WO2020086273A1 - Polypropylene-based impact copolymers - Google Patents

Abstract

The present disclosure provides polypropylene compositions that provide consistent elongation at break properties with high melt strength and/or broad molecular weight distribution. The polypropylene compositions contain one or more impact copolymers and one or more polypropylene resins. The impact copolymer contains propylene and ethylene and has a melt flow rate (MFR) of greater than 4 g/10 min. The polypropylene resin has an MFR of less than 5 g/10 min. The polypropylene compositions maintain high impact strength, tensile strength, and elongation at break. For example, the polypropylene compositions have an Izod impact strength of greater than 20 J/m, a tensile strength of greater than 10 MPa, and an elongation at break of greater than 3%.

Description

POLYPROPYLENE-BASED IMPACT COPOLYMERS

PRIORITY

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 62/749,269, filed October 23, 2018, and European Patent Application No. 18207161.3 filed November 20, 2018, the disclosures of which are incorporated herein by reference.

FIELD

[0002] The present disclosure provides compositions propylene-based impact copolymers.

BACKGROUND

[0003] An impact copolymer of polypropylene (ICP) is a kind of polypropylene-based material produced by the copolymerization of propylene and ethylene. It is designed to meet the performance requirements for the consumer and industrial application in automotive, appliance, rigid packaging fields, and the like. However, the ICPs lack the desired mechanical properties in various applications when being applied independently, and improvements in elongation, stiffness, and/or toughness of ICPs remain a challenge. A typical case is that a compounder may formulate an ICP with improved toughness, but the ICP will sacrifice its stiffness at the same time.

[0004] To measure elongation, several tests (e.g., ISO-527 and ASTM D638) are used to determine the elongation at break property which is one of the critical properties for ICPs and has stringent requirements to meet. Unfortunately, most ICPs provide elongation at break properties that have poor reproducibility during testing and as such the values for elongation at break have large standard deviations. As such, compounders have difficulty in setting a specification or minimum requirement for elongation at break property and have to depend on unreliable data, lots of trial and error, experience, feedbacks from OEMs, and the like.

[0005] Therefore, there is a need for improved polypropylene-based impact copolymers having high and consistent elongation at break properties along with high impact strength, flex modulus, and tensile strength compared to traditional impact copolymers.

[0006] References of interest include: US 4,354,959; US 6,130,180; US 6,221,974; US 7,396,950; US 8,822,602; US 9,243,081; US 9,255,166; US 9,416,262; US 9,587,050; US 9,809,660; US 2004/054101; US 2005/032991; US 2011/034651; US 2012/004378; US 2012/062738; US 2015/197583; US 2016/009836; US 2016/198344; US 2017/129711; US 2018/0094089; EP 1 908 767 Al; EP 2 360 190 Al; and JP 2005220281.

SUMMARY

[0007] The present disclosure provides polypropylene compositions that contain one or more impact copolymers and one or more polypropylene resins. In any embodiment, the impact copolymer contains propylene and ethylene and has a melt flow rate (MFR) of greater than 4 g/lO min and the polypropylene resin has an MFR of less than 5 g/lO min. The polypropylene compositions maintain high impact, tensile, and elongation at break. For example, the polypropylene compositions have an Izod impact strength of greater than 20 J/m, a tensile strength of greater than 10 MPa, and an elongation at break of greater than 3%.

[0008] In any embodiments, a polypropylene composition contains 40 wt% to 80 wt% of an impact copolymer, 2 wt% to 20 wt% of a polypropylene resin, and 2 wt% to 20 wt% of a plastomer. The impact copolymer contains propylene and ethylene and has an MFR of greater than 20 g/lO min and the polypropylene resin has an MFR of less than 5 g/lO min. The polypropylene composition has an Izod impact strength of greater than 90 J/m and an elongation at break of greater than 12%.

[0009] In other embodiments, a polypropylene composition contains an impact copolymer containing propylene and ethylene and having an MFR of greater than 20 g/lO min to 200 g/lO min and a polypropylene resin having an MFR of 0.1 g/lO min to less than 5 g/lO min. The polypropylene composition has a tensile strength of greater than 20 MPa to 30 MPa and an elongation at break of greater than 12% to 40%.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] FIG. 1 is a bar graph depicting Izod impact strengths for polypropylene compositions, according to one or more embodiments.

[0011] FIG. 2 is a bar graph depicting flex modulus strengths for polypropylene compositions, according to one or more embodiments.

[0012] FIG. 3 is a bar graph depicting tensile strengths for polypropylene compositions, according to one or more embodiments.

[0013] FIG. 4 is a bar graph depicting elongation at break for polypropylene compositions, according to one or more embodiments.

[0014] FIGS. 5A and 5B are line graphs depicting normalized data distribution of elongation at break for two different impact copolymers, according to one or more embodiments. [0015] FIGS. 6A-6D are bar graphs depicting Izod impact, flex modulus, tensile, and elongation at break for polypropylene compositions containing a mixture of impact copolymers, according to one or more embodiments.

[0016] 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.

DFTA11 FD DESCRIPTION

[0017] The present disclosure provides polypropylene-based impact copolymers having high and consistent elongation at break properties along with high impact strength, flex modulus, and tensile strength compared to traditional impact copolymers.

Polypropylene Compositions

[0018] It has been found that by combining one or more impact copolymers (ICPs) and one or more polypropylene resins (MFR of less than 10 g/lO min, such as less than 5 g/lO min), a polypropylene composition is produced. These polypropylene compositions have high impact and tensile strengths, while also having high and consistent elongation at break properties and high flex modulus relative to ICPs without the polypropylene resin. The polypropylene resins can be or include broad molecular weight distribution polypropylene (BMWD PP), high melt strength polypropylene (HMS PP), and other poly propylenes.

