 1.2 wt% organic peroxide is mixed with the granules.

[0073] The mixing of the polypropylene granules with peroxide and subsequent melt blending imparts certain properties to the resulting LCB polypropylene. In any embodiment, the polypropylene granules have a branching index (g'vis) of greater than 0.97, where the LCB polypropylene has a g'vis value of less than 0.95.

[0074] In one or more examples, the LCB polypropylene can have a g'vis value of less than 0.95, less than 0.94, or less than 0.93, such as from 0.80, 0.82, 0.84, 0.85, or 0.86, to 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, or 0.94. Lor example, the LCB polypropylene can have a g'vis value of 0.80 to less than 0.95, 0.82 to less than 0.95, 0.84 to less than 0.95, 0.86 to less than 0.95, 0.88 to less than 0.95, 0.90 to less than 0.95, 0.91 to less than 0.95, 0.92 to less than 0.95, 0.93 to less than 0.95, 0.80 to less than 0.93, 0.82 to less than 0.93, 0.84 to less than 0.93, 0.86 to less than 0.93, 0.88 to less than 0.93, 0.90 to less than 0.93, 0.91 to less than 0.93, 0.80 to 92, 0.82 to 92, 0.84 to 92, 0.86 to 92, 0.88 to 92, or 0.90 to 92.

[0075] In any embodiment, the LCB polypropylene exhibits a strain hardening index (SHI, strain rate of 1 sec ¹, 190°C) of at least 1.5, or 2, or 3 or from 1.5, or 2, or 3 to 7, or 8, or 9 when calculated as the ratio of the strain at an apparent elongational speed of 3 sec ¹ divided by the strain at the elongational speed of 1 sec ¹ (83/81 ), which is essentially the slope of the extensional viscosity versus strain rate plots in the region of linear increase relative to the LVE. The polypropylene granules exhibit a SHI of less than 1.5.

[0076] In any embodiment, the polypropylene granules and/or the LCB polypropylene has a melt flow rate (MLR) from 1 g/10 min, 1.2 g/10 min, 1.5 g/10 min, 1.8 g/10 min, 2 g/10 min, 2.2 g/10 min, 2.5 g/10 min, 2.8 g/10 min, or 3 g/10 min to 3.2 g/10 min, 3.5 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 10 g/10 min, 20 g/10 min, 40 g/10 min, or 50 g/10 min, as determined according to ASTM D1238 Condition L. Lor example, the polypropylene granules and/or the LCB polypropylene has an MLR from 1 g/10 min to 50 g/10 min, 1 g/10 min to 30 g/10 min, 1 g/10 min to 20 g/10 min, 1 g/10 min to 15 g/10 min, 1 g/10 min to 10 g/10 min, 1 g/10 min to 5 g/10 min, 1 g/10 min to 4 g/10 min, 1 g/10 min to 3 g/10 min, 1 g/10 min to 2.5 g/10 min, 1 g/10 min to 2.2 g/10 min, 1 g/10 min to 2 g/10 min, 1 g/10 min to 1.8 g/10 min, 1.5 g/10 min to 50 g/10 min, 1.5 g/10 min to 30 g/10 min, 1.5 g/10 min to 20 g/10 min, 1.5 g/10 min to 15 g/10 min, 1.5 g/10 min to 10 g/10 min, 1.5 g/10 min to 5 g/10 min, 1.5 g/10 min to 4 g/10 min, 1.5 g/10 min to 3 g/10 min, 1.5 g/10 min to 2.5 g/10 min, 1.5 g/10 min to 2.2 g/10 min, 1.5 g/10 min to 2 g/10 min, 1.5 g/10 min to 1.8 g/10 min, 1.8 g/10 min to 50 g/10 min, 1.8 g/10 min to 30 g/10 min, 1.8 g/10 min to 20 g/10 min, 1.8 g/10 min to 15 g/10 min, 1.8 g/10 min to 10 g/10 min, 1.8 g/10 min to 5 g/10 min, 1.8 g/10 min to 4 g/10 min, 1.8 g/10 min to 3 g/10 min, 1.8 g/10 min to 2.5 g/10 min, 1.8 g/10 min to 2.2 g/10 min, 1.8 g/10 min to 2 g/10 min, 2 g/10 min to 50 g/10 min, 2 g/10 min to 30 g/10 min, 2 g/10 min to 20 g/10 min, 2 g/10 min to 15 g/10 min, 2 g/10 min to 10 g/10 min, 2 g/10 min to 5 g/10 min, 2 g/10 min to 4 g/10 min, 2 g/10 min to 3 g/10 min, 2 g/10 min to 2.5 g/10 min, 2 g/10 min to 2.2 g/10 min, 2.2 g/10 min to 50 g/10 min, 2.2 g/10 min to 30 g/10 min, 2.2 g/10 min to 20 g/10 min, 2.2 g/10 min to 15 g/10 min, 2.2 g/10 min to 10 g/10 min, 2.2 g/10 min to 5 g/10 min, 2.2 g/10 min to 4 g/10 min, 2.2 g/10 min to 3 g/10 min, or 2.2 g/10 min to 2.5 g/10 min, as determined according to ASTM D1238 Condition L. The pellets typically have a lower MFR (higher number and weight average molecular weight) than the granules, as the pellets are the product of the reactive extrusion between the granules and organic peroxide.

[0077] In any embodiment, the LCB polypropylene has a number average molecular weight (Mn) of 25,000 g/mol to 35,000 g/mol, 27,000 g/mol to 33,000 g/mol, 28,000 g/mol to 32,000 g/mol, or 29,000 g/mol to 31,000 g/mol. The LCB polypropylene has a weight average molecular weight (Mw) of 400,000 g/mol to 460,000 g/mol, 410,000 g/mol to 450,000 g/mol, or 420,000 g/mol to 445,000 g/mol. The LCB polypropylene has an average molecular weight (Mz) of 2,000,000 g/mol to 3,000,000 g/mol, 2,000,000 g/mol to 2,800,000 g/mol, 2,100,000 g/mol to 2,800,000 g/mol, 2,200,000 g/mol to 2,600,000 g/mol, or 2,250,000 g/mol to 2,550,000 g/mol. The LCB polypropylene has a Z+l average molecular weight (Mz+l) of 4,000,000 g/mol to 6,000,000 g/mol, 4,200,000 g/mol to 5,800,000 g/mol, 4,400,000 g/mol to 5,600,000 g/mol, 4,600,000 g/mol to 5,400,000 g/mol, or 4,700,000 g/mol to 5,250,000 g/mol.

[0078] The LCB polypropylene has an Mz/Mw molecular weight distribution of 4.5, 4.8, 5, or 5.2 to 5.3, 5.5, 5.8, 6, or 6.5. For example, the LCB polypropylene has an Mz/Mw molecular weight distribution of 4.5 to 6.5, 4.5 to 6, 4.5 to 5.8, 4.5 to 5.5, 4.5 to 5.2, 4.5 to 5, 5 to 6.5, 5 to 6, 5 to 5.8, 5 to 5.5, 5 to 5.2, 5.8 to 6.5, 5.8 to 6, or 5.5 to 5.8.

[0079] The LCB polypropylene has an Mw/Mn molecular weight distribution of 12, 12.5, 13, or 13.4 to 13.5, 14, 14.5, 15, 15.5, 16, or 17. For example, the LCB polypropylene has an Mw/Mn molecular weight distribution of 12 to 17, 12 to 16, 12 to 15.5, 12 to 15, 12 to 14.5, 12 to 14, 13 to 17, 13 to 16, 13 to 15.5, 13 to 15, 13 to 14.5, 13 to 14, 13.4 to 17, 13.4 to 16, 13.4 to 15.5, 13.4 to 15, 13.4 to 14.5, or 13.4 to 14.

[0080] The polyolefin composition containing one or more LCB polypropylenes and one or more linear polypropylenes can be formed into useful films, foams, and other articles. For instance, in any embodiment, a foamed article can be formed from the polypropylene or polypropylene in a blend with another polymer and/or additive (e.g., filler, anti-oxidant, etc.). Foaming agents useful in forming foamed articles described herein may be normally gaseous, liquid or solid compounds or elements, or mixtures thereof. These foaming agents may be characterized as either physically-expanding or chemically decomposing. Of the physically expanding foaming agents, the term "normally gaseous" is intended to mean that the expanding medium employed is a gas at the temperatures and pressures encountered during the preparation of the foamable compound, and that this medium may be introduced either in the gaseous or liquid state as convenience would dictate. Such agents can be added to the polypropylenes by blending the dry polymer with the foaming agent followed by melt extrusion, or by blending the agents in the polymer melt during extrusion. The foaming agent, especially gaseous agent, may be blended with the polymer melt as it exits the melt extruder or mold that is used for forming the foamed articles. The concentration of the foaming agent may be from 100 ppm, or 200 ppm, or 500 ppm to 1,000 ppm, or 2,000 ppm, or 3,000 ppm, or 4,000 ppm, or 5,000 ppm within the polypropylene.

[0081] Included among exemplary, normally gaseous and liquid foaming agents are the halogen derivatives of methane and ethane, such as methyl fluoride, methyl chloride, difluoromethane, methylene chloride, perfluoromethane, trichloromethane, difluoro- chloromethane, dichlorofluoromethane, dichlorodifluoromethane, trifluorochloromethane, trichloromonofluoromethane, ethyl fluoride, ethyl chloride, 2,2,2-trifluoro-l,l-dichloroethane, 1,1,1-trichloroethane, difluoro-tetrachloroethane, 1,1-dichloro-l-fluoroethane, 1,1-difluoro-l- chloroethane, dichloro-tetrafluoroethane, chlorotrifluoroethane, trichlorotrifluoroethane, 1- chloro-l,2,2,2-tetrafluoroethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1, 1,1,2- tetrafluoroethane, perfluoroethane, pentafluoroethane, 2,2-difluoropropane, 1,1,1- trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, chloroheptafluoropropane, dichlorohexafluoropropane, perfluorobutane, perfluorocyclobutane, sulfur-hexafluoride, and mixtures thereof. Other normally gaseous and liquid foaming agents that may be employed are hydrocarbons and other organic compounds such as acetylene, ammonia, butadiene, butane, butene, isobutane, isobutylene, dimethylamine, propane, dimethylpropane, ethane, ethylamine, methane, monomethylamine, trimethylamine, pentane, cyclopentane, hexane, propane, propylene, alcohols, ethers, ketones, and the like. Inert gases and compounds, such as nitrogen, argon, neon or helium, can also be used as foaming agents.

[0082] Solid, chemically decomposable foaming agents, which decompose at elevated temperatures to form gasses, can be used to expand the polypropylenes. In general, the decomposable foaming agent will have a decomposition temperature (with the resulting liberation of gaseous material) from 130°C to 200°C, or 250°C, or 300°C, or 350°C. Exemplary chemical foaming agents include azodicarbonamide, p,p'-oxybis(benzene) sulfonyl hydrazide, p-toluene sulfonyl hydrazide, p-toluene sulfonyl semicarbazide, 5-phenyltetrazole, ethyl-5- phenyltetrazole, dinitroso pentamethylenetetramine, and other azo, N-nitroso, carbonate and sulfonyl hydrazide compounds as well as various acid/bicarbonate compounds which decompose when heated. Representative volatile liquid foaming agents include isobutane, difluoroethane or blends of the two. In one or more examples, an azodicarbonamide is used as a decomposable solid foaming agent, and carbon dioxide is used as an inert gas or a foaming gas.

[0083] The art of producing foam structures is known, and those processes used for, for example, polystyrene, are useful for the LCB polypropylene described and discussed herein. The foamed articles may take any physical configuration known in the art, such as sheet, plank, other regular or irregular extruded profile, and regular or irregular molded bun stock. Exemplary of other useful forms of foamed or foamable objects known in the art include expandable or foamable particles, moldable foam particles, or beads, and articles formed by expansion and/or consolidation and fusing of such particles. In any embodiment, the foamable article or polypropylenes may be cross-linked prior to expansion, such as for the process of free- radical initiated chemical cross-linking or ionizing radiation, or subsequent to expansion. Cross-linking subsequent to expansion may be effected if desired by exposure to chemical cross-linking agents or radiation or, when silane-grafted polymers are used, exposure to moisture optionally with a suitable silanolysis catalyst. [0084] The LCB polypropylenes described and discussed herein can be used to make foamed structures having any desired density, but a density from 0.1 to 0.6 g/cm³. For certain applications that require higher density such as structural components or automotive components, a lower melt strength polypropylene can be used alone or blended with a higher melt strength polypropylene to obtain a polypropylene that can form foam densities from 0.4 g/cm³ to 0.5 g/cm³, for example. For lower foam density applications such as in food containers, the higher melt strength polypropylenes described herein can be used alone or also blended to adjust the foam density to within, for example, a foam density of 0.1 g/cm³ to 0.3 g/cm³. Thus, for example, polypropylene granules (reactor grade PP) can be blended with the LCB polypropylene (organic peroxide treated) to produce any desired foaming density for a particular end use.

[0085] Methods of combining the various ingredients of the foamable polypropylenes include but are not limited to melt-blending, diffusion-limited imbibition, liquid-mixing, and the like, optionally with prior pulverization or other particle-size reduction of any or all ingredients. Melt-blending may be accomplished in a batchwise or continuous process, and is carried out with temperature control. Furthermore, many suitable devices for melt-blending are known to the art, including those with single and multiple Archimedean- screw conveying barrels, high-shear "Banbury" type mixers, and other internal mixers. The object of such blending or mixing is to provide a uniform mixture. One or more components may be introduced in a step-wise fashion, either later during an existing mixing operation, during a subsequent mixing operation or, as would be the case with an extruder, at one or more downstream locations into the barrel.

[0086] Expandable or foamable polypropylenes will have a foaming agent incorporated therein, such as a decomposable or physically expandable chemical blowing agent, so as to effect the expansion in a mold upon exposure of the composition to the appropriate conditions of heat and, optionally, the sudden release of pressure. The polypropylenes find many uses as foamed articles including automotive components, insulation and other construction components, food containers, sports equipment, and other domestic and commercial uses.