[0019] The polypropylene resins have high melt strength due to chain entanglements and strain hardening. Without being bound by theory, it is believed that by using the polypropylene resins as modifiers in ICPs, the chain entanglements will occur more in the homo polypropylene matrix of the polypropylene resins, which is one of the critical properties of elongation at break. It is believed that the polypropylene resins manage to “lock-in” the homo polypropylene matrix which improves the chain entanglement which increases the consistency of the elongation at break for the overall polypropylene composition containing polypropylene-based impact copolymers. These polypropylene compositions have the performance requirements and mechanical properties needed for the consumer and industrial application in automotive, appliance, rigid packaging fields, and the like. Specifically, the polypropylene compositions have high and consistent elongation at break properties along with high impact strength, flex modulus, and tensile strength compared to traditional impact copolymers. [0020] In any embodiment, the polypropylene composition contains one or more ICPs and one or more polypropylene resins. The polypropylene composition includes 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, or 60 wt% to 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%, of the ICP, based on the total weight of the polypropylene composition. For example, the polypropylene composition includes 20 wt% to 95 wt%, 30 wt% to 90 wt%, 30 wt% to 80 wt%, 40 wt% to 80 wt%, 45 wt% to 80 wt%, 50 wt% to 80 wt%, 55 wt% to 80 wt%, 60 wt% to 80 wt%, 65 wt% to 80 wt%, 70 wt% to 80 wt%, 30 wt% to 70 wt%, 40 wt% to 70 wt%, 45 wt% to 70 wt%, 50 wt% to 70 wt%, 55 wt% to 70 wt%, 60 wt% to 70 wt%, 65 wt% to 70 wt%, 70 wt% to 75 wt%, 30 wt% to 60 wt%, 40 wt% to 60 wt%, 45 wt% to 60 wt%, 50 wt% to 60 wt%, 55 wt% to 60 wt%, 55 wt% to 65 wt%, or 60 wt% to 65 wt% of the ICP, based on the total weight of the polypropylene composition.

[0021] The polypropylene composition includes 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 7 wt%, 8 wt%, or 10 wt% to 12 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, or 30 wt% of the polypropylene resin, based on the total weight of the polypropylene composition. For example, the polypropylene composition includes 0.5 wt% to 30 wt%, 0.8 wt% to 30 wt%, 1 wt% to 30 wt%, 1 wt% to 25 wt%, 0.5 wt% to 20 wt%, 0.8 wt% to 20 wt%, 1 wt% to 20 wt%, 2 wt% to 20 wt%, 3 wt% to 20 wt%, 5 wt% to 20 wt%, 6 wt% to 20 wt%, 8 wt% to 20 wt%, 10 wt% to 20 wt%, 12 wt% to 20 wt%, 15 wt% to 20 wt%, 1 wt% to 15 wt%, 2 wt% to 15 wt%, 3 wt% to 15 wt%, 5 wt% to 15 wt%, 6 wt% to 15 wt%, 8 wt% to

15 wt%, 10 wt% to 15 wt%, 12 wt% to 15 wt%, 1 wt% to 12 wt%, 2 wt% to 12 wt%, 3 wt% to 12 wt%, 5 wt% to 12 wt%, 6 wt% to 12 wt%, 8 wt% to 12 wt%, or 10 wt% to 12 wt% of the polypropylene resin, based on the total weight of the polypropylene composition.

[0022] In one or more examples, the polypropylene composition includes 40 wt% to 80 wt% of the ICP and 2 wt% to 20 wt% of the polypropylene resin. In some examples, the polypropylene composition includes 50 wt% to 70 wt% of the ICP and 5 wt% to 15 wt% of the polypropylene resin. In other examples, the polypropylene composition includes 55 wt% to 65 wt% of the ICP and 8 wt% to 12 wt% of the polypropylene resin.

[0023] The polypropylene composition can include one or more plastomers and/or one or more elastomers. The plastomer or elastomer can be or include one or more polyolefin elastomers (POEs) or copolymers, such as ethylene-propylene, ethylene-butene, ethylene- hexene, ethylene-octene, derivatives thereof, or any combination thereof. In one example, the plastomer is an ethylene-butene copolymer with a melt index (MI) of <3, which is commercially available as EXACT™ 9182 plastomer from ExxonMobil Chemical.

[0024] The polypropylene composition includes 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% to 6 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, or 30 wt% of the plastomer, based on the total weight of the polypropylene composition. For example, the polypropylene composition includes 0.5 wt% to 30 wt%, 0.5 wt% to 25 wt%, 0.5 wt% to 20 wt%, 1 wt% to 30 wt%, 1 wt% to 25 wt%, 1 wt% to 20 wt%, 1 wt% to 15 wt%, 1 wt% to 10 wt%, 1 wt% to 5 wt%, 2 wt% to 30 wt%, 2 wt% to 25 wt%, 2 wt% to 20 wt%, 2 wt% to 15 wt%, 2 wt% to 10 wt%, 2 wt% to 5 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 5 wt% to 15 wt%, 5 wt% to 10 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, 10 wt% to 15 wt%, or 10 wt% to 12 wt% of the plastomer.

[0025] The polypropylene composition can include one or more fillers and/or one or more additives. The filler can be or include talc, titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, clay, carbon nanotubes, or any combination thereof. Exemplary additives can be or include one or more antioxidants, one or more colorants, one or more weighting agents, one or more clarifiers, one or more nucleating agent, or any combination thereof.

[0026] The polypropylene composition includes 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 5 wt%, 7 wt%, or 10 wt% to 12 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, or 50 wt% of the filler and/or the additive, based on the total weight of the polypropylene composition. For examples, the polypropylene composition includes 1 wt% to 50 wt%, 5 wt% to 50 wt%, 5 wt% to 40 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 5 wt% to 10 wt%, 10 wt% to 50 wt%, 10 wt% to 40 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, 15 wt% to 50 wt%, 15 wt% to 40 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt%, or 15 wt% to 20 wt% of the filler and/or the additive, based on the total weight of the polypropylene composition.