[0087] The LCB polypropylenes can also be thermoformed to make useful thermoformed articles. Thermoforming is a manufacturing process where the polypropylene sheet is heated to a pliable forming temperature, formed to a specific shape in a mold, and trimmed to create a usable product. The sheet, or "film" when referring to thinner gauges and certain material types, is heated in an oven to a high-enough temperature that permits it to be stretched into or onto a mold and cooled to a finished shape. Its simplified version is vacuum forming. The polypropylenes described herein can desirably be formed into films or sheets suitable for thermoforming processes.

[0088] In any embodiment, a small tabletop or lab size machine can be used to heat small cut sections of polypropylene sheet and stretch it over a mold using vacuum. This method is often used for sample and prototype parts. In complex and high- volume applications, very large production machines can be utilized to heat and form the polypropylene sheet and trim the formed parts from the sheet in a continuous high-speed process. The polypropylenes described herein are suitable for both types of thermoforming.

[0089] One desirable type of thermoforming is thin-gauge thermoforming. Thin-gauge thermoforming is primarily the manufacture of disposable cups, containers, lids, trays, blisters, clamshells, and other products for the food, medical, and general retail industries. Thick-gauge thermoforming includes parts as diverse as vehicle door and dash panels, refrigerator liners, utility vehicle beds, and plastic pallets. Heavy-gauge forming utilizes the same basic process as continuous thin-gauge sheet forming, typically draping the heated plastic sheet over a mold. Many heavy-gauge forming applications use vacuum only in the form process, although some use two halves of mating form tooling and include air pressure to help form.

[0090] In any embodiment, a sheet comprising (or consisting essentially of) the polypropylene is fed from a roll or from an extruder into a set of indexing chains that transport the sheet through an oven for heating to forming temperature. The heated sheet then indexes into a form station where a mating mold and pressure-box close on the sheet, with vacuum then applied to remove trapped air and to pull the material into or onto the mold along with pressurized air to form the plastic to the detailed shape of the mold. Plug-assists are typically used in addition to vacuum in the case of taller, deeper-draw formed parts in order to provide the needed material distribution and thicknesses in the finished parts. In any case, after a short cycle, a burst of reverse air pressure can be actuated from the vacuum side of the mold as the form tooling opens to break the vacuum and assist the formed parts off of, or out of, the mold. A stripper plate may also be utilized on the mold as it opens for ejection of more detailed parts or those with negative-draft, undercut areas. The polypropylene sheet containing the formed parts then indexes into a trim station, where a die cuts the parts from the remaining sheet web, or indexes into a separate trim press where the formed parts are trimmed. The sheet web remaining after the formed parts are trimmed is typically wound onto a take-up reel or fed into an inline granulator for recycling.

[0091] Generally, the polypropylenes made using the processes herein find use in making many thermoformed articles such as automotive components, construction components, electronic devices, medical equipment, sports equipment, food containers, appliances, and other domestic and commercial uses. Similarly, the polypropylenes can find use thermoformed articles made from injection molding, blow molding, and rotational molding processes.

Linear Polvpropylenes

[0092] The polyolefin compositions of the present disclosure include one or more broad molecular weight distribution (BMWD) polypropylenes which are or contain one or more linear polypropylenes. One or more linear polypropylene materials with improved melt strength, MWD, and high MFRs can be produced in a single stage polymerization conducted in the presence of certain Ziegler-Natta catalysts, which may optionally be supported, a non-aromatic internal electron donor, and a blend of two external electron donors. In any embodiment, a linear polypropylene can have a melt strength of at least 5 cN, 8 cN, or 10 cN to 15 cN, 20 cN, 25 cN, or 30 cN, as determined using an extensional rheometer at 190°C, a branching index (g'vis) of 0.95 or greater, and an MWD (Mw/Mn) of greater than 12 or greater than 14. In any embodiment, a Ziegler-Natta catalyst system may contain a Ziegler-Natta catalyst containing a non-aromatic internal electron donor, and first and second external electron donors containing different organosilicon compounds. In any embodiment, a method for making a linear polypropylene may contain contacting propylene monomers at a temperature and a pressure or other appropriate propylene polymerization conditions in the presence of the catalyst system to produce a linear polypropylene containing at least 50 mol% propylene and a melt strength of at least 5 cN to 30 cN as determined using an extensional rheometer at 190°C. In any embodiment, the catalyst system may contain a Ziegler-Natta catalyst containing a non-aromatic internal electron donor and a first external electron donor having the formula R¹2Si(OR²)2, where each R¹ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and where each R² is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms. In any embodiment, the catalyst system further may contain a second external electron donor having the formula R³ _nSi(OR⁴)4-_n, where each R³ and R⁴ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms, n is 1, 2, or 3, and the second external electron donor is different than the first external electron donor.

[0093] For the purposes of this invention and the claims thereto, the new numbering scheme for the Periodic Table Groups is used as in Chem. Eng. News, 1985, 63, 27. Therefore, a "Group 4 metal" is an element from Group 4 of the Periodic Table.

[0094] The terms "hydrocarbyl radical," "hydrocarbyl" and "hydrocarbyl group" are used interchangeably throughout this document unless otherwise specified. For purposes of this disclosure, a hydrocarbyl radical is defined to be Ci to C20 radicals, or Ci to C10 radicals, or Ce to C20 radicals, or C7 to C20 radicals that may be linear, branched, or cyclic where appropriate (aromatic or non-aromatic); and includes hydrocarbyl radicals substituted with other hydrocarbyl radicals and/or one or more functional groups containing elements from Groups 13 - 17 of the periodic table of the elements. In addition, two or more such hydrocarbyl radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, which may include heterocyclic radicals.

[0095] The term "substituted" means that a hydrogen atom and/or a carbon atom in the base structure has been replaced with a hydrocarbyl radical, and/or a functional group, and/or a heteroatom or a heteroatom containing group. Accordingly, the term hydrocarbyl radical includes heteroatom containing groups. For purposes herein, a heteroatom is defined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (MeCp) is a Cp group, which is the base structure, substituted with a methyl group, which may also be referred to as a methyl functional group, ethyl alcohol is an ethyl group, which is the base structure, substituted with an -OH functional group, and pyridine is a phenyl group having a carbon in the base structure of the benzene ring substituted with a nitrogen atom.

[0096] For purposes herein, unless otherwise stated, a hydrocarbyl radical may be independently selected from substituted or unsubstituted methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl.

[0097] For purposes herein, unless otherwise stated, hydrocarbyl radicals may also include isomers of saturated, partially unsaturated and aromatic cyclic structures where the radical may additionally be subjected to the types of substitutions described above. The term "aryl", "aryl radical", and/or "aryl group" refers to aromatic cyclic structures, which may be substituted with hydrocarbyl radicals and/or functional groups as defined herein. Examples of aryl radicals include: acenaphthenyl, acenaphthylenyl, acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl, benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls, benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl, carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, dibenzoanthracenyls, fluoranthenyl, fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyls, indolyl, indolinyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isoxazolyl, methyl benzyl, methylphenyl, naphthyl, oxazolyl, phenanthrenyl, phenyl, purinyl, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolonyl, quinoxalinyl, thiazolyl, thiophenyl, and the like.

[0098] For purposes herein the term "non-aromatic" refers to compounds, radicals, and/or functional groups without aromatic character attributed to cyclic conjugated sp² carbons having protons with a chemical shift relative to TMS consistent with aromatic protons, or greater than 6, as readily understood by one of minimal skill in the art.

[0099] It is to be understood that for purposes herein, when a radical is listed, it indicates that the base structure of the radical (the radical type) and all other radicals formed when that radical is subjected to the substitutions defined above. Alkyl, alkenyl, and alkynyl radicals listed include all isomers including where appropriate cyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l- propenyl, l-methyl-2-propenyl, 2-methyl- 1-propenyl, and 2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cyclic compounds having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3, 5 -dimethylphenyl.

[00100] Likewise the terms "functional group", "group" and "substituent" are also used interchangeably throughout this document unless otherwise specified. For purposes herein, a functional group includes both organic and inorganic radicals or moieties containing elements from Groups 13, 14, 15, 16, and 17 of the periodic table of elements. Suitable functional groups may include hydrocarbyl radicals, e.g., alkyl radicals, alkene radicals, aryl radicals, and/or halogen (Cl, Br, I, F), O, S, Se, Te, NR*_X, OR*, SeR*, TeR*, PR*_X, AsR*_x, SbR*_x, SR*, BR*_X, SiR*_x, GeR*_x, SnR*_x, PbR*_x, and/or the like, where R is a Ci to C20 hydrocarbyl as defined above, and where x is the appropriate integer to provide an electron neutral moiety. Other examples of functional groups include those typically referred to as amines, imides, amides, ethers, alcohols (hydroxides), sulfides, sulfates, phosphides, halides, phosphonates, alkoxides, esters, carboxylates, aldehydes, and the like.

[00101] Polypropylene microstructure is determined by ¹³C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). The designation "m" or "r" describes the stereochemistry of pairs of contiguous propylene groups, "m" referring to meso, and "r" to racemic. Samples are dissolved in d₂-l,l,2,2-tetrachloroethane, and spectra recorded at 125°C using a 100 MHz (or higher) NMR spectrometer. Polymer resonance peaks are referenced to mmmm = 21.8 ppm. Calculations involved in the characterization of polymers by NMR are described by F. A. Bovey in Polymer Conformation and Configuration (Academic Press, New York 1969) and J. Randall in Polymer Sequence Determination, ¹³C-NMR Method (Academic Press, New York, 1977).

[00102] For purposes herein, a supported catalyst and/or activator refers to a catalyst compound, an activator, or a combination thereof located on, in, or in communication with a support where the activator, the catalyst compound, or a combination thereof are deposited on, vaporized with, bonded to, incorporated within, adsorbed or absorbed in, adsorbed or absorbed on, the support.

[00103] For purposes herein an "olefin," alternatively referred to as "alkene," is a linear, branched, or cyclic compound containing carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.

[00104] For purposes herein a "polymer" has two or more of the same or different "mer" units. A "homopolymer" is a polymer having mer units that are the same. A "copolymer" is a polymer having two or more mer units that are different from each other. A "terpolymer" is a polymer having three mer units that are different from each other. "Different" in reference to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. An oligomer is typically a polymer having a low molecular weight, such an Mn of less than 25,000 g/mol, or in an embodiment less than 2,500 g/mol, or a low number of mer units, such as 75 mer units or less. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene derived units.

[00105] For the purposes of this disclosure, the term "a-olefin" includes C2 to C22 olefins. Non- limiting examples of cc-olefins include ethylene, propylene, 1 -butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1- tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1- eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl- 1-pentene, 3 -methyl- 1- pentene, 5-methyl-l-nonene, 3,5,5-trimethyl-l-hexene, vinylcyclohexane, and vinylnorbornane. Non-limiting examples of cyclic olefins and diolefins include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbomene, 4-methylnorbomene, 2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane, norbomadiene, dicyclopentadiene, 5-ethylidene-2-norbomene, vinylcyclohexene, 5-vinyl-2-norbomene, 1,3-divinylcyclopentane, 1 ,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-di vinylcyclohexane, 1,5-divinylcyclooctane, l-allyl-4- vinylcyclohexane, 1,4-diallylcyclohexane, l-allyl-5-vinylcyclooctane, and 1,5- diallylcyclooctane.

[00106] The terms "catalyst" and "catalyst compound" are defined to mean a compound capable of initiating polymerization catalysis under the appropriate conditions. In the description herein, the catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably. A catalyst compound may be used by itself to initiate catalysis or may be used in combination with an activator, an internal electron donor, one or more external electron donors, and/or a co catalyst to initiate catalysis. When the catalyst compound is combined with electron donors and/or co-catalysts to initiate catalysis, the catalyst compound is often referred to as a pre catalyst or catalyst precursor. A "catalyst system" is a combination of at least one catalyst compound, at least one internal electron donor, one or more external electron donors, a co catalyst, and/or a support where the system can polymerize monomers to produce a polymer under polymerization conditions of suitable temperature and pressure. For the purposes of this invention and the claims thereto, when catalyst systems are described as containing neutral stable forms of the components, it is well understood by one of ordinary skill in the art that the ionic form of the component is the form that reacts with the monomers to produce polymers.

[00107] For purposes herein the term "catalyst productivity" is a measure of how many grams of polymer (P) are produced using a polymerization catalyst containing (W) grams of catalyst (cat), over a period of time of (T) hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcat ¹hr¹. "Conversion" is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor. Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kg P/mol cat).

[00108] A "scavenger" is a compound that is typically added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form a catalyst system. In an embodiment, a co activator can be pre-mixed with the catalyst compound to form an alkylated catalyst compound.

[00109] A "propylene polymer" is a polymer having at least 50 mol% of propylene. As used herein, Mn is number average molecular weight as determined by proton nuclear magnetic resonance spectroscopy ( ¹ H NMR) or by gel permeation chromatography (GPC) unless stated otherwise, Mw is weight average molecular weight determined by gel permeation chromatography (GPC), Mz is z average molecular weight determined by GPC, and Mz+1 is z+1 average molecular weight determined by GPC, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD) is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz, or Mz+1, are g/mol.

[00110] The following abbreviations may be used through this specification: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iso- butyl is isobutyl, sec-butyl refers to secondary butyl, tert-butyl, refers to tertiary butyl, n-butyl is normal butyl, pMe is para-methyl, Bz is benzyl, THF is tetrahydrofuran, Mes is mesityl, also known as 1,3,5-trimethylbenzene, Tol is toluene, TMS is trimethylsilyl, and MAO is methylalumoxane. For purposes herein, "RT" is room temperature, which is defined as 25°C unless otherwise specified. All percentages are in weight percent (wt%) unless otherwise specified.

[00111] For purposes herein, Mw, Mz number of carbon atoms, g value and g'vis may be determined by using a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), equipped with three in-line detectors, a differential refractive index (DRI) detector, a light scattering (LS) detector, and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001), and references therein. Three Polymer Laboratories PLgel 10mm Mixed-B LS columns are used. The nominal flow rate is 0.5 cm³/min, and the nominal injection volume is 300 pL. The various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 145°C. Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 pm glass pre-filter and subsequently through a 0.1 pm Teflon filter. The TCB is then degassed with an online degasser before entering the Size Exclusion Chromatograph. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous agitation for 2 hours. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 145°C. The injection concentration is from 0.75 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample. The LS laser is turned on 1 to 1.5 hours before running the samples. The concentration, c, at each point in the chromatogram is calculated from the baseline- subtracted DRI signal, IDRI, using the following equation: c = KDRIIDRI /(dn/dc), where KDRI is a constant determined by calibrating the DRI, and (dn dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and l= 690 nm. For purposes of this invention and the claims thereto (dn/dc) = 0.104 for propylene polymers, 0.098 for butene polymers and 0.1 otherwise. Units on parameters throughout this description of the SEC method are such that concentration is expressed in g/cm³, molecular weight is expressed in g/mol, and intrinsic viscosity is expressed in dL/g.

[00112] The LS detector is a Wyatt Technology High Temperature mini-DAWN. The molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971):

[00113] Here, AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q, c is the polymer concentration determined from the DRI analysis, A2 is the second virial coefficient [for purposes of this invention, A2 = 0.0006 for propylene polymers, 0.0015 for butene polymers and 0.001 otherwise], (dn/dc) = 0.104 for propylene polymers, 0.098 for butene polymers, and 0.1 otherwise, R(q) is the form factor for a monodisperse random coil, and K_o is the optical constant for the system:

47t²n² (dn / dc)²

K

l⁴N_A

[00114] where NA is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and l = 690 nm.

[00115] A high temperature Viscotek Corporation viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, rp, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [h], at each point in the chromatogram is calculated from the following equation: rp = c| h | + 0.3(c[q])², where c is concentration and was determined from the DRI output. [00116] The branching index (g'vis) is calculated using the output of the SEC-DRI-LS-VIS method as follows. The average intrinsic viscosity, |h | _ivg, of the sample is calculated by:

[00117] where the summations are over the chromatographic slices, i, between the integration limits. The branching index g'vis, which is also referred to simply as g'vis is defined as:

[00118] where, for purpose of this invention and claims thereto, a = 0.695 and k = 0.000579 for linear ethylene polymers, a = 0.705 k = 0.000262 for linear propylene polymers, and a = 0.695 and k = 0.000181 for linear butene polymers. M_v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.

[00119] The term "g" also called a "g value" is defined to be Rg² _pm/Rg²i_s, where Rg_pm is the radius of gyration for the polymacromer, Rg²i_s is the radius of gyration for the linear standard, and Rgi_s = K_SM⁰·⁵⁸, where K_s is the power law coefficient (0.023 for linear polyethylene, 0.0171 for linear polypropylene, and 0.0145 for linear polybutene), and M is the molecular weight as described above, Rg_pm = KTM“^s. CC_S is the size coefficient for the polymacromer, KT is the power law coefficient for the polymacromer. See Macromolecules, 2001, 34, 6812-6820, for guidance on selecting a linear standard having the molecular weight and comonomer content, and determining K coefficients and a exponents.

[00120] For purposes herein, a functionalized polymer contains greater than 0.1 wt% of a functional group and/or a g'vis < 0.95, and/or is the product of a post reactor functionalization or grafting process. Accordingly, for purposes herein a non-functionalized polymer contains less than 0.1 wt% of a functional group, and/or is not the product of a post-reactor functionalization process, and/or is not a post-reactor grafted polymer, and/or has a g'vis > 0.95 determined as described herein.

Ziegler-Natta Catalyst

[00121] In any embodiment, Ziegler-Natta catalysts suitable for use herein include solid titanium supported catalyst systems described in U.S. Pat. Nos. 4,990,479 and 5,159,021, and PCT Pub. No. WO 00/63261, and others. Briefly, the Ziegler-Natta catalyst can be obtained by: (1) suspending a dialkoxy magnesium compound in an aromatic hydrocarbon that is liquid at ambient temperatures; (2) contacting the dialkoxy magnesium hydrocarbon composition with a titanium halide and with a diester of an aromatic dicarboxylic acid; and (3) contacting the resulting functionalized dialkoxy magnesium-hydrocarbon composition of step (2) with additional titanium halide.

[00122] In any embodiment, the catalyst system may be a solid titanium catalyst component containing magnesium, titanium, halogen, a non-aromatic internal electron donor, and two or more external electron donors. The solid titanium catalyst component, also referred to as a Ziegler-Natta catalyst, can be prepared by contacting a magnesium compound, a titanium compound, and at least the internal electron donor. Examples of the titanium compound used in the preparation of the solid titanium catalyst component include tetravalent titanium compounds having the formula: (R_nO)TiX4-_n , where R is a hydrocarbyl radical, each X is independent a halogen atom (Cl, Br, I, or F), and n is an integer of 0, 1, 2, 3, or 4.

[00123] In any embodiment, suitable titanium compounds for use herein include: titanium tetra-halide compounds such as TiCU, TiBr4, and/or TiLq alkoxy titanium trihalide compounds including (CH 0)TiCl3, (C₂H₅0)TiCl3, (n-C H₉0)TiCl3, (C₂H₅0)TiBr , and/or (iso- CTHyOjTiBn; dialkoxytitanium dihalide compounds including (CH₃0)₂TiCl₂, (C₂H₅0)₂TiCl₂, (n-C4HciO)₂TiCl₂, and/or (C₂H₅0)₂TiBr₂; trialkoxytitanium monohalide compounds including (CH30)3TiCl, (C₂H50)3TiCl, (n-C4HciO)3TiCl, and/or (C₂H50)3TiBr; and/or titanium tetraalkoxy compounds including (CITO^Ti, (C₂H₅0)₄Ti, and/or (n-G_tHyOqTi; and/or any combination thereof.

[00124] In any embodiment, the halogen-containing titanium compound may be a titanium tetrahalide, or titanium tetrachloride. The titanium compounds may be used singly or in combination with each other. The titanium compound may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

[00125] In any embodiment, the magnesium compound to be used in the preparation of the solid titanium catalyst component may include a magnesium compound having reducibility and/or a magnesium compound having no reducibility. Suitable magnesium compounds having reducibility may, for example, be magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Suitable examples of such reducible magnesium compounds include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, magnesium ethyl chloride, magnesium propyl chloride, magnesium butyl chloride, magnesium hexyl chloride, magnesium amyl chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and/or butyl magnesium halides. These magnesium compounds may be used singly or they may form complexes with the organoaluminum co-catalyst as described herein. These magnesium compounds may be a liquid or a solid.

[00126] Suitable examples of the magnesium compounds having no reducibility include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides, such as magnesium methoxy chloride, magnesium ethoxy chloride, magnesium isopropoxy chloride, magnesium phenoxy chloride, and magnesium methylphenoxy chloride; alkoxy magnesiums, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethylhexoxy magnesium; aryloxy magnesiums such as phenoxy magnesium and dimethylphenoxy magnesium; and/or magnesium carboxylates, such as magnesium laurate and magnesium stearate.

[00127] In any embodiment, non-reducible magnesium compounds may be compounds derived from the magnesium compounds having reducibility, or may be compounds derived at the time of preparing the catalyst component. The magnesium compounds having no reducibility may be derived from the compounds having reducibility by, for example, contacting the magnesium compounds having reducibility with polysiloxane compounds, halogen- containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, and the like.

[00128] In any embodiment, the magnesium compounds having reducibility and/or the magnesium compounds having no reducibility may be complexes of the above magnesium compounds with other metals, or mixtures thereof with other metal compounds. They may also be mixtures of two or more types of the above compounds. In any embodiment, halogen- containing magnesium compounds, including magnesium chloride, alkoxy magnesium chlorides and aryloxy magnesium chlorides may be used.

[00129] In any embodiment, a suitable solid catalyst component containing a non-aromatic internal electron donor may be a catalyst solid Ziegler-Natta type catalyst. Such a catalyst is used to exemplify the invention, other titanium supported catalyst systems are contemplated. Other catalyst use mechanisms are contemplated. Including, but not limited to, batch prepolymerization, in situ prepolymerization and other such mechanisms. Co-Catalyst

[00130] In any embodiment, supported Ziegler-Natta catalysts may be used in combination with a co-catalyst, also referred to herein as a Ziegler-Natta co-catalyst. In any embodiment, compounds containing at least one aluminum-carbon bond in the molecule may be utilized as the co-catalysts, also referred to herein as an organoaluminum co-catalyst. Suitable organoaluminum compounds include organoaluminum compounds of the general formula: R^l _niAl(OR²) H_pX_L| , where R¹ and R² are identical or different, and each represents a hydrocarbyl radical containing from 1 to 15 carbon atoms, or 1 to 4 carbon atoms; X represents a halogen atom; and 0 < m < 3, 0 < n < 3, 0 £ p < 3, and 0 < q < 3, and m+n+p+q = 3.

[00131] Other suitable organoaluminum compounds include complex alkylated compounds of metals of Group I and aluminum represented by the general formula: IVLAIR^, where M¹ is Li, Na, or K and R¹ is as defined above. Suitable organoaluminum compounds include compounds represented by the following general formulas:

[00132] R ¹ _ri K OR² b- _n, where R ¹ and R² are as defined above, and m is 1.5 < m < 3;

[00133] R'_nAKH) 3__m, where R¹ is as defined above, X is halogen, and m is 0 < m < 3, or 2 < m < 3; and/or

[00134] R¹ _mAl(OR²)nXq, where R ¹ and R² are as defined above, X is halogen, 0 < m < 3, 0 < n < 3, 0 < q < 3, and m+n+q = 3.

[00135] Suitable examples of the organoaluminum compounds include trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum ethoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui-butoxide; partially alkoxylated alkyl aluminums having an average composition represented by the general formula R¹ _2.5A1(OR²)_O.5; partially halogenated alkyl aluminums, for example, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; partially hydrogenated alkyl aluminums, for example, alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxychloride, butyl aluminum butoxychloride, and ethyl aluminum ethoxybromide.

[00136] In any embodiment, the organoaluminum compound may contain two or more aluminum atoms bonded through an oxygen or nitrogen atom. Examples include (C2H5)2A10A1(C2H5)2, (C4H I)2A10A1(C4H I)2, and/or methylaluminoxane (MAO). Other suitable examples include Li AKCLIL^ and LiAl(C7Hi5)4. In any embodiment, the trialkyl aluminums and alkyl-aluminums resulting from bonding of at least two aluminum compounds may be used.

[00137] In any embodiment, the co-catalyst may be an organo aluminum compound that is halogen free. Suitable halogen free organoaluminum compounds are, in particular, branched unsubstituted alkylaluminum compounds of the formula AIR3, where R denotes an alkyl radical having 1 to 10 carbon atoms, such as for example, trimethylaluminum, triethylaluminum, triisobutylaluminum and tridiisobutylaluminum. Additional compounds that are suitable for use as a co-catalyst are readily available and amply disclosed in the prior art including U.S. Pat. No. 4,990,477. In any embodiment, the organoaluminum Ziegler-Natta co-catalyst may be trimethyl aluminum, triethylaluminum (TEAL), or a combination thereof.

Internal Electron Donors

[00138] Electron donors suitable for use herein generally may be used in two ways in the formation of Ziegler-Natta catalysts and catalyst systems. In any embodiment, an internal electron donor may be used in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl. Examples of suitable internal electron donors include amines, amides, ethers, esters, esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, and salts of organic acids. In any embodiment, the internal donor may be non-aromatic. In any embodiment, the non-aromatic internal electron donor may contain an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioethers, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof.

[00139] In any embodiment, the solid titanium catalyst component may be prepared using a non-aromatic internal electron donor. Examples of suitable non-aromatic internal electron donors include oxygen-containing electron donors such as alcohols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic oxides, ethers, acid amides and acid anhydrides; nitrogen-containing electron donors such as ammonia, amines, nitriles, and/or isocyanates. Suitable examples include alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, and the like; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, and the like; organic acid esters having 2 to 30 carbon atoms including the esters desired to be included in the titanium catalyst component, such as methyl formate, ethyl formate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, ethylcyclo-hexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di(2-ethylhexyl) 1,2-cyclohexanedicarboxylate, gamma-butyrolactone, delta-valerolactone, and/or ethylene carbonate; inorganic acid esters such as ethyl silicate and butyl silicate; acid halides having 2 to 15 carbon atoms such as acetyl chloride and the like; ethers having 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and the like; acid amides such as acetamide, and the like; acid anhydrides such as acetic anhydride, and the like; amines such as methylamine, ethylamine, triethylamine, tributylamine, tetramethyl-ethylenediamine, and the like; and nitriles such as acetonitrile, trinitrile, and the like.

[00140] In any embodiment, the non-aromatic internal electron donor may contain a Ci to

C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid. In any embodiment, the non-aromatic internal electron donor may be a succinate according to the following formula:

[00141] where each R¹ and R² is independently Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals; R³ to R⁶ are independently, hydrogen, halogen, or Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals, where the R³ to R⁶ radicals are not joined together, where at least two of the R³ to R⁶ radicals are joined to form a cyclic divalent radical, or a combination thereof.

[00142] In any embodiment, R³ to R⁵ may be hydrogen and R⁶ may be a radical selected from the group consistent of a primary branched, secondary or tertiary alkyl, or cycloalkyl radical having from 3 to 20 carbon atoms. [00143] In any embodiment, the internal donor may be a monosubstituted non-aromatic succinate compound. Suitable examples include diethyl secbutylsuccinate, diethylhexylsuccinate, diethyl cyclopropylsuccinate, diethyl trimethylsilylsuccinate, diethyl methoxy succinate, diethyl cyclohexylsuccinate, diethyl (cyclohexylmethyl) succinate, diethyl t-butylsuccinate, diethyl isobutylsuccinate, diethyl isopropylsuccinate, diethyl neopentylsuccinate, diethyl isopentylsuccinate, diethyl (l,l,ltrifluoro-2-propyl) succinate, diisobutyl sec-butylsuccinate, diisobutylhexylsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl trimethylsilylsuccinate, diisobutyl methoxysuccinate, diisobutyl cyclohexylsuccinate, diisobutyl (cyclohexylmethyl) succinate, diisobutyl t-butylsuccinate, diisobutyl isobutylsuccinate, diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate, diisobutyl isopentylsuccinate, diisobutyl (l,l,l-trifluoro-2-propyl) succinate, dineopentyl sec butylsuccinate, dineopentyl hexylsuccinate, dineopentyl cyclopropylsuccinate, dineopentyl trimethylsilylsuccinate, dineopentyl methoxysuccinate, dineopentyl cyclohexylsuccinate, dineopentyl (cyclohexylmethyl) succinate, dineopentyl tbutylsuccinate, dineopentyl isobutylsuccinate, dineopentyl isopropylsuccinate, dineopentyl neopentylsuccinate, dineopentyl isopentylsuccinate, and/or dineopentyl (l,l,l-trifluoro-2propyl) succinate.