[0027] In some examples, the additive in the polypropylene composition is or contains one or more antioxidants. The antioxidant can be or include one or more hindered phenolics. Exemplary antioxidants can be or include IRGANOX™ 1010 antioxidant and/or IRGANOX™ 1076 antioxidant, commercially available from Ciba-Geigy. The polypropylene composition can include 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, or 1 wt% to 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, or 12 wt% of the antioxidant, based on the total weight of the polypropylene composition. For example, the polypropylene composition can include 0.1 wt% to 12 wt%, 0.2 wt% to 10 wt%, 0.2 wt% to 8 wt%, 0.2 wt% to 5 wt%, 0.2 wt% to 3 wt%, 0.2 wt% to 2 wt%, 0.2 wt% to 1 wt%, 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%, 0.7 wt% to 10 wt%, 0.7 wt% to 8 wt%, 0.7 wt% to 5 wt%, 0.7 wt% to 3 wt%, 0.7 wt% to 2 wt%, 0.7 wt% to 1 wt%, 1 wt% to 10 wt%, 1 wt% to 8 wt%, 1 wt% to 5 wt%, 1 wt% to 3 wt%, 1 wt% to 2 wt%, or 1 wt% to 1.5 wt% of the antioxidant, based on the total weight of the polypropylene composition.

[0028] The polypropylene composition has a melt flow rate (MFR) of 8, 10, 12, or 15 g/lO min to 18, 20, 23, 25, 28, or 30 g/lO min (230°C/2.l6 kg), as determined according to ASTM D1238. For example, the polypropylene composition has an MFR of 8 g/lO min to 30 g/lO min, 10 g/lO min to 30 g/lO min, 10 g/lO min to 25 g/lO min, 10 g/lO min to 23 g/lO min, 10 g/lO min to 20 g/lO min, 12 g/lO min to 30 g/lO min, 12 g/lO min to 25 g/lO min, 12 g/lO min to 23 g/lO min, 12 g/lO min to 20 g/lO min, 15 g/lO min to 30 g/lO min, 15 g/lO min to 25 g/lO min, 15 g/lO min to 23 g/lO min, or 15 g/lO min to 20 g/lO min.

[0029] The polypropylene composition has an Izod impact strength (at 22.8°C) of greater than 20 J/m, 25 J/m, 30 J/m, 50 J/m, 70 J/m, 80 J/m, 90 J/m, 92 J/m, 95 J/m, 97 J/m, 100 J/m, 110 J/m, or 120 J/m to 125 J/m, 130 J/m, 140 J/m, 150 J/m, 170 J/m, 180 J/m, 200 J/m, 220 J/m, 250 J/m, 300 J/m, 350 J/m, 400 J/m, 450 J/m, 480 J/m, or 500 J/m, as determined according to ASTM D256A. In some examples, the polypropylene composition has an Izod impact strength (at 22.8°C) of greater than 20 J/m, greater than 50 J/m, or greater than 90 J/m. For example, the polypropylene composition has an Izod impact strength (at 22.8°C) of 20 J/m to 500 J/m, 20 J/m to 480 J/m, 20 J/m to 450 J/m, 20 J/m to 400 J/m, 20 J/m to 350

J/m, 20 J/m to 300 J/m, 20 J/m to 200 J/m, 20 J/m to 100 J/m, 25 J/m to 480 J/m, 50 J/m to 500 J/m, 50 J/m to 480 J/m, 50 J/m to 450 J/m, 50 J/m to 400 J/m, 50 J/m to 350 J/m, 50 J/m to 300 J/m, 50 J/m to 200 J/m, 50 J/m to 100 J/m, greater than 90 J/m to 480 J/m, greater than 90 J/m to 400 J/m, greater than 90 J/m to 300 J/m, greater than 90 J/m to 200 J/m, greater than 90 J/m to 180 J/m, greater than 90 J/m to 160 J/m, greater than 90 J/m to 150 J/m, greater than 90 J/m to 140 J/m, greater than 90 J/m to 120 J/m, 95 J/m to 220 J/m, 95 J/m to 200 J/m, 95 J/m to 180 J/m, 95 J/m to 160 J/m, 95 J/m to 150 J/m, 95 J/m to 140 J/m, 95 J/m to 120 J/m, 100 J/m to 220 J/m, 100 J/m to 200 J/m, 100 J/m to 180 J/m, 100 J/m to 160 J/m, 100 J/m to 150 J/m, 100 J/m to 140 J/m, 100 J/m to 120 J/m, 120 J/m to 220 J/m, 120 J/m to 200 J/m, 120 J/m to 180 J/m, 120 J/m to 160 J/m, 120 J/m to 150 J/m, 120 J/m to 140 J/m, or 120 J/m to 130 J/m, as determined according to ASTM D256A.

[0030] The polypropylene composition has a tensile strength (2.0 in/min) of greater than 10 MPa, greater than 15 MPa, or greater than 20 MPa, such as 21 MPa, 22 MPa, 23 MPa, 24 MPa, or 25 MPa to 26 MPa, 27 MPa, 28 MPa, 29 MPa, or 30 MPa, as determined according to ASTM D638. For example, the polypropylene composition has a tensile strength of greater than 10 MPa to 30 MPa, greater than 20 MPa to 30 MPa, 22 MPa to 30 MPa, 24 MPa to 30 MPa, 25 MPa to 30 MPa, 26 MPa to 30 MPa, 28 MPa to 30 MPa, 22 MPa to 28 MPa, 24 MPa to 28 MPa, 25 MPa to 28 MPa, or 26 MPa to 28 MPa, as determined according to ASTM D638.

[0031] The polypropylene composition has an elongation at break of greater than 3%, greater than 5%, greater than 10%, or greater than 12%, such as 14%, 15%, 16%, 18%, 20%, 22%, or 25% to 26%, 28%, 30%, 32%, 35%, 38%, or 40%, as determined according to ASTM D638. For examples, the polypropylene composition has an elongation at break of greater than 3% to 40%, greater than 3% to 35%, greater than 3% to 32%, greater than 3% to

30%, greater than 3% to 28%, greater than 3% to 25%, greater than 3% to 22%, greater than 3% to 20%, greater than 3% to 18%, greater than 12% to 40%, greater than 12% to 35%, greater than 12% to 32%, greater than 12% to 30%, greater than 12% to 28%, greater than 12% to 25%, greater than 12% to 22%, greater than 12% to 20%, greater than 12% to 18%, 14% to 40%, 14% to 35%, 14% to 30%, 14% to 25%, 14% to 22%, 14% to 20%, 15% to

40%, 15% to 35%, 15% to 32%, 15% to 30%, 15% to 28%, 15% to 25%, 15% to 22%, 15% to 20%, 15% to 18%, 20% to 40%, 20% to 35%, 20% to 32%, 20% to 30%, 20% to 28%, 20% to 25%, or 20% to 22%, as determined according to ASTM D638.