[00144] In any embodiment, the internal electron donor having a structure consistent with formula (I) may contain at least two radicals from R³ to R⁶, which are different from hydrogen and are selected from Ci to C20 linear or branched alkyl, alkenyl, and/or cycloalkyl hydrocarbyl groups, which may contain heteroatoms. In any embodiment, two radicals different from hydrogen may be linked to the same carbon atom. Suitable examples include 2,2-disubstituted succinates including diethyl 2,2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-(cyclohexylmethyl)-2-isobutylsuccinate, diethyl 2-cyclopentyl-2-n-propylsuccinate, diethyl 2,2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2- methylsuccinate, diethyl 2,2-diisopropyl diethyl 2isobutyl-2-ethylsuccinate, diethyl 2-(l,l,l- trifluoro-2-propyl)-2-methylsuccinate, diethyl 2 isopentyl-2-isobutylsuccinate, diisobutyl 2,2dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-(cyclohexylmethyl)- 2-isobutylsuccinate, diisobutyl 2-cyclopentyl-2-n-propylsuccinate, diisobutyl 2,2- diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate, diisobutyl 2-isopropyl-2- methylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2-( 1,1,1 -trifluoro-2- propyl)-2-methylsuccinate, diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2,2- diisopropylsuccinate, dineopentyl 2,2-dimethylsuccinate, dineopentyl 2-ethyl-2- methylsuccinate, dineopentyl 2-(cyclohexylmethyl)-2isobutylsuccinate, dineopentyl 2- cyclopentyl-2-n-propylsuccinate, dineopentyl 2,2-diisobutylsuccinate, dineopentyl 2- cyclohexyl-2-ethylsuccinate, dineopentyl 2-isopropyl-2methylsuccinate, dineopentyl 2- isobutyl-2-ethylsuccinate, dineopentyl 2-(l,l,l-trifluoro-2- propyl)-2-methylsuccinate, dineopentyl 2,2-diisopropylsuccinate, and/or dineopentyl 2-isopentyl-2isobutylsuccinate.

[00145] In any embodiment, at least two radicals different from hydrogen may be linked to different carbon atoms between R³ and R⁶. Examples include R³ and R⁵ or R⁴ and R⁶. Suitable non-aromatic succinate compounds include: diethyl 2,3-bis (trimethylsilyl) succinate, diethyl

2.2-secbutyl-3-methylsuccinate, diethyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl

2.3-bis (2-ethylbutyl) succinate, diethyl 2,3-diethyl-2-isopropylsuccinate, diethyl 2,3- diisopropyl-2methylsuccinate, diethyl 2,3-dicyclohexyl-2-methylsuccinate, diethyl 2,3- diisopropylsuccinate, diethyl 2,3-bis (cyclohexylmethyl) succinate, diethyl 2,3- ditbutylsuccinate, diethyl 2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl

2.3-diisopentylsuccinate, diethyl 2,3-(l-trifluoromethyl-ethyl) succinate, diethyl 2-isopropyl-3- isobutylsuccinate, diethyl 2-t-butyl-3isopropylsuccinate, diethyl 2-isopropyl-3- cyclohexylsuccinate, diethyl 2-isopentyl-3cyclohexylsuccinate, diethyl 2-cyclohexyl-3- cyclopentylsuccinate, diethyl 2,2,3,3-tetramethylsuccinate, diethyl 2,2,3,3-tetraethylsuccinate, diethyl 2,2,3,3-tetrapropylsuccinate, diethyl 2,3-diethyl-2,3-diisopropylsuccinate, diisobutyl

2.3-bis (trimethylsilyl) succinate, diisobutyl 2,2-sec-butyl-3-methylsuccinate, diisobutyl 2- (3,3,3-trifluoropropyl)-3- methylsuccinate, diisobutyl 2,3-bis (2-ethylbutyl) succinate, diisobutyl 2,3-diethyl-2 isopropylsuccinate, diisobutyl 2,3-diisopropyl-2-methylsuccinate, diisobutyl 2,3-dicyclohexyl2-methylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisobutyl

2.3-bis (cyclohexylmethyl) succinate, diisobutyl 2,3-di-t-butylsuccinate, diisobutyl 2,3- diisobutylsuccinate, diisobutyl 2,3-dineopentylsuccinate, diisobutyl 2,3diisopentylsuccinate, diisobutyl 2,3-(l,l,l-trifluoro-2-propyl) succinate, diisobutyl 2,3-n-propylsuccinate, diisobutyl

2-isopropyl-3ibutylsuccinate, diisobutyl 2-terbutyl-3-ipropylsuccinate, diisobutyl 2-isopropyl-

3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate, diisobutyl 2-n-propyl-3 (cyclohexylmethyl) succinate, diisobutyl 2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl

2.2.3.3-tetramethylsuccinate, diisobutyl 2,2,3,3-tetraethylsuccinate, diisobutyl 2,2,3,3- tetrapropylsuccinate, diisobutyl 2,3-diethyl-2,3-diisopropylsuccinate, dineopentyl 2,3bis (trimethylsilyl) succinate, dineopentyl 2,2-di-sec-butyl-3-methylsuccinate, dineopentyl 2 (3,3,3-trifluoropropyl)-3-methylsuccinate, dineopentyl 2,3 bis (2-ethylbutyl) succinate, dineopentyl 2,3-diethyl-2-isopropylsuccinate, dineopentyl 2,3-diisopropyl-2-methylsuccinate, dineopentyl 2,3-dicyclohexyl-2-methylsuccinate, dineopentyl 2,3-diisopropylsuccinate, dineopentyl 2,3-bis (cyclohexylmethyl) succinate, dineopentyl 2,3-di-t-butylsuccinate, dineopentyl 2,3-diisobutylsuccinate, dineopentyl 2,3 dineopentylsuccinate, dineopentyl 2,3- diisopentylsuccinate, dineopentyl 2,3-(l,l,l-trifluoro-2propyl) succinate, dineopentyl 2,3-n- propylsuccinate, dineopentyl 2-isopropyl-3-isobutylsuccinate, dineopentyl 2-t-butyl-3- isopropylsuccinate, dineopentyl 2-isopropyl-3-cyclohexylsuccinate, dineopentyl 2-isopentyl-3 cyclohexylsuccinate, dineopentyl 2-n-propyl-3-(cyclohexylmethyl) succinate, dineopentyl 2 cyclohexyl-3-cyclopentylsuccinate, dineopentyl 2,2,3,3-tetramethylsuccinate, dineopentyl 2,2,3,3-tetraethylsuccinate, dineopentyl 2,2,3,3-tetrapropylsuccinate, and/or dineopentyl 2,3- diethyl 2,3-diisopropylsuccinate.

[00146] In any embodiment, the compounds according to formula (I) may include two or four of the radicals R³ to R⁶ joined to the same carbon atom which are linked together to form a cyclic multivalent radical. Examples of suitable compounds include l-(ethoxycarbonyl)-l- (ethoxyacetyl)-2,6-dimethylcyclohexane, l-(ethoxycarbonyl)-l-(ethoxyacetyl)-2, 5-dimethyl- cyclopentane, l-(ethoxycarbonyl)-l-(ethoxyacetylmethyl)-2-methylcyclohexane, and/or 1- (ethoxycarbonyl)-l-(ethoxy (cyclohexyl) acetyl) cyclohexane.

[00147] For purposes herein, all the above mentioned compounds can be used either in form of pure stereoisomers or in the form of mixtures of enantiomers, or mixture of diastereoisomers and enantiomers. When a pure isomer is to be used it may be isolated using the common techniques known in the art. In particular, some of the succinates can be used as a pure rac or meso forms, or as mixtures thereof, respectively.

[00148] In any embodiment, the internal electron donor compound may be selected from diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3- diisopropylsuccinate, diethyl 2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,3-dicyclohexyl-

2-methylsuccinate, diisobutyl 2,2-dimethylsuccinate, diethyl 2,2-dimethylsuccinate, diethyl 2- ethyl-2-methylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-(cyclohexylmethyl)-

3-ethyl-3-methylsuccinate, diisobutyl 2-(cyclohexylmethyl)-3-ethyl-3-methylsuccinate, or combinations thereof.

External Electron Donors

[00149] In any embodiment, in conjunction with an internal donor, two or more external electron donors may also use in combination with a catalyst. External electron donors include, but are not limited to, organic silicon compounds, e.g., tetraethoxysilane (TEOS), methylcyclohexyldimethoxysilane (MCMS), propyltriethoxysilane (PTES) and dicyclopentydimethoxysilane (DCPMS). Internal and external-type electron donors are described, for example, in U.S. Pat. No. 4,535,068. The use of organic silicon compounds as external electron donors is described, for example, in U.S. Pat. Nos. 4,218,339; 4,328,122; 4,395,360; and 4,473,660. The external electron donors act to control stereoregularity, which affects the amount of isotactic versus atactic polymers produced in a given system. The more stereoregular isotactic polymer is more crystalline, which leads to a material with a higher flexural modulus. Highly crystalline, isotactic polymers also display lower MFRs, as a consequence of a reduced hydrogen response during polymerization. The stereoregulating capability and hydrogen response of a given external electron donor are directly and inversely related. The DCPMS donor has a substantially lower hydrogen response than the PTES donor, but produces a significantly higher level of stereoregularity than PTES.

[00150] In any embodiment, the two external electron donors A and B, also referred to herein as the first external electron donor and the second external electron donor, may be selected such that the melt flow rate MFR (A) of homopolypropylene obtained by homopolymerizing propylene by using the first external electron donor (A) in combination with the solid titanium catalyst component and the organoaluminum compound catalyst component and the MFR (B) of homopolypropylene obtained by homopolymerizing propylene by using the second external electron donor (B) under the same conditions as in the case of using the external electron donor (A) have the following relation:

1.2 < log [MFR (B)/MFR (A)] < 1.4.

[00151] The external electron donors to be used in the preparation of the electron donor catalyst component may be those electron donors which are used in preparing the solid titanium catalyst component. In any embodiment, each of the external electron donors (A) and (B) may contain organic silicon compounds.

[00152] In any embodiment, one or more of the external electron donors may contain an organic silicon compound of formula: R³ _nSi(OR⁴)4-_n, where R³ and R⁴ independently represent a hydrocarbyl radical and 0 < n < 4.

[00153] Examples of the suitable organic silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diiso-propyldiethoxysilane, t-butylmethyl- n-diethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o- tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p- tolyldimethoxysilane, bisethylphenyldimethoxy-silane, dicyclohexyldiethoxysilane, cyclohexylmethyl-dimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyl-trimethoxysilane, methyltrimethoxysilane, n-propyl-triethoxysilane, decyltrimethoxysilane, decyltriethoxy-silane, phenyltrimethoxysilane, [gamma]- chloropropyltri-methoxysilane, methyltriethoxysilane, ethyltriethoxy-silane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, gamma-aminopropyltriethoxysilane, chlorotriethoxysilane, vinyltributoxysilane, cyclo-hexyltrimethoxysilane, cyclohexyltriethoxysilane, 2- norbornanetriethoxysilane, 2-norbomanemethyldimethoxy-silane, ethyl silicate, butyl silicate, trimethyl-phenoxysilane, methylallyloxy silane, vinyltris(beta-methoxyethoxysilane), vinyltriacetoxysilane, and/or dimethyltetraethoxydisiloxane.

[00154] In any embodiment, one of the two or more organic silicon compounds may contain the formula: R¹2Si(OR²)2, where R¹ represents a hydrocarbyl radical in which the carbon adjacent to Si is secondary or tertiary. Suitable examples include substituted and unsubstituted alkyl groups such as isopropyl, sec -butyl, t-butyl and t-amyl groups, cyclo-alkyl groups such as cyclopentyl and cyclohexyl groups, cycloalkenyl groups such as a cyclopentenyl group, and aryl groups such as phenyl and tolyl groups. In any embodiment, R² may represent a hydrocarbyl radical, or a hydrocarbyl radical having 1 to 5 carbon atoms, or a hydrocarbyl radical having 1 or 2 carbon atoms.

[00155] Examples of suitable organic silicon compound include diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-sec -butyldimethoxysilane, di-t- butyldimethoxysilane, di-t-amyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxy-silane, diphenyldimethoxysilane, bis-o-tolyldimethoxy-silane, bis-m- tolyldimethoxysilane, bis-p-tolyldi-methoxysilane, and/or bis-ethylphenyldimethoxysilane.

[00156] In any embodiment, the organic silicon compound may be represented by the following general formula: R¹ _nSi(OR²)4-_n, where n is 2, R¹ each represents a hydrocarbyl radical and at least one of the two hydrocarbyl radicals is a hydrocarbon group in which the carbon adjacent to Si is a primary carbon. Examples of suitable hydrocarbon groups include alkyl groups such as ethyl, n-propyl and n-butyl groups, aralkyl groups such as cumyl and benzyl groups, and alkenyl groups such as a vinyl group, and the like.

[00157] In any embodiment, R² may represent a hydrocarbyl radical having 1 to 5 carbon atoms, or from 1 to 2 carbon atoms. Suitable examples of the organic silicon compounds in which n is 2 include diethyldimethoxysilane, dipropyldimethoxysilane, di-n- butyldimethoxysilane, dibenzyldimethoxy silane, and/or divinyldimethoxysilane.

[00158] Examples of suitable compounds when 0 < n < 2 or 2 < n < 4 include R¹ being an alkyl, cycloalkyl, alkenyl, aryl or aralkyl group and R² represents a hydrocarbyl radical having 1 to 5 carbon atoms, or 1 to 2 carbon atoms.

[00159] Suitable examples of the organic silicon compounds in which 0 < n < 2 or 2 < n < 4 include trimethylmethoxysilane, trimethylethoxysilane, methyl-phenyldimethoxysilane, methyltrimethoxysilane, t-butyl-methyldimethoxysilane, t-butylmethyldiethoxysilane, t- amylmethyldimethoxysilane, phenylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldi-ethoxysilane, ethyltrimethoxysilane, ethyltriethoxy-silane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, 2-norbornanetrimethoxysilane, and/or 2- norbornanetriethoxy- silane .

[00160] In any embodiment, the external electron donors include methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane and/or cyclohexyltrimethoxysilane.

[00161] In any embodiment, the above disclosed organic silicon compounds may be used such that a compound capable of being changed into such an organic silicon compound is added at the time of polymerizing or preliminarily polymerizing an olefin, and the organic silicon compound may be formed in situ during the polymerization or the preliminary polymerization of the olefin.

[00162] In any embodiment, a first external electron donor may have the formula R¹2Si(OR²)2, where each R¹ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and each R² is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms. A second external electron donor can have the formula R³ _nSi(OR⁴)4 n, where each R³ and R⁴ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms, and n is 1, 2, or 3. The second external electron donor can be different than the first external electron donor.

[00163] In any embodiment, the first external electron donor and the second external electron donor may be selected from tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltriethoxysilane, dicyclopentydimethoxysilane, or combinations thereof. In any embodiment, the Ziegler-Natta catalyst system may contain 2.5 mol% to less than 50 mol% of the first external electron donor and greater than 50 mol% of a second external electron donor based on total mol% of external electron donors. In any embodiment, the first electron donor may contain, consist of, or consist essentially of dicyclopentyldimethoxysilane (DCPMS) and the second external electron donor may contain, consist of, or consist essentially of propyltriethoxysilane (PTES).

[00164] In any embodiment, a relationship between the first external electron donor and the second external electron donor may be defined by the equation:

1.2 < log [MFR(B )/MFR( A)] < 1.4,

[00165] where MFR(A) is a first melt flow rate of a homopolymer formed by polymerizing propylene monomers in the presence of the Ziegler-Natta catalyst and the first external electron donor, and where MFR(B) is a second melt flow rate of a homopolymer formed by polymerizing propylene monomers in the presence of the Ziegler-Natta catalyst and the second external electron donor, and where the MFR(A) is lower than the MFR(B).

Polymerization Process

[00166] In any embodiment, a method to make the linear polypropylene may contain contacting propylene monomers at propylene polymerization conditions with a catalyst system to produce a linear polypropylene containing at least 50 mol% propylene, an MWD greater than 5 and a melt strength of at least 5 cN to 30 cN as determined using an extensional rheometer at

190°C, the catalyst system containing: a Ziegler-Natta catalyst containing a non-aromatic internal electron donor; and first and second external electron donors containing different organosilicon compounds. In any embodiment, the first external electron donor may have the formula R¹2Si(OR²)2, where each R¹ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and where each R² is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms; and the second external electron donor has the formula R³ _nSi(OR⁴)4-_n, where each R³ and R⁴ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms, n is 1, 2, or 3, and the second external electron donor is different than the first external electron donor.

[00167] In any embodiment, the non-aromatic internal electron donor may contain an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioether, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof, or a Ci to C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid, or a succinate according to the formula:

[00168] where R¹ and R² are, independently, Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals; R³ to R⁶ are, independently, hydrogen, halogen, or Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals, where the R³ to R⁶ radicals are not joined together, or where at least two of the R³ to R⁶ radicals are joined to form a cyclic divalent radical, or a combination thereof.

[00169] In any embodiment, the polymerization process according to the instant disclosure may include contacting propylene with any embodiment herein described of the catalyst system under polymerization conditions. The polymerization process may include a preliminary polymerization step. The preliminary polymerization may include utilizing the Ziegler-Natta catalyst system containing the non-aromatic internal electron donor in combination with at least a portion of the organoaluminum co-catalyst where at least a portion of the external electron donors are present where the catalyst system is utilized in a higher concentration than utilized in the subsequent "main" polymerization process.

[00170] In any embodiment, the concentration of the catalyst system in the preliminary polymerization, based on the moles of titanium present, may be 0.01 to 200 millimoles, or 0.05 to 100 millimoles, calculated as a titanium atom, per liter of an inert hydrocarbon medium. The organoaluminum co-catalyst may be present in an amount sufficient to produce 0.1 to 500 g, or 0.3 to 300 g, of a polymer per gram of the titanium catalyst present, and may be present at 0.1 to 100 moles, or 0.5 to 50 moles, per mole of the titanium atom present in the catalyst component.

[00171] In any embodiment, the preliminary polymerization may be carried out under mild conditions in an inert hydrocarbon medium in which an olefin and the catalyst components are present. Examples of the inert hydrocarbon medium used include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene and xylene; halogenated hydrocarbons, such as ethylene chloride and chlorobenzene; and mixtures thereof. The olefin used in the preliminary polymerization may be the same as an olefin to be used in the main polymerization.

[00172] In any embodiment, the reaction temperature for the preliminary polymerization may be a point at which the resulting preliminary polymerization does not dissolve substantially in the inert hydrocarbon medium, which may be -20°C to 100°C, -20°C to 80°C, or 0°C to 40°C.

[00173] In any embodiment, during the preliminary polymerization, a molecular weight controlling agent such as hydrogen may be used. The molecular weight controlling agent may desirably be used in such an amount that the polymer obtained by preliminary polymerization has properties consistent with the intended product. In any embodiment, the preliminary polymerization may be carried out so that 0.1 to 1,000 g, or 0.3 to 300 g, of a polymer forms per gram of the titanium catalyst.

[00174] In any embodiment, a method for making the linear polypropylene may contain contacting propylene monomers at a temperature and a pressure in the presence of catalyst system to produce a propylene resin containing at least 50 mol% propylene, where the catalyst system contains: a Ziegler-Natta catalyst containing a non-aromatic internal electron donor; a first external electron donor having the formula R¹2Si(OR²)2, where each R¹ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and where each R² is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms; and a second external electron donor having the formula R³ _nSi(OR⁴)4-_n, where each R³ and R⁴ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms, n is 1, 2, or 3; and the second external electron donor is different than the first external electron donor.

[00175] In any embodiment, the propylene polymer resin may have a melt strength of at least 5 cN to 30 cN or 50 cN as determined using an extensional rheometer at 190°C. In any embodiment, the olefin may contain or consist essentially of propylene. In any embodiment, the olefin may contain from 0 wt % to 49 wt % of an alpha olefin other than propylene, as defined herein. In any embodiment, the alpha olefin may include ethylene, 1-butene, 4-methyl-l- pentene, 1-octene, or a combination thereof. In any embodiment, the olefin may contain at least 50 wt % propylene, or at least 75 wt%, or at least 99 wt% propylene.

[00176] In any embodiment, the polymerization of the olefin may be carried out in the gaseous phase, the liquid phase, bulk phase, slurry phase, or any combination thereof. In any embodiment, polymerization may be carried out by slurry polymerization where the inert hydrocarbon may be used as a reaction solvent, or an olefin liquid under the reaction conditions may be used as the solvent.

[00177] In any embodiment, the titanium catalyst may be present in the reactor at 0.005 to 0.5 millimoles, such as 0.01 to 0.5 millimoles, based on Ti moles per liter of the reaction zone. In any embodiment, the organoaluminum co-catalyst may be present in an amount sufficient to produce 1 to 2,000 moles, or 5 to 500 moles of aluminum per mole of the titanium atom in the catalyst system. In any embodiment, the internal electron donor may be present at 0.2 to 5.0, or 0.5 to 2.0 per mole of Ti. In any embodiment, the total amount of the external electron donors may be 0.001 to 50 moles, or 0.01 to 20 moles, or 0.05 to 10 mole Si per mole of Ti present. In any embodiment, the first external electron donor may be present in the catalyst system at from 2.5 to 50 mol%, or 2.5 to 10 mol% of the total amount of external electron donor present.

[00178] In any embodiment, the polymerization process may include contacting the titanium catalyst component, the internal electron donor, the organoaluminum co-catalyst, and the two external electron donors with each other at the time of the main polymerization, before the main polymerization, for example, at the time of the preliminary polymerization, or a combination thereof. In contacting the components before the main polymerization, any two or more of these components may be freely selected and contacted. In any embodiment, two or more of the components may be contacted individually or partly and then contacted with each other in total to produce the catalyst system.

[00179] In any embodiment, the catalyst system components may be contacted with each other before the polymerization in an inert gaseous atmosphere, the individual catalyst components may be contacted with each other in an olefin atmosphere, or any combination thereof. In any embodiment, hydrogen may be used during the polymerization to control the molecular weight and other properties of the resulting polymer (e.g., the linear polypropylene). [00180] In any embodiment, polymerization conditions may include a polymerization temperature of 20°C to 200°C, or 50°C to 180°C, and a pressure from atmospheric pressure to 100 kg/cm², or from 2 to 50 kg/cm². The polymerization process according to the instant disclosure may be carried out batchwise, semi-continuously, or continuously. The polymerization may be carried out in two or more stages, using two or more reactors under different reaction conditions, utilizing different internal electron donors, different external electron donors, and/or different catalyst systems.

[00181] In any embodiment, the linear polypropylene according to the instant disclosure may be produced in a bulk continuous reactor. A catalyst system containing a magnesium chloride supported titanium catalyst according to one or more embodiments of the instant disclosure is utilized. Catalyst preparation may be carried out continuously in situ by contacting the catalyst solids, triethylaluminum, and the external electron donor system under conditions known in the art to yield active, stereospecific catalyst for polymerization of propylene. The activated catalyst may then be continuously fed into a prepolymerization reactor where it was continuously polymerized in propylene to a productivity of approximately 100 to 400 g- polymer/g-cat. The prepolymerized catalyst may then be continuously fed into a bulk slurry reactor, and polymerization continued at 70°C to 80°C, for a residence time of 90 minutes. The reaction slurry (homopolymer granules in bulk propylene) may then be removed from the reactor and the polymer granules continuously separated from the liquid propylene. The polymer granules may then be separated from the unreacted monomer to produce a granular product for compounding and/or mechanical properties. In any embodiment, hydrogen may be used in the reactor to control the MFR of the linear polypropylene.

[00182] In the case of impact copolymer resin production, the granules from the bulk reactor, after removing the monomer, may be fed directly into a gas phase reactor (GPR) where polymerization is continued under conditions known in the art to produce ethylene-propylene bipolymer within the pores of the polymer granules. The final product, referred to in the art as an "impact copolymer," may be continuously withdrawn from the gas phase reactor and separated from unreacted monomer to produce a granular product for compounding and further processing. The molecular weight of the ethylene-propylene rubber or more appropriately, Intrinsic Viscosity (IV) of the rubber phase may be controlled by the concentration of hydrogen in the GPR.

[00183] In any embodiment, the granules from the reactor may be stabilized with at least 0.01 wt% of an additive, e.g., 0.15 wt% Irganox™ 1010, 0.05 wt% Ultranox™ 626A, and/or with 0.075 wt% sodium benzoate (fine form) and then pelletized, e.g., on a 30 mm Werner & Pfleiderer twin screw extruder. The pellets may then be injection molded, and/or subjected to further processing.

[00184] In any embodiment, a linear polypropylene may contain at least 50 mol% propylene and has a melt strength of at least 5 cN to 30 cN or 50 cN as determined using an extensional rheometer at 190°C. For purposes herein, the melt strength of a polymer at a particular temperature, e.g., 190°C, is determined with a Gottfert Rheotens Melt Strength Apparatus (e.g., Gottfert Rheotens 71.97). The measurement is accomplished by grasping the extrudate from a capillary rheometer (e.g., a Gottfert Rheograph 2002 capillary rheometer), or from an extruder equipped with a capillary die, after the extrudate has been extruded 100 mm using variable speed gears and increasing the gear speed at a constant acceleration (12 mm/s², starting from an initial, zero-force calibration velocity of 10 mm/s) until the molten polymer strand breaks. The force in the strand is measured with a balance beam in conjunction with a linear variable displacement transducer. The force required to extend and then break the extrudate is defined as the melt strength. The force is measured in centinewtons (cN). A typical plot of force vs. wheel velocity is known in the art to include a resonate immediately before the strand breaks. In such cases, the plateau force is approximated by the midline between the oscillations.

[00185] One of the most distinctive improvements of the instant disclosure is an unexpectedly high melt strength of the linear polyethylenes and/or the polyolefin compositions. Melt strength is a key property of products used in blown film, thermoforming, blow molding processes, and the like. In a blown film process, high melt strength maintains a stable bubble when running at high temperatures and/or at high production rates, especially on large lines. If the melt strength is unacceptably low, holes form in a molten web, which causes the bubble to collapse and occasionally tear off. This, in turn, results in loss of production, and can lead to subsequent quality problems if the material in the extruder begins to degrade during the down time. Low melt strength in the linear polyethylenes precludes the film manufacturer from taking advantage of the excellent draw-down characteristics inherent with most linear polyethylenes unless a melt strength enhancer, such as LDPE, is added.