[0032] The polypropylene composition has a flex modulus (at 1% Secant) of greater than 1,500 MPa, such as 1,600 MPa, 1,650 MPa, 1,700 MPa, 1,750 MPa, 1,800 MPa, 1,850 MPa, or 1,900 MPa to 1,950 MPa, 2,000 MPa, 2,050 MPa, 2,100 MPa, 2,150 MPa, or 2,200 MPa, as determined according to ASTM D790. For example, the polypropylene composition has a flex modulus of greater than 1,500 MPa to 2,200 MPa, greater than 1,500 MPa to 2,100 MPa, greater than 1,500 MPa to 2,000 MPa, greater than 1,500 MPa to 1,900 MPa, greater than 1,500 MPa to 1,800 MPa, greater than 1,500 MPa to 1,700 MPa, 1,600 MPa to 2,200 MPa,

1,600 MPa to 2,100 MPa, 1,600 MPa to 2,000 MPa, 1,600 MPa to 1,900 MPa, 1,600 MPa to 1,800 MPa, 1,600 MPa to 1,700 MPa, 1,700 MPa to 2,200 MPa, 1,700 MPa to 2,100 MPa, 1,700 MPa to 2,000 MPa, 1,700 MPa to 1,900 MPa, 1,700 MPa to 1,800 MPa, as determined according to ASTM D790.

[0033] The polypropylene compositions described herein are suitable for use in processes such as injection molding, blow molding and thermoforming for making useful articles for automotives and appliances, as the relatively high MFR provides for ease of processing, while the desirable physical properties are maintained. In particular, the polypropylene compositions can be formed into automotive components, either alone or in a mixture with other polymers, exemplary components can include the interior dashboard, interior side trim, handles, interior door facing and components, exterior bumpers, wheel trim, and various fascia used for decorative purposes.

Impact Copolymer (ICP)

[0034] In any embodiment, the ICP is a propylene-based ICP. In one or more examples, the ICP contains one or more ethylene-propylene copolymers. In some examples, the ICP contains one or more propylene homopolymers. In other examples, the ICP contains one or more ethylene-propylene copolymers and one or more propylene homopolymers.

[0035] In any embodiment, the propylene-based ICP contains from 5 wt% or 8 wt% to 20 wt%, 25 wt%, or 30 wt% of an ethylene-propylene copolymer, by weight of the propylene- based impact copolymer, and is imbedded in a continuous phase of polypropylene. In some examples, the ethylene-propylene copolymer contains from 25 wt%, 30 wt%, or 35 wt% to 40 wt%, 45 wt%, 50 wt%, or 55 wt% ethylene-derived units (or 55 wt% monomer units derived from ethylene and/or C4 to C10 a-olefms, by weight of the ethylene-propylene copolymer) by weight of the ethylene-propylene copolymer.

[0036] The ICP contains an ethylene-propylene copolymer component with a high viscosity, high molecular weight, and a large amount of high molecular weight component, while the polypropylene portion of the ICP tends to have low molecular weight and a relatively high MFR.

[0037] In any embodiment, the ICP has an MFR of greater than 4, greater than 10, or greater than 20, such as 25, 30, 40, 50, 60, 80, or 100 g/lO min to 120, 130, 150, 170, 180, 200, or 220 g/lO min. For example, the ICP has an MFR of greater than 4 to 220 g/lO min, greater than 10 to 220 g/lO min, greater than 20 to 220 g/lO min, greater than 4 to 200 g/lO min, 10 to 200 g/lO min, greater than 10 to 200 g/lO min, greater than 20 to 200 g/lO min, greater than 20 to 180 g/lO min, greater than 20 to 150 g/lO min, greater than 20 to 120 g/lO min, greater than 20 to 100 g/lO min, 25 to 220 g/lO min, 25 to 200 g/lO min, 25 to 180 g/lO min, 25 to 150 g/lO min, 25 to 120 g/lO min, 25 to 100 g/lO min, 30 to 220 g/lO min, 30 to 200 g/lO min, 30 to 180 g/lO min, 30 to 150 g/lO min, 30 to 120 g/lO min, 30 to 100 g/lO min, 50 to 220 g/lO min, 50 to 200 g/lO min, 50 to 180 g/lO min, 50 to 150 g/lO min, 50 to 120 g/lO min, 50 to 100 g/lO min, 80 to 220 g/lO min, 80 to 200 g/lO min, 80 to 180 g/lO min, 80 to 150 g/lO min, 80 to 120 g/lO min, or 80 to 100 g/lO min.

[0038] In any embodiment, the ICPs have an Mw/Mn ranging from 10, 12, or 14 to 20, 24, 26, or 30. Also in any embodiment the ICPs have an z-average molecular weight (Mz) value of greater than 2,800, 3,000, or 3,200 kg/mole, or ranging from 2,800, 3,000, or 3,200 kg/mole to 3,600, 3,800, 4,000, or 4,200 kg/mole. In any embodiment, the ICPs have a ratio of MW(EP)/MW(PP) of greater than 5, 6, or 10, or ranging from 5, 6, or 10 to 14, 16, or 20.

[0039] In any embodiment, the polypropylene portion of the ICP has an MFR of at least 100, 120, 160, 200, 220, 260, or 300 g/lO min; or ranging from 100, 120, 160, 200, 220, 260, or 300 g/lO min to 340, 360, 400, 420, 480, or 500 g/lO min. The polypropylene has a pentad fraction greater than 0.95 or 0.96 by ¹³C NMR, and a triad fraction greater than 0.97, 0.975, or 0.98 by ¹³C NMR. The polypropylene has an Mw/Mn ranging from 4 or 6 to 8, 10, or 12; and an Mz/Mw of less than 5, 4.8, 4.2, or 4, or ranging from 2.5, 3, or 3.2 to 4, 4.2, 4.8, or 5.

[0040] The ethylene-propylene copolymer portion of the ICP has an Mw/Mn ranging from 6, 8, or 10 to 14, 16, or 20. The ethylene-propylene copolymer has an Mz value of greater than 3,000, 3,200, or 3,400 kg/mole, or ranging from 3,000, 3,200, or 3,400 kg/mole to 3,800, 4,000, 4,200, or 4,400 kg/mole. The ethylene-propylene copolymer has an Mz/Mw value of less than 4, 3.5, or 3, or ranging from 2.2 or 2.4 to 3, 3.5, 4, or 5. The ethylene- propylene copolymer has an intrinsic viscosity (IV) ranging from 3 or 4 dL/g to 7, 8, or 10 dL/g.

[0041] The ICPs typically have a Rockwell hardness ranging from 95 or 95 to 105, 110, or 120. The ICPs also typically have a heat deflection temperature (HDT) (0.45 MPa) ranging from 90°C, l00°C, or H0°C to l20°C, l30°C, or l40°C; and ranging from 50°C or 55°C to 70°C, 75°C, or 80°C (1.8 MPa).

[0042] In any embodiment, the propylene-based impact copolymers have a flexural modulus of at least 1,600, or 1,660, or 1,700 MPa, or ranging from 1,600, or 1,660, or 1,700 MPa to 1,800, or 1,840, or 1,880, or 1,900, or 1,940, or 2,000 MPa. In any embodiment, the propylene-based impact copolymers also have a notched Izod impact strength of at least 3, 3.2, 3.6, 4, 4.2, or 4.6 kJ/m², or ranging from 3, 3.2, 3.6, 4, 4.2, or 4.6 kJ/m² to 5.2, 5.4, 5.6, 5.8, 6, or 6.2 kJ/m².

[0043] In any embodiment, other desirable polymers used to blend with the ICP include propylene-based elastomers, plastomers, EPDM, ethylene-propylene rubber, polyethylenes (LLDPE, HDPE, LDPE), homopolypropylene, styrenic block copolymers, hydrocarbon resins, cyclic-olefin copolymers, polyacrylates, polyesters, butyl rubber, polyisobutylene, polyisoprene, derivatives thereof, or any combination thereof.

Polypropylene resin

[0044] The “polypropylene resin” or“polypropylene resin” described and discussed herein refers to one or more polypropylenes having an MFR (230°C/2.l6 kg) of less than 25 g/lO min. Examples of the polypropylene resin can be or include a broad molecular weight distribution polypropylene (BMWD PP), a high melt strength polypropylenes (HMS PP), a control grade polypropylene homopolymer, or combinations thereof.

[0045] In any embodiment, the polypropylene resin has an MFR of less than 25 g/lO min, less than 20 g/lO min, less than 10 g/lO min, less than 5 g/lO min, less than 4 g/lO min, less than 3 g/lO min, less than 2.5 g/lO min, less than 2 g/lO min, less than 1.5 g/lO min, or less than 1 g/lO min, as determined according to ASTM D1238 Condition L (230°C/2. l6 kg). In any embodiment, the polypropylene resin has an MFR of 0.1, 0.5, 1, 1.5, 2, or 2.5 g/lO min to 3, 3.5, 4, 5, 8, 10, 12, 15, 18, 20, or 25 g/lO min. For example, the polypropylene resin has an MFR of 0.1 to 25 g/lO min, 0.5 to 25 g/lO min, 1 to 25 g/lO min, 1.5 to 25 g/lO min, 2 to

25 g/lO min, 2.5 to 25 g/lO min, 3 to 25 g/lO min, 4 to 25 g/lO min, 5 to 25 g/lO min, 8 to 25 g/lO min, 10 to 25 g/lO min, 15 to 25 g/lO min, 0.1 to 20 g/lO min, 0.5 to 20 g/lO min, 1 to 20 g/lO min, 1.5 to 20 g/lO min, 2 to 20 g/lO min, 2.5 to 20 g/lO min, 3 to 20 g/lO min, 4 to 20 g/lO min, 5 to 20 g/lO min, 8 to 20 g/lO min, 10 to 20 g/lO min, 15 to 20 g/lO min, 0.1 to 10 g/lO min, 0.5 to 10 g/lO min, 1 to 10 g/lO min, 1.5 to 10 g/lO min, 2 to 10 g/lO min, 2.5 to

10 g/lO min, 3 to 10 g/lO min, 4 to 10 g/lO min, 5 to 10 g/lO min, 8 to 10 g/lO min, 0.1 to 5 g/lO min, 0.1 to 3 g/lO min, or 0.1 to 1 g/lO min.

High Melt Strength Polypropylene (HMS PP)

[0046] The polypropylene resins contains one or more polypropylenes having a relatively high melt strength (greater than 15 cN or greater than 20 cN), referred to herein as a“high melt strength polypropylene” (or HMS PP) having one or more features as described here, made according to the disclosure in WO 2014/070386. As such the polypropylene resin can be or include one or more BMWD PPs. In some examples, the polypropylene resin can be or include one or more propylene homopolymers.

[0047] In any embodiment, the HMS PP contains at least 50 mol%, 60 mol%, 70 mol%,

80 mol%, or 90 mol% propylene-derived monomer units, or ranging from 50 mol%, 60 mol%, or 80 mol% to 95 mol%, 97 mol%, or 99 mol% propylene-derived units, the remainder being a comonomer selected from ethylene and Cr to C20 a-olefms, for example, ethylene or l-butene. In some examples, the HMS PP can include 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, or 1 wt% to 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, or 5 wt% of ethylene units. For example, the HMS PP contains 0.1 wt% to 5 wt% or 0.1 wt% to 4 wt% of ethylene derived units. In any embodiment, the HMS PP is a homopolymer of propylene-derived monomer units. In some examples, the HMS PP has an isotactic pentad percentage of greater than 90%, 92%, or 95% as determined by ¹³C NMR spectroscopy.