[00186] In any embodiment, a linear polypropylene, according to any of the embodiments disclosed herein, can have a melt strength of at least 5 cN, 8 cN, 10 cN, 12 cN, 15 cN, 18 cN, or 20 cN to 22 cN, 25 cN, 28 cN, 30 cN, 35 cN, 40 cN, 45 cN, 50 cN, 60 cN, 70 cN, 80 cN, 90 cN, 100 cN, or greater, as determined using an extensional rheometer at 190°C as described herein. For example, the linear polypropylene can have a melt strength of at least 5 cN to 100 cN, at least 5 cN to 70 cN, at least 5 cN to 50 cN, at least 5 cN to 40 cN, at least 5 cN to 35 cN, at least 5 cN to 30 cN, at least 5 cN to 25 cN, at least 5 cN to 20 cN, at least 5 cN to 18 cN, at least 5 cN to 15 cN, at least 5 cN to 12 cN, at least 5 cN to 10 cN, at least 5 cN to 8 cN, 10 cN to 100 cN, 10 cN to 80 cN, 10 cN to 65 cN, 10 cN to 50 cN, 10 cN to 40 cN, 10 cN to 35 cN, 10 cN to 30 cN, 10 cN to 25 cN, 10 cN to 20 cN, 10 cN to 18 cN, 10 cN to 15 cN, 10 cN to 12 cN, 15 cN to 100 cN, 15 cN to 80 cN, 15 cN to 50 cN, 15 cN to 40 cN, 15 cN to 35 cN, 15 cN to 30 cN, 15 cN to 25 cN, 15 cN to 20 cN, 15 cN to 18 cN, 25 cN to 100 cN, 25 cN to 80 cN, 25 cN to 50 cN, 25 cN to 40 cN, 25 cN to 35 cN, 25 cN to 30 cN, 30 cN to 100 cN, 30 cN to 80 cN, 30 cN to 50 cN, 30 cN to 45 cN, 30 cN to 40 cN, or 30 cN to 35 cN, as determined using an extensional rheometer at 190°C as described herein.

[00187] In any embodiment, the linear polypropylene has an MFR from 1 g/10 min, 1.1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.4 g/10 min, or 1.5 g/10 min to 1.6 g/10 min, 1.7 g/10 min, 1.8 g/10 min, 1.9 g/10 min, less than 2 g/10 min, 2 g/10 min, 2.5 g/10 min, 3 g/10 min, 3.5 g/10 min, 4 g/10 min, or 5 g/10 min, as determined according to ASTM D1238 Condition L. For example, the linear polypropylene has an MFR from 1 g/10 min to 5 g/10 min, 1 g/10 min to 4 g/10 min, 1 g/10 min to 3.5 g/10 min, 1 g/10 min to 3 g/10 min, 1 g/10 min to 2.5 g/10 min, 1 g/10 min to 2 g/10 min, 1 g/10 min to less than 2 g/10 min, 1 g/10 min to 1.9 g/10 min, 1 g/10 min to 1.8 g/10 min, 1 g/10 min to 1.6 g/10 min, 1 g/10 min to 1.5 g/10 min, 1 g/10 min to 1.4 g/10 min, 1 g/10 min to 1.2 g/10 min, 1.5 g/10 min to 5 g/10 min, 1.5 g/10 min to 4 g/10 min, 1.5 g/10 min to 3.5 g/10 min, 1.5 g/10 min to 3 g/10 min, 1.5 g/10 min to 2.5 g/10 min, 1.5 g/10 min to 2 g/10 min, 1.5 g/10 min to less than 2 g/10 min, 1.5 g/10 min to 1.9 g/10 min, 1.5 g/10 min to 1.8 g/10 min, or 1.5 g/10 min to 1.6 g/10 min, as determined according to ASTM D1238 Condition L.

[00188] In any embodiment, the linear polypropylene can have a branching index (g'vis) of 0.95 or greater, such as 0.96 or greater, 0.97 or greater to 0.98 or greater, 0.99 or greater, or 1. For example, the linear polypropylene can have a branching index (g'vis) of 0.95 to 1, 0.96 to 1, 0.97 to 1, 0.98 to 1, or 0.99 to 1.

[00189] In any embodiment, the linear polypropylene has a number average molecular weight (Mn) of 30,000 g/mol to 50,000 g/mol, 35,000 g/mol to 45,000 g/mol, 37,000 g/mol to 42,000 g/mol, or 39,000 g/mol to 40,000 g/mol. The linear polypropylene has a weight average molecular weight (Mw) of 500,000 g/mol to 700,000 g/mol, 550,000 g/mol to 600,000 g/mol, or 570,000 g/mol to 585,000 g/mol. The linear polypropylene has an average molecular weight (Mz) of 2,500,000 g/mol to 4,000,000 g/mol, 2,800,000 g/mol to 3,700,000 g/mol, 3,000,000 g/mol to 3,500,000 g/mol, or 3,100,000 g/mol to 3,300,000 g/mol. The linear polypropylene has a Z+l average molecular weight (Mz+1) of 6,000,000 g/mol to 7,000,000 g/mol, 6,200,000 g/mol to 6,700,000 g/mol, or 6,350,000 g/mol to 6,550,000 g/mol.

[00190] The linear polypropylene has an Mz/Mw molecular weight distribution of 5, 5.1, 5.2, 5.3, 5.4, or 5.5 to 5.6, 5.7, 5.8, 5.9, or 6. For example, the linear polypropylene has an Mz/Mw molecular weight distribution of 5 to 6, 5.2 to 6, 5.4 to 6, 5.5 to 6, 5.6 to 6, 5.8 to 6, 5 to 5.8, 5.2 to 5.8, 5.4 to 5.8, 5.5 to 5.8, 5.6 to 5.8, 5.8 to 5.8, 5 to 5.6, 5.2 to 5.6, 5.4 to 5.6, 5.5 to 5.6, 5 to 5.5, 5.2 to 5.5, 5.4 to 5.5, 5 to 5.4, 5 to 5.3, or 5 to 5.2.

[00191] The linear polypropylene has an Mw/Mn molecular weight distribution of 13, 13.5,

13.8, 14, 14.2, 14.4, 14.5, 14.6, 14.8, 15, 15.5, or 16. For example, the linear polypropylene has an Mw/Mn molecular weight distribution of 13 to 16, 13.5 to 15.5, 13.8 to 15.3, 14 to 15, 14.2 to 15, 14.4 to 15, 14.6 to 15, 14.8 to 15, 14.2 to 14.8, 14.4 to 14.8, 14.6 to 14.8, 14.7 to

14.8, 14.2 to 14.6, 14.4 to 14.6, or 14.5 to 14.6.

[00192] A linear polypropylene, according to any of the embodiments disclosed herein, further may contain at least 75 mol%, or at least 80 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mol% propylene. In any embodiment, a linear polypropylene, according to any of the embodiments disclosed herein, may be a propylene homopolymer.

[00193] A linear polypropylene, according to any of the embodiments disclosed herein, may contain from 0.1 to 10 mol% of a comonomer. In any embodiment, the comonomer may be one or more alpha olefins. In any embodiment, the comonomer may be selected from ethylene and/or C4 to C20 olefins.

[00194] A linear polypropylene, according to any of the embodiments disclosed herein, may have a stiffness of greater than 2,000 MPa, or greater than 2,100 MPa, or 290 kpsi (2,000 MPa) to 360 kpsi (2,500 MPa) determined according to ASTM D790A on nucleated samples with 0.1% sodium benzoate. A linear polypropylene, according to any of the embodiments disclosed herein, may have a viscosity ratio of greater than or equal to 35, or 40, or 45, or from 35 to 80 determined at an angular frequency ratio of 0.01 and at an angular frequency ratio of 100 rad/s (at an angular frequency ratio of 0.01 to 100 rad/s) at a fixed strain of 10% at 190°C.

[00195] A linear polypropylene, according to any of the embodiments disclosed herein, may be an impact copolymer. For purposes herein, an impact copolymer refers to a resin containing a homopolymer made in a bulk polymerization reactor followed by transferring the granules to the gas phase reactor and making ethylene-propylene rubber within the granules.

[00196] In any embodiment, the linear polypropylene may be a non-functionalized polymer or resin. For purposes herein, a non-functionalized resin does not contain grafted or otherwise post-reactor processed olefin polymers. By functionalized (or grafted) it is meant that various functional groups are incorporated, grafted, bonded to, and/or physically or chemically attached to the polymer backbone of the polymer being functionalized after formation of the base polymer. Examples of functionalized polymers include polymers in which functional groups are grafted onto the polymer backbone or pendent groups utilizing radical copolymerization of a functional group, referred to in the art as graft copolymerization. Examples of functional groups utilized to produce functionalized polymers include unsaturated carboxylic acids, esters of the unsaturated carboxylic acids, acid anhydrides, di-esters, salts, amides, imides, aromatic vinyl compounds, hydrolyzable unsaturated silane compounds, and unsaturated halogenated hydrocarbons. Specific examples of unsaturated carboxylic acids and acid derivatives include, but are not limited to, maleic anhydride, citraconic anhydride, 2-methyl maleic anhydride, 2- chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicyclo[2,2,l]-5-heptene-2,3- dicarboxylic anhydride and 4-methyl-4-cyclohexene- 1 ,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10- octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-l,3-diketospiro(4.4)non-7-ene, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophtalic anhydride, norbom-5-ene-2,3-dicarboxylic acid anhydride, nadic anhydride, methyl nadic anhydride, himic anhydride, methyl himic anhydride, and x-methyl- bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride (XMNA). Examples of the esters of the unsaturated carboxylic acids include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Hydrolyzable unsaturated silane compounds useful as functional groups present in functionalized polymers include a radical polymerizable unsaturated group having an alkoxysilyl group or a silyl group in its molecule. Examples include a compound having a hydrolyzable silyl group bonded to a vinyl group and/or a hydrolyzable silyl group bonded to the vinyl group via an alkylene group, and/or a compound having a hydrolyzable silyl group bonded to an ester or an amide of acrylic acid, methacrylic acid, or the like. Examples thereof include vinyltrichlorosilane, vinyltris(beta- methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma- methacryloxypropyltrimethoxysilane, monovinylsilane, and monoallylsilane. Examples of unsaturated halogenated hydrocarbons useful as functional groups include vinyl chloride and vinylidene chloride. For purposes herein, functionalized polymers further include polymers grafted onto other polymers.

[00197] A functionalized polymer is considered to have indications of long chain branching (e.g., a g'vis of less than 0.95), consistent with the cross-linking and intermolecular bonding associated with functionalized polymers. The resin may be produced by contacting propylene monomers at propylene polymerization conditions with a catalyst system containing a Ziegler- Natta catalyst containing a non-aromatic internal electron donor, and first and second external electron donors containing different organosilicon compounds.

[00198] In any embodiment, the resin may be free of functionalized polypropylene or contains less than 5 weight percent of functional groups selected from hydroxide, aryls, substituted aryls, halogens, alkoxys, carboxylates, esters, acrylates, and carboxyl, based upon the weight of the linear polypropylene, and where the number of carbons of the linear polypropylene involved in olefinic bonds is less than 5% of the total number of carbon atoms in the resin. In any embodiment, the resin may be free of post-reactor grafted polypropylene or contains less than 5 percent by weight of post-reactor grafted polypropylene.

[00199] A linear polypropylene, according to any of the embodiments disclosed herein, may have a heat distortion temperature of greater than or equal to 100°C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi).

[00200] A linear polypropylene, according to any of the embodiments disclosed herein, may have an isopentad percentage of greater than 90%, or greater than 95%, or greater than 99%.

[00201] A linear polypropylene, according to any of the embodiments disclosed herein, may contain a blend of various components. The blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti- static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like. Accordingly, a linear polypropylene, according to any of the embodiments disclosed herein, further may contain greater than or equal to 0.01 wt% of one or more fillers; antioxidants; anti-cling agents; tackifiers; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; talc; or a combination thereof.

[00202] A linear polypropylene, according to any of the embodiments disclosed herein, may contain at least 50 mol% propylene, has a melt strength of at least 5 cN determined using an extensional rheometer at 190°C, and an MWD (Mw/Mn) of greater than 5, where the resin is produced by contacting propylene monomers at a temperature and a pressure according to any method or process disclosed herein utilizing any embodiment or combination of embodiments of the catalyst system as disclosed herein.

[00203] A linear polypropylene, according to any of the embodiments disclosed herein, may contain at least 50 mol% propylene, has a melt strength of at least 5 cN determined using an extensional rheometer at 190°C, and an MWD (Mw/Mn) of greater than 5, where the resin is produced by contacting propylene monomers at a temperature and a pressure in the presence of catalyst system containing a Ziegler-Natta catalyst containing a non-aromatic internal electron donor and two or more external electron donors. In any embodiment, the first external electron donor may have the formula R¹2Si(OR²)2, where each R¹ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and where each R² is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms; and the second external electron donor has the formula R³ _nSi(OR⁴)4-_n, where each R³ and R⁴ is independently a hydrocarbyl radical containing from 1 to 10 carbon atoms, where n is 1, 2, or 3; and where the second external electron donor is different than the first external electron donor. Additives and other Polymers

[00204] In some embodiments, other "additives" may also be present in the polyolefin composition, articles, pellets, layers, and/or films thereof. These additives may be added before, during, and/or after the formation of the coextruded sheets or films or other articles. Such additives include antioxidants (e.g., hindered phenol- and phosphite-type compounds), stabilizers such as lactone and vitamin E, nucleators (both a-nucleators and b-nucleators), clarifying agents, colorants (dyes or pigments), fillers (silica or talc), UV stabilizers, release agents, slip agents, tackifiers, anti-static agents, acid scavengers (e.g., calcium stearate), anti blocking agents, anti-blooming agents, polymer processing aid masterbatch (PPA MB) additives/agents, hydrocarbon resins such as Oppera™ type resins, or combinations thereof.

[00205] In any embodiment, the polyolefin composition contains one or more additives in an amount from 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% to 6 wt%, 8 wt%, or 10 wt%, based on the weight of the composition/layer. For example, the polyolefin composition contains from 0.5 wt% to 10 wt%, 0.5 wt% to 8 wt%, 0.5 wt% to 5 wt%, 0.5 wt% to 3 wt%, 0.5 wt% to 2 wt%, 0.5 wt% to 1 wt%, 1 wt% to 10 wt%, 1 wt% to 8 wt%, 1 wt% to 5 wt%, 1 wt% to 3 wt%, or 1 wt% to 2 wt% of the additive. In other embodiments, the polyolefin composition contains one or more additives in an amount from 50 ppm, 100 ppm, 150 ppm, 200 ppm, 300 ppm, 350 ppm, 400 ppm, 420 ppm, 450 ppm, 500 ppm, 750 ppm, or 1,000 ppm to 1,500 ppm, 2,000 ppm, 2,500 ppm, 3,000 ppm, 4,000 ppm, 4,500 ppm, or 5,000 ppm. For example, the polyolefin composition contains 50 ppm to 5,000 ppm, 100 ppm to 5,000 ppm, 150 ppm to 5,000 ppm, 200 ppm to 5,000 ppm, 300 ppm to 5,000 ppm, 420 ppm to 5,000 ppm, 500 ppm to 5,000 ppm, 1,000 ppm to 5,000 ppm, 1,500 ppm to 5,000 ppm, 2,000 ppm to 5,000 ppm, 2,500 ppm to 5,000 ppm, 3,000 ppm to 5,000 ppm, 50 ppm to 3,000 ppm, 100 ppm to 3,000 ppm, 150 ppm to 3,000 ppm, 200 ppm to 3,000 ppm, 300 ppm to 3,000 ppm, 420 ppm to 3,000 ppm, 500 ppm to 3,000 ppm, 1,000 ppm to 3,000 ppm, 1,500 ppm to 3,000 ppm, 2,000 ppm to 3,000 ppm, or 2,500 ppm to 3,000 ppm of the additive.

[00206] In any embodiment, nucleating agents are absent, for example, a-nucleating agents are absent, meaning nucleating agents are not added to the composition or any components of the composition at any stage of the process of formation. Examples of a-nucleating agents include salts of monocarboxylic acids and polycarboxylic acids, sorbitols such as dibenzylidenesorbitol, salts of diesters of phosphoric acid, vinylcycloalkane polymers, or combinations thereof. [00207] The polyolefin compositions of the present disclosure are particularly useful in films and articles that include films or film coatings. Films of less than 250 pm average thickness can be made using the polyolefin compositions and can contain any number of layers, such as additional layers of LLDPE, HDPE, LDPE, iPP, EP copolymers, and combinations thereof. Also, the polyolefin compositions can contain a composition including any of these polymers or combinations of polymers and be present in any desirable amount. Furthermore, sheets having an average thickness of 250 pm or more can be made using the polyolefin compositions described herein, or may contain one or more layers containing polyolefin compositions and another material such as linear low-density polyethylene (LLDPE), HDPE, LDPE, iPP, EP copolymers, and combinations thereof. Such sheets, films, or other desirable structures or articles made using the polyolefin compositions described herein, may be thermoformed, blow molded, injection molded, or extruded into useful articles, and further, polyolefin compositions may be rotomolded to form useful articles.

[00208] In any embodiment, the polyolefin composition can include one or more LLDPEs. The LLDPE is in a concentration of from 5 wt%, 10 wt%, 15 wt%, 20 wt% to 25 wt%, 30 wt%, 40 wt%, or 50 wt% by weight of the overall polyolefin composition. In some examples, the LLDPE contains ethylene derived units and comonomers selected from C3 to CIO alpha-olefin derived units.

[00209] The various descriptive elements and numerical ranges disclosed herein for the polyolefin compositions and methods of forming the polyolefin compositions and films therefrom can be combined with other descriptive elements and numerical ranges to describe the embodiments; further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein, including the examples.

Films formed from the Polyolefin Compositions

[00210] Many articles can be formed from the polyolefin compositions described herein such as thermoformed articles, blow molded articles, injection molded articles, sheets, fibers, fabrics, and other useful items. For example, the polyolefin compositions can be used to produce industrial and food package articles that have a PP/PE film structure. The polyolefin compositions can be formed into films using any suitable method, especially cast films, extrusion coated films, and blown films, and/or included as at least part of one or more layers of a multi-layered film. Such types of films may have two, three, four or more layers represented such as S/C, S/C/S, S/C/C, S/T/C/S, S/T/C/T/S, where "C" is a core layer, "T" is a tie-layer, and "S" is a skin layer, each of which may be made from the same or different materials. Any one or more layers (e.g., core, tie, and/or skin layers) can contain or comprise, consist essentially of, or consist of one or more polyolefin compositions. In some examples, structures include those that contain a layer having a range from 50 wt%, 55 wt%, or 60 wt% to 80 wt%, 85 wt%, or 90 wt%, based on weight of the components of that layer, of one or more polyolefin compositions. In other examples, that layer is a core layer with at least one skin layer containing a polyethylene and/or polypropylene. The polyolefin compositions can replace the HDPE in many known film structures and allow down-gauging by 10% to 30% relative to when HDPE is used.

[00211] The polyolefin compositions can be used in making blown films. In a typical blown film process the ingredients used to form the film are added in any desirable form, such as granules, into a hopper which feeds the material to an extruder, where the materials are melt blended at a desirable temperature through shear forces and/or heating. The molten material is then fed, with or without filtering, to a die which may have just one, or have multiple cavities corresponding to each of multiple layers that will form the film. The die is also heated to a desired temperature and then forced from the die in a direction away from the die. The cooling of the forming film takes place via a device that blows air or one or more other gases (e.g., nitrogen, argon, mixtures thereof) that is at least 5°C or 10°C cooler than the surrounding air, where the "surrounding air" is air that is at least 1 meter from the cooling device, but less than 5 meters. For example, the air can blow against the outside of the film, such as around the entire circumference formed by the film. There is also air blown internally that both cools and blows the film up like a bubble/balloon. The film starts to expand where the film eventually cools and crystallizes to form a blown film. Conventional polypropylenes can be difficult to use for blown film processes because they typically have low melt strength, which will promote breakage of the bubble, balloon, or film. However, the polyolefin compositions of the present disclosure can provide improved melt strength for improved polypropylene -based blown film processes. In addition, the polyolefin compositions of the present disclosure have an enhanced toughness and a greater stiffness compared to conventional polypropylenes.

[00212] The performance of the compositions containing the polypropylenes being formed into a film can be characterized by its Maximum Die Rate. The "Maximum Die Rate" is a normalized extrusion rate by die size which is commonly used in the blown film industry. The Maximum Die Rate as used herein is expressed as follows: Maximum Die Rate [lb/in-hr] = Extrusion Rate [lb/hr] / Die Circumference [inch]. Another definition of the Maximum Die Rate is expressed as follows: Maximum Die Rate [kg/mm-hr] = Extrusion Rate [kg/hr] / Die Diameter [mm]. The Maximum Die Rate at which the film is formed is greater than 13 lb/in- hr (0.73 kg/mm-hr) or 16 lb/in-hr (0.90 kg/mm-hr) or 24 lb/in-hr (1.34 kg/mm-hr), or from 13 lb/in-hr (0.73 kg/mm-hr) or 16 lb/in-hr (0.90 kg/mm-hr), or 24 lb/in-hr (1.34 kg/mm-hr) to 30 (1.69 kg/mm-hr), or 40 lb/in-hr (2.25 kg/mm-hr). Note that for the "Maximum Die Rate" in the English unit, the die dimension is the die circumference, while in metric units, the die dimension is the die diameter. Thus, for die factor in lb/in-hr, the full expression is lb/die circumference (in unit of inch)/hr; and for die factor in kg/mm-hr, the full expression is kg/die diameter (in unit of mm)/hr.

[00213] The polyolefin compositions can be processed at low temperatures. In any embodiment, the polyolefin composition can be processed, such as melt extruded, at barrel temperatures of less than 210°C, 200°C, or 190°C, or from 160°C, 170°C, 175°C, 180°C, or 185°C to 190°C, 195°C, 200°C, 205°C, or 210°C; and die temperatures of less than 210°C, or from 190°C, 200°C, or 205 °C to 210°C.

[00214] In any embodiment, a method for forming or otherwise producing one or more articles containing a polyolefin composition is provided. The method can include extruding, thermoforming, or rolling the polyolefin composition to produce one or more films or one or more sheets. In other embodiments, the method can include flowing a gas through the polyolefin composition to produce one or more foam articles, such as by a blown foam process.

[00215] In some embodiments, a method of forming a finished film or sheet includes extruding a molten polyolefin composition through a die opening to form a film or sheet and causing the film or sheet to progress in a direction away from the die opening, such as in the molten state, partially molten, or softened due to some partial cooling. The method also includes cooling the molten polyolefin composition in the form of a film or sheet at a distance from the die opening, the distance adjusted to effect the properties of the film (e.g., to allow relaxation of the molten polyolefin composition prior to solidification and/or crystallization upon cooling), and isolating a finished film or sheet therefrom.

[00216] In some examples, a method of forming a film or sheet includes extruding the polyolefin composition through one or more die openings to form the film or sheet. For example, the method can include extruding a molten polyolefin composition containing one or more LCB polypropylenes and one or more linear polypropylenes through the die opening to form the film or sheet, and then cooling the film or sheet at a distance away from the die opening to produce a finished film. The film or sheet can be cooled by blowing air, nitrogen, argon, or other gases on at least a portion of the film or sheet. In one or more examples, the molten polyolefin composition can include 10 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 90 wt% of the linear polypropylene, by weight of the polyolefin composition. In some examples, the molten polyolefin composition can include 40 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 60 wt% of the linear polypropylene, by weight of the polyolefin composition. In other examples, the molten polyolefin composition can include 70 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 30 wt% of the linear polypropylene, by weight of the polyolefin composition.

[00217] In any embodiment, a film or other article containing the polyolefin composition has a thickness of from 10 pm, 30 pm, or 50 pm to 100 pm, 200 pm, 300 pm, or 500 pm. In some examples, the film is a monolayer that has a thickness of from 10 pm to 100 pm, 20 pm to 80 pm, or 30 pm to 60 pm. In other examples, the film has a thickness of from 50 pm to 300 pm, 60 pm to 200 pm, or 80 pm to 150 pm.

[00218] In some examples, the film or other article containing the polyolefin composition has a melt strength of greater than 20 cN to 80 cN and a melt flow rate from 0.8 g/10 min to 20 g/10 min. In other examples, the film or other article containing the polyolefin composition has a melt strength of greater than 22 cN to 0 cN and a melt flow rate from 1 g/10 min to 10 g/10 min, 1.3 g/10 min to 5 g/10 min, or 1.5 g/10 min to 3.5 g/10 min.

[00219] By "extruding" what is meant is that the polymer and/or polymer blend if formed into a melt such as by heating and/or sheer forces and is forced to blend with other polymers and/or components (e.g., the polyethylene and the modifier) and is then forced out of a die in a desirable form or shape to affect the form or shape of the emanating polymer melt, such as in a film, such as a tubular film. Any suitable apparatus will be appropriate to provide "extrusion" such as a single or twin-screw extruder, or other melt-blending device as is known in the art and that can be fitted with a suitable die.

[00220] By "at a distance from the die", what is meant is that the "cooling device", such as a cooling ring that blows air on the forming film, is located at least 1 cm, 2 cm, 4 cm, or 8 cm from the die (or other distance as described herein) such as measured from the top or outer edge of the die to the base of the cooling device. [00221] By "causing the film to progress", what is meant is that the film forming from the die opening from hardening polyethylene is pulled or pushed mechanically or by some other means such as by air pressure (negative or positive) away from the die to create a continuous finished film.

[00222] In a typical process, a polyethylene melt is extruded through a die such as an annular slit die, usually vertically, to form a thin walled tube. Cooling can be conducted in the air or other gas which is introduced via a ring in the center of the die to blow up the tube like a balloon. Cooling could also be provided by other means, and the air may be nitrogen/oxygen or other gases or mixtures of gases or liquids. Mounted on top of the die, a high-speed air ring blows onto the hot film to cool the film. The cooling occurs at some distance from the die, which is at least 1 cm as described above. The tube of film can then continue upwards, continually cooling, until it may pass through nip rolls where the tube is flattened to create what is known as a "lay-flat" tube of film. This lay-flat or collapsed tube can then be taken back down the extrusion "tower" via more rollers. On higher output lines, the air inside the bubble is also exchanged. This is known as IBC (Internal Bubble Cooling).

[00223] The lay-flat film is then either kept as such or the edges of the lay-flat are slit off to produce two flat film sheets and wound up onto reels. Articles such as bags can be made from such lay-flat films. In this regard, if kept as lay-flat, the tube of film is made into bags by sealing across the width of film and cutting or perforating to make each bag. This is done either in line with the blown film process or at a later stage.

[00224] In some examples, the expansion ratio between die and blown tube of film would be 1.5 times to 4 times the die diameter. The films were blown at a temperature of 400°F (204°C) to 500°F (260°C), such as 410°F (210°C) to 465 °F (241°C). The drawdown between the melt wall thickness and the cooled film thickness occurs in both radial and longitudinal directions and is easily controlled by changing the volume of air inside the bubble and by altering the haul off speed. This gives blown film a better balance of properties than traditional cast or extruded film which is drawn down along the extrusion direction only.

[00225] In any embodiment, the polyolefin compositions described herein are suitable for forming articles by foaming, thermoforming, sheet extrusion, blown film, injection molding, and/or other processes. In one or more examples, the polyolefin compositions described herein are used to produce stand up, but flexible, packs or pouches. Such packs would be stiff enough to be formed into a shape to allow it to stand upright, for instance, with labeling on the front, but flexible and soft enough to allow a user to bend and/or squeeze the pack to force and/or pour liquid, gel, or flowable solids from an opening or open top of the pack. The polyethylene content can be adjusted to provide the toughness and low temperature packaging integrity for the pouch while the polypropylene content can be adjusted to provide stiffness and heat resistance during defrosting and/or microwave reheating of the pouch or pack. The packs and pouch can be used for collecting, storing and serving food items such as juice, vegetables, dairy products, desserts, flowable solids, and/or purees. Thus, in any of the embodiments, a flexible food pack contains the polyolefin composition, as described and discussed herein. The polyolefin compositions contain one or more LCB polypropylenes and one or more linear polypropylenes. The polyolefin composition contains 10 wt% to 90 wt% of the LCB polypropylene and 10 wt% to 90 wt% of the linear polypropylene, by weight of the polyolefin composition.