[0048] In any embodiment, the HMS PP has an MFR ranging from 0.1, 0.5, 1, 2, 2.5, 3,

4, 5 g/lO min to 6, 8, 10, 12, 16, 20, or 25 g/lO min, as determined according to ASTM D1238 Condition L (230°C/2. l6 kg). In one or more examples, the HMS PP has an MFR ranging from 0.5 g/lO min to 20 g/lO min.

[0049] In any embodiment, the HMS PP has a weight average molecular weight (Mw) ranging from 200,000 g/mol, 300,000 g/mol, or 350,000 g/mol to 500,000 g/mol, 600,000 g/mol, or 700,000 g/mol; a number average molecular weight (Mn) ranging from 15,000 g/mol or 20,000 g/mol to 30,000 g/mol, 35,000 g/mol, or 40,000 g/mol; and/or a z-average molecular weight ranging from 900,000 g/mol, 1,000,000 g/mol, or 1,200,000 g/mol to 1,800,000 g/mol, 2,000,000 g/mol, or 2,200,000 g/mol, as determined by Size Exclusion Chromatography (“SEC”).

[0050] In any embodiment, the HMS PP has a molecular weight distribution (Mw/Mn) of greater than 6, 7, or 8; or ranging from 6, 7, 8, 10, or 12 to 14, 16, 18, 20, or 24. For example, the Mw/Mn value can range from 6 to 24 or 8 to 18. In any embodiment, the HMS PP has an Mz/Mw of greater than 3, greater than 3.4, greater than 3.6, greater than 3.8, greater than 4, or ranging from 3, 3.4, or 3.6 to 3.8, 4, 4.2, 4.4, or 4.6. The HMS PP can have a Mz/Mn of greater than 35, 40, 55, or 60, or ranging from 35, 40, or 55 to 60, 65, 70, 75, or 80. Polymer molecular weight (weight-average molecular weight, Mw, number-average molecular weight, Mn, and z-averaged molecular weight, Mz) and molecular weight distribution (Mw/Mn) are determined using SEC. Equipment includes of a High Temperature Size Exclusion Chromatography (either from Waters Corporation or Polymer Laboratories), with a differential refractive index detector (DRI) or infrared (IR) detector.

[0051] The HMS PPs can be linear as evidenced by a high branching index. In any embodiment, the HMS PPs have a branching index (g¹, also referred to in the literature as gVis avg) of at least 0.95, 0.97, or 0.98, as determined in column 37 of U.S. Pat. No. 7,807,769 determined by using a High Temperature Size Exclusion Chromatography (either from Waters Corporation or Polymer Laboratories), equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer.

[0052] In any embodiment, the HMS PP has a melt strength of at least 15 cN or 20 cN determined using an extensional rheometer at l90°C; or ranging from 10 cN, 15 cN, or 20 cN to 35 cN, 40 cN, 60 cN, 80 cN, or 100 cN.

[0053] In any embodiment, the HMS PP has an MFR ranging from 0.1, 0.5, 1, 2, 2.5, 3, 4, 5 g/lO min to 6, 8, 10, 12, 16, 20, 25, 30 g/lO min, as determined according to ASTM D1238 Condition L (230°C/2. l6 kg). In some examples, the HMS PP has an MFR ranging from 0.5 g/lO min to 30 g/lO min, 0.5 g/lO min to 20 g/lO min, 1 g/lO min to 30 g/lO min, or 1 g/lO min to 20 g/lO min.

[0054] In any embodiment, the HMS PP has a viscosity ratio ranging from 35 to 80 determined from the complex viscosity ratio at 0.01 to 100 rad/s angular frequency at a fixed strain of 10% at l90°C. Also In any embodiment, the HMS PP has a Peak Extensional Viscosity (annealed) ranging from 10 kPa^»s or 20 kPa^»s to 40 kPa^»s, 50 kPa^»s, 55 kPa^»s, 60 kPa^»s, 80 kPa^»s, or 100 kPa^»s at a strain rate of 0.01 /sec (l90°C).

[0055] In any embodiment, the HMS PP has a heat distortion temperature of greater than or equal to l00°C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi). In any embodiment, the HMS PP has a flexural modulus of at least 1,200 MPa, at least 1,300 MPa, or at least 1,380 MPa, such as ranging from 1,400 MPa, 1,500 MPa, 1,600 MPa, 1,800 MPa, or 2,000 MPa to 2,400 MPa, 2,500 MPa, 2,700 MPa, 3,000 MPa, 3,200 MPa, or 3,500 MPa, determined according to ASTM D790A (0.05 in/min) on nucleated samples with 0.01 wt% to 0.1 wt% of a-nucleating agent. For example, the flexural modulus can range from 1,500 MPa to 3,500 MPa.

[0056] The HMS PP can have a peak melting point temperature (second melt, Tr ) of greater than l60°C or l64°C, or ranging from l60°C or l64°C to l68°C or l70°C (by DSC); and a crystallization temperature (Tc) of greater than l00°C, l05°C, or H0°C, or ranging from l00°C, l05°C, or H0°C to H5°C or l20°C (by DSC). [0057] In any embodiment, the HMS PP used to make the polypropylene composition and films therefrom are a reactor-grade material, meaning that HMS PP is used as it comes out of the reactor used to produce it, optionally having been further made into pellets of material that has not altered any of its properties such as the branching index, MWD, or MFR by more than 1% of its original value. In any embodiment, the HMS PP has not been cross- linked or reacted with any radiation or chemical substance to cause cross-linking and/or long- chain branching. Typical forms of radiation known to cause cross-linking and/or long-chain branching include use of so-called e-beams or other radiation (beta or gamma rays) that interact with the polymer.

Broad Molecular Weight Distribution Polypropylene (BMWD PP)

[0058] In any embodiment, the polypropylene resin is or contains one or more BMWD PPs. In some examples, the BMWD PP includes at least 50 mol% propylene and has a melt strength of at least 20 cN determined using an extensional rheometer at l90°C. For purposes herein, the melt strength of a polymer at a particular temperature, e.g., l90°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.