EXAMPLES

[00226] Samples of the polyolefin composition were prepared with various concentrations of a BMWD linear polypropylene (referred to as linear-PP, commercially available as Achieve™ Advanced PP628NE1 from ExxonMobil Chemical Co.) and a BMWD long chain branched (LCB) polypropylene (referred to as branched-PP, commercially available as a branch polypropylene from ExxonMobil Chemical Co.). The linear-PP and the branched-PP were blended and then compounded on PTL's 30mm Werner Pfleiderer extruder. No additional additive were added to produce the polyolefin compositions. The branched-PP: linear-PP blends were produced in 10 wt% increments from 100:0 to 0:100 (weight percent) totaling 11 total samples, as well as a pre-compounding sample for each of the linear-PP and the branched- PP, as listed in the first column of Table 1.

[00227] Table 1 also lists the MFR values for each of the samples of the polyolefin compositions. These MFR values are graphed based on the concentration of the linear-PP, as depicted in FIG. 1. The MFR of branched-PP shows significant upward shift when comparing pre- and post- compounded resin indicating possible degradation of the molecular structure. Pre-compounded resins are virgin resins. Post-compounded resins are produced via one pass through a PTL 30 mm extruder.

[00228] Table 2 lists the melt strength values at 190°C for each of the samples of the polyolefin compositions. These melt strength values are also graphed in FIG. 2. Melt strength curves of blend sample set and virgin uncompounded resin demonstrate that the melt strength of the branched-PP decreases after experiencing a thermal processing cycle. Addition of the linear-PP to the branched-PP allows for improved melt strength. Blending of the linear-PP into the branched-PP enables the branched-PP to maintain/improve melt strength even through exposure to heat cycles. Implications for blending the linear-PP and the branched-PP to produce the polyolefin compositions provide improving and/or increasing the use of regrind/scrap material, as well as for allowing to tailor the polyolefin compositions to create customer-specific solutions during plastic processing.

[00229] FIG. 3 depicts a graph illustrating molecular weight distribution (MWD) of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes. Blending of the linear- PP with the branched-PP produces a more prominent right shoulder and right tail on the GPC curve (which provide the high Mz value of the linear polypropylene) and increases the high molecular weight portion of the polymer. The GPC was performed under established Method ID EM0318.

[00230] FIG. 4 depicts a graph illustrating long chain branching of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes. Blending of the linear-PP with the branched-PP follows a predictable LCB trend. An increase in the branched-PP leads to greater LCB in the sample.

[00231] For each of the samples of the polyolefin compositions and the pre-compounded samples, Table 3 lists the molecular weight (Mn, Mw, Mz, and Mz+l), the polydispersity index (PDI), and the branching index (g'vis) values.

[00232] FIG. 5 depicts a graph illustrating the PDI of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes. Blending of the linear- PP with the branched- PP allows the sample to maintain the broad molecular weight distribution as seen by the polydispersity index.

[00233] FIG. 6 depicts a graph illustrating extensional viscosity at 190°C of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes. When factoring in baseline differences, strain hardening of 100% branched-PP is comparable to the non-compounded branched-PP sample. The branched- PP:linear-PP = 50:50 blend sample shows decreased strain hardening as compared to the virgin branched-PP and the compounded branched-PP samples.

[00234] FIG. 7 depicts another graph illustrating extensional viscosity at 190°C of the polyolefin compositions relative to different concentrations of the linear and branched polypropylenes. The branched-PP:linear-PP = 50:50 blend sample shows increased strain hardening response as compared to the compounded linear-PP sample.

[00235] The 1 % secant flexural modulus determined by the following: Equipment used: The United Six (6) station, 60 Degree machine contains the following: A load frame testing console containing an electrically driven crosshead mounted to give horizontal movement. Opposite the crosshead are mounted six (6) separate load cells. These load cells are tension load cells. [00236] Units #1 and #3 have load cells with a range of 0-35 pounds. Unit #2 has load cells with a range of 0-110 pounds. Each load cell is equipped with a set of air-actuated jaws. Each jaw has faces designed to form a line grip. The jaw combines one standard flat rubber face and an opposing face from which protrudes a metal half-round. Units #1 and #3 have 1 1/4" wide jaws and Unit #2 has 2 1/4" wide jaws. Secant Modulus is to be tested on Units #1 and #3 only.

[00237] Sample preparation: The specimens are conditioned and tested under ASTM laboratory conditions. They are maintained at 23 ± 2° C and 50% + 10% relative humidity. Conditioning time is a minimum of 40 hours under lab conditions and 48 hours after manufacturing. Prepare 12 specimens of each material; six in the machine direction (MD), the direction of flow as polymer exits the die, and six in the transverse direction (TD), the direction perpendicular to the flow as polymer exits the die.

[00238] Note: It is recommended that materials only 0-3 mils should be tested on Units #1 and #3 and all material thickness can be tested on Unit #2. But note that oriented PP which measures 0.7 mils can have loads up to 35 lbs. When testing unfamiliar materials, use caution and watch loads.

[00239] Each specimen should be 1 " wide and 7" long. The width (1 ") of the samples should be cut with the JDC precision, fixed-blade cutters. These cutters are used since nicks or cuts in specimens initiate premature breaks. After cutting each specimen, examine visually to insure the edges are undamaged (free of nicks). On a periodic basis the owner of the cutters will monitor specimen edge quality by microscopic examination·

[00240] Testing information: Secant Modulus: (Based on ASTM-D882-10)

Template (#) Test Method:

• (5) 1% Secant Modulus Properties of Film - ORG (Units #1 and #3 Only)

• (9) 1% and 2% Secant Modulus Properties of Film - ORG (Units #1 and #3 Only)

• (14) 1% and 5% Secant Modulus Properties of Film - ORG (Units #1 and #3 Only)

[00241] Methods of film fabrication, density, resin grade, resin type, and thickness all affect testing data. The stiffness properties are determined based on ASTM D882-10. These methods use a jaw separation of 5 inches and a sample 1-inch wide. The index of stiffness of thin films is determined by pulling the specimen at a rate of jaw separation (crosshead speed) of 0.5 inches per minute to a designated strain of 1%, or 1% and 2%, or 1% and 5% of its original length and [00242] recording the load at these points.

[00243] Overall, polyolefin compositions of the present disclosure and films and other articles made therefrom provide high melt strength and strain hardening.

[00244] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby

[00245] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below.

Claims

CLAIMS:

1. A polyolefin composition, comprising:

a) 10 wt% to 90 wt%, by weight of the polyolefin composition, of a long chain branched (LCB) polypropylene comprising:

i. a melt strength of 10 cN to 100 cN; and

ii. a branching index (g'vis) of less than 0.95;

b) 10 wt% to 90 wt%, by weight of the polyolefin composition, of a linear polypropylene comprising:

i. a melt strength of 10 cN to 100 cN; and

ii. a branching index (g'vis) of 0.95 or greater;

c) a melt strength of greater than 10 cN to 100 cN; and

d) a melt flow rate from 0.8 g/10 min to 20 g/10 min.

2. The polyolefin composition of claim 1 , wherein the LCB polypropylene has a branching index (g'vis) of less than 0.94.

3. The polyolefin composition of claim 2, wherein the LCB polypropylene has a branching index (g'vis) of 0.86 to 0.92.

4. The polyolefin composition according to any one of claims 1-3, wherein the linear polypropylene has a branching index (g'vis) of 0.97 or greater.

5. The polyolefin composition of claim 4, wherein the linear polypropylene has a branching index (g'vis) of 0.98 to 1.

6. The polyolefin composition according to any one of claims 1-5, wherein the melt strength of the polyolefin composition is 20 cN to 50 cN.

7. The polyolefin composition according to any one of claims 1-6, wherein the melt strength of the LCB polypropylene is 10 cN to 50 cN.

8. The polyolefin composition according to any one of claims 1-7, wherein the melt strength of the linear polypropylene is 25 cN to 50 cN.

9. The polyolefin composition according to any one of claims 1-8, wherein the melt strength of the LCB polypropylene is 12 cN to 30 cN, and wherein the melt strength of the linear polypropylene is 30 cN to 45 cN.

10. The polyolefin composition according to any one of claims 1-9, wherein the melt flow rate of the polyolefin composition is 1 g/10 min to 10 g/10 min.

11. The polyolefin composition of claim 10, wherein the melt flow rate of the polyolefin composition is 1.3 g/10 min to 5 g/10 min.

12. The polyolefin composition of claim 11, wherein the melt flow rate of the polyolefin composition is 1.5 g/10 min to 3.5 g/10 min.

13. The polyolefin composition according to any one of claims 1-12, wherein the melt flow rate of the LCB polypropylene is 1 g/10 min to 5 g/10 min.

14. The polyolefin composition according to any one of claims 1-13, wherein the melt flow rate of the linear polypropylene is 1 g/10 min to 5 g/10 min.

15. The polyolefin composition according to any one of claims 1-14, wherein the melt flow rate of the LCB polypropylene is 1.8 g/10 min to 4 g/10 min, and the melt flow rate of the linear polypropylene is 1.5 g/10 min to less than 2.5 g/10 min.

16. The polyolefin composition according to any one of claims 1-15, wherein the polyolefin composition comprises:

40 wt% to 90 wt%, by weight of the polyolefin composition, of the LCB polypropylene; and

10 wt% to 60 wt%, by weight of the polyolefin composition, of the linear polypropylene.

17. The polyolefin composition of claim 16, wherein the polyolefin composition comprises:

70 wt% to 90 wt%, by weight of the polyolefin composition, of the LCB polypropylene; and

10 wt% to 30 wt%, by weight of the polyolefin composition, of the linear polypropylene.

18. The polyolefin composition according to any one of claims 1-17, wherein the polyolefin composition has an extensional viscosity greater than an extensional viscosity of the linear polypropylene and less than an extensional viscosity of the LCB polypropylene, wherein the extensional viscosities are measured at 190°C.

19. The polyolefin composition according to any one of claims 1-18, wherein the polyolefin composition has an extensional viscosity at 190°C from 15 kPa-s to 700 kPa-s.

20. The polyolefin composition according to any one of claims 1-19, wherein each of the LCB polypropylene and the linear polypropylene is independently a broad molecular weight distribution (BMWD) polypropylene.

21. The polyolefin composition according to any one of claims 1-20, wherein the LCB polypropylene has an average molecular weight (Mz) of 2,000,000 g/mol to 2,800,000 g/mol, and wherein the linear polypropylene has an average molecular weight (Mz) of 3,000,000 g/mol to 3,500,000 g/mol.

22. The polyolefin composition of claim 21, wherein the LCB polypropylene has an average molecular weight (Mz) of 2,200,000 g/mol to 2,600,000 g/mol, and wherein the linear polypropylene has an average molecular weight (Mz) of 3,100,000 g/mol to 3,300,000 g/mol.

23. The polyolefin composition according to any one of claims 1-22, wherein the LCB polypropylene has an Mz/Mw molecular weight distribution of 5.2 to 5.8, and wherein the linear polypropylene has an Mz/Mw molecular weight distribution of 5.5 to 5.6.

24. The polyolefin composition according to any one of claims 1-23, wherein the LCB polypropylene has an Mw/Mn molecular weight distribution of 13.4 to 15.5, and wherein the linear polypropylene has an Mw/Mn molecular weight distribution of 14.4 to 14.8.

25. The polyolefin composition according to any one of claims 1-24, wherein the polyolefin composition comprises a flexural modulus of greater than 250 MPa to 1,500 MPa.

26. The polyolefin composition according to any one of claims 1 -24, wherein the polyolefin composition comprises a flexural modulus of 50 MPa to 250 MPa.

27. The polyolefin composition according to any one of claims 1-24, wherein the polyolefin composition comprises a flexural modulus of 1,500 MPa to 2,300 MPa.

28. The polyolefin composition of claim 27, wherein the polyolefin composition comprises a flexural modulus of 1,700 MPa to 2,250 MPa.

29. A polyolefin composition, comprising:

a) 60 wt% to 90 wt%, by weight of the polyolefin composition, of a long chain branched (LCB) polypropylene comprising:

i. a melt strength of 10 cN to 50 cN; and

ii. a branching index (g'vis) of 0.86 to 0.92;

b) 10 wt% to 40 wt%, by weight of the polyolefin composition, of a linear polypropylene comprising:

i. a melt strength of 25 cN to 50 cN; and

ii. a branching index (g'vis) of 0.98 to 1;

c) a melt strength of 22 cN to 40 cN; and

d) a melt flow rate from 1.3 g/ 10 min to 5 g/ 10 min.

30. A method of forming articles from a polyolefin composition, comprising:

combining 10 wt% to 90 wt%, by weight of the polyolefin composition, of a long chain branched (LCB) polypropylene and 10 wt% to 90 wt%, by weight of the polyolefin composition, of a linear polypropylene to produce the polyolefin composition;

wherein the LCB polypropylene comprises:

a melt strength of 10 cN to 100 cN; and

a branching index (g'vis) of less than 0.95;

wherein the linear polypropylene comprises:

a melt strength of 10 cN to 100 cN; and

a branching index (g'vis) of 0.95 or greater; and

wherein the polyolefin composition has:

a melt strength of greater than 20 cN to 80 cN; and

a melt flow rate from 0.8 g/10 min to 20 g/10 min.

31. A method of forming articles from a polyolefin composition comprising a mixture of two polypropylenes, comprising:

combining a LCB polypropylene and a linear polypropylene, wherein:

a greater concentration of the LCB polypropylene in the polyolefin composition relative to the concentration of the linear polypropylene provides a stiff article having a high flexural modulus of greater than 250 MPa to 1,500 MPa, or

a greater concentration of the linear polypropylene in the polyolefin composition relative to the concentration of the LCB polypropylene provides a flexible article having a low flexural modulus of 50 MPa to

250 MPa.

32. A method of forming an article comprising a polyolefin composition, comprising: a) extruding or rolling the polyolefin composition to produce a film or a sheet; or b) flowing a gas through the polyolefin composition to produce a foam article, wherein the polyolefin composition comprises 10 wt% to 90 wt%, by weight of the polyolefin composition, of a long chain branched (LCB) polypropylene having a branching index (g'vis) of less than 0.95 and 10 wt% to 90 wt%, by weight of the polyolefin composition, of a linear polypropylene having a branching index (g'vis) of 0.95 or greater, and

wherein the polyolefin composition has:

i. a melt strength of greater than 20 cN to 80 cN and

ii. a melt flow rate from 0.8 g/ 10 min to 20 g/10 min.