[0059] One of the most distinctive properties of the BMWD PP is a high melt strength. 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 is required to maintain 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 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.

[0060] In one or more examples, the BMWD PP includes at least 50 mol% propylene and has a melt strength of greater than 15 cN, greater than 20 cN, greater than 25 cN, greater than 30 cN, greater than 35 cN, greater than 40 cN, greater than 45 cN, or greater than 50 cN to 60 cN, 80 cN, 100 cN, 120 cN, 150 cN, 180 cN, or 200 cN, determined using an extensional rheometer at l90°C. For example, the BMWD PP has a melt strength of greater than 15 cN to 200 cN, greater than 20 cN to 200 cN, greater than 30 cN to 200 cN, 50 cN to 200 cN, 60 cN to 200 cN, 80 cN to 200 cN, or 100 cN to 200 cN.

[0061] In other examples, the BMWD PP includes at least 50 mol% propylene and has an

MWD (Mw/Mn) of greater than 5, or greater than or equal to 6, or from 6 to 20, or from 6 to 15, or any combination thereof.

[0062] In some examples, the BMWD PP includes 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, the BMWD PP is or contains a propylene homopolymer.

[0063] In other examples, the BMWD PP includes from 0.1 to 10 mol% of a comonomer. In any embodiment, the comonomer may be an alpha olefin. The comonomer may be ethylene, one or more Cr to C20 olefins, or any combination thereof.

[0064] The BMWD PP has a branching index (g¹) of at least 0.95, or at least 0.99. The BMWD PP has a stiffness of greater than 2,000 MPa or greater than 2,100 MPa, such as from 2,000 MPa (290 kpsi) to 2,500 MPa (360 kpsi), as determined according to ASTM D790A on nucleated samples with 0.1% sodium benzoate. The BMWD PP has a viscosity ratio of greater than or equal to 35, or 40, or 45, or from 35 to 80 determined at an angular frequency of 0.01 and at an angular frequency of 100 rad/s (at an angular frequency of 0.01 to 100 rad/s) at a fixed strain of 10% at l90°C.

[0065] In any embodiment, the BMWD PP has an MFR ranging from 0.1, 0.5, 1, 2, 2.5, 3, 4, 5 g/lO min to 6, 8, 10, 12, 16, 20, or 25 g/lO min, as determined according to ASTM D1238 Condition L (230°C/2.16 kg). In some examples, the BMWD PP has an MFR ranging from 0.5 g/lO min to 20 g/lO min.

[0066] In any embodiment, the BMWD PP may be a non-functionalized polymer or resin.

For purposes herein, a non-functionalized resin does not include 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-l,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. l)hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophtalic anhydride, norbom-5-ene-2,3-di carboxylic acid anhydride, nadic anhydride, methyl nadic anhydride, himic anhydride, methyl himic anhydride, and x-methyl- bicyclo(2.2. l)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. [0067] A functionalized polymer is considered to have indications of long chain branching (e.g., a g' of less than 0.95), consistent with the cross-linking and intermolecular bonding associated with functionalized polymers.

[0068] For purposes herein, a functionalized polymer contains greater than 0.1 wt% of a functional group and/or a g' < 0.95, and/or is the product of a post reactor functionalization or grafting process. Accordingly, In any embodiment, the non-functionalized polymer may include 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' > 0.95 determined as described herein.

[0069] The resin may be produced by contacting propylene monomers at propylene polymerization conditions with a catalyst system containing a Ziegler-Natta catalyst that includes a non-aromatic internal electron donor, and first and second external electron donors that includes different organosilicon compounds.

[0070] In any embodiment, the resin may be free of functionalized polypropylene or contain 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 BMWD PP, and wherein the number of carbons of the BMWD PP 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.

[0071] The BMWD PP has a heat distortion temperature of greater than or equal to l00°C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi). The BMWD PP has an isopentad percentage of greater than 90%, or greater than 95%, or greater than 99%.

[0072] The BMWD PP includes 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 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 BMWD PP includes 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.

[0073] In any embodiment, the BMWD PP includes at least 50 mol% propylene, has a melt strength of at least 20 cN determined using an extensional rheometer at l90°C, and an MWD (Mw/Mn) of greater than 5. The resin can be produced by contacting propylene monomers at a temperature and a pressure in the presence of catalyst system containing a Ziegler-Natta catalyst that includes a non-aromatic internal electron donor and two or more external electron donors. In some examples, the first external electron donor may have the formula R Si(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. 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, and n is 1, 2, or 3. In some examples, the second external electron donor is different than the first external electron donor.

[0074] The various descriptive elements and numerical ranges disclosed herein for the polypropylene compositions and methods of forming the polypropylene compositions and films therefrom can be combined with other descriptive elements and numerical ranges to describe the invention. Further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein, including the examples in jurisdictions that allow such combinations. The features of the inventions are demonstrated in the following non-limiting examples.

Experiments

[0075] Table 1 provides a variety of polypropylene compositions labeled as Samples 1- 10. Each composition contains at least one impact copolymer (ICP1, ICP2), a polypropylene resin (PP1, PP2, PP3), a plastomer or polyolefin elastomer (POE), a filler, and two or more antioxidants (AO). All values listed in Table 1 for each component are weight percent (wt%), unless otherwise noted.

[0076] The impact copolymers were: ICP1, a propylene-ethylene copolymer with an MFR of 30, commercially available as AP03B polypropylene impact copolymer from ExxonMobil Chemical; and ICP2, a propylene-ethylene copolymer with an MFR of 50, commercially available as PP7555KNE2 polypropylene impact copolymer from ExxonMobil Chemical.

[0077] The polypropylene resins were: PP1, a control grade polypropylene with an MFR of 4, commercially available as PP2822E1 polypropylene homopolymer from ExxonMobil Chemical; PP2, a broad molecular weight distribution polypropylene (BMWD PP) with an MFR of <2.5, commercially available as ACHIEVE™ Advanced PP6282NE1 polypropylene homopolymer from ExxonMobil Chemical; and PP3, a high melting strength polypropylene (HMS PP) with an MFR of <2.5, commercially available as PP6203E1 polypropylene homopolymer from ExxonMobil Chemical.

[0078] The plastomer was POE, an ethylene-butene copolymer with a melt index (MI) of <3, commercially available as EXACT™ 9182 plastomer from ExxonMobil Chemical. The filler was talc. The antioxidants were a high molecular weight sterically hindered phenolic antioxidant, commercially available as IRGANOX^® 1010 antioxidant from BASF; and a sterically hindered phosphite antioxidant (e.g., di -tertiary butyl phenyl phosphite), commercially available as IRGAFOS^® 168 antioxidant from BASF.

[0079] Sample 1 is a base matrix and contains 70 wt% of the ICP1 and the remainder is the POE, the filler, and the AO mixture (the remainder, 30 wt%, is the same for Samples 1- 10). Samples 2 is the control and contains 60 wt% ICP1 and 10 wt% of PP1, Samples 3-4 contain 60 wt% of the ICP1, 10 wt% of the PP2, or PP3, respectively. Samples 5 and 6 contain mixtures of ICP1 and ICP2 with different polypropylene resins. Sample 5 contains 40 wt% of the ICP1, 20 wt% of the ICP2, and 10 wt% of the PP1. Sample 6 contains 40 wt% of the ICP1, 20 wt% of the ICP2, and 10 wt% of the PP3. Sample 7 is another base matrix and contains 70 wt% of the ICP2. Samples 8 is the control and contains 60 wt% ICP2 and 10 wt% of PP1, Samples 9-10 contain 60 wt% of the ICP2, 10 wt% of the PP2, or PP3, respectively.

[0080] The compounding process was mixed and extruded by a TSE-26 twin screw extruder. The MFR test was conducted according to ASTM Dl238-04c standard. The Izod impact test was conducted according to the ASTM D256 standard and flex modulus test was conducted according to the ExxonMobil internal test standard for flex modulus. All testing was repeated 5 times for each formulation of Samples 1-10. Tensile and elongation at break tests were conducted following the ASTM D638-14 standard with different test times. Each of the Samples 1-10 was tested for 15 times.

[0081] The obtained data was analyzed by Grubbs' test in a Minitab 17 to check data quality. In general, test data from one formulation should match the normal distribution. If one of data point did not fit the distribution curve, the data point was identified as abnormal data and removed so to not cause an exaggerating effect on the standard deviation. After Grubbs' test, all checked data was included in calculations of average and standard deviation. In addition, for tensile and elongation test, one abnormal data for one run was found in Sample 3 and one abnormal data for one run was found in Sample 7 (see Table 1). Both of these data points were excluded for average and standard deviation calculations, which means their average and standard deviation are calculated by the rest of 14 data points. [0082] The MFR values were determined for Samples 1-10 to be 16.2, 10.3, 10.7, 12.0, 13.2, 13.5, 23.1, 16.5, 14.6, 16.1 g/lOmin, respectively, as determined according to ASTM D1238.

Impact Strength

[0083] FIG. 1 is a bar graph depicting Izod impact strengths for polypropylene compositions for Samples 1-4 and 7-10. The Izod impact strengths were determined for Samples 1-4 to be 88.2 ± 3.68 J/m; 100.09 ± 6.09 J/m; 97.09 ± 3.54 J/m; and 102.13 ± 4.73 J/m, respectively, and for Samples 7-10 to be 109.07 ± 5.24 J/m; 156.6 ± 9.18 J/m; 181.64 ± 2.19 J/m; and 159.79 ± 3.94 J/m, respectively.

[0084] The polypropylene compositions (Samples 2-4 and 8-10) containing mixtures of an impact copolymer (ICP1 or ICP2) and a polypropylene resins (PP1, PP2, or PP3) have improved impact strength compared to the base matrix which is same impact copolymer without the polypropylene resin (Samples 1 and 7).

[0085] As to ICP1, Izod impact strength gets an over 10% increase from 88.2 J/m (Sample 1) to over 100 J/m (Samples 2 and 4). Specificly, PP3 (Sample 4) contributes to a 15.8% increase, which is 13.5% greater than the control grade(Sample 2). PP2 (Sample 3) gives rise to a 10.1% increase, which is not as good as the control grade(Sample 2). The results indicate that PP3 addition shows better effect in ICP1 case than PP2.

[0086] In ICP2 case, adding three kinds of PPs reuslts in larger improvent compare with those in ICP1. PP2, PP3 (Samples 9 and 10), as well as the control grade PP1 (Sample 8), all contribute to over 40% increase for the impact strength over Sample 7. Moreover, both PP2 and PP3 work better than control grade PP1 with 66.5% and 46.5% increase, respectivly. For the control grade PP1, it shows a 43.6% improvement over Sample 7.

[0087] Therefore, the Izod impact test demonstrates that PP3 shows better effect in ICP1 case, while both PP2 and PP3 work better than the control grade PP1 does in ICP2 case.

Flex modulus

[0088] FIG. 2 is a bar graph depicting flex modulus strengths for polypropylene compositions for Samples 1-4 and 7-10. The flex modulus strengths were determined for Samples 1-4 to be 1,779 ± 56 MPa; 1,917 ± 20 MPa; 2,085 ± 28 MPa; and 1,837 ± 39 MPa, respectively, and for Samples 7-10 to be 1,666 ± 17 MPa; 1,737 ± 24 MPa; 1,868 ± 43 MPa; and 1,736 ± 15 MPa, respectively.

[0089] Flex modulus of resulting compounds are also increased when adding the two kinds of PP. In ICP1 case, PP2 (Sample 3) contributes a 17.2% increase in flex modulus which is higher than the control grade PP1 (Sample 2) does (7.8%), while PP3 (Sample 4) shows a lower contribution (3.3% increase) than the control grade PP1.

[0090] As to ICP2 case, PP2 (Sample 9) still results in a greater increase (12.1%) when comparing with the control grade PP1 (Sample 8), while the contribution of the control grade PP1 and PP3 (Samples 8 and 10) is comparable (4.3% and 4.2%, respectively). Therefore, PP2 shows the best effect on flex modulus improvement either in ICP1 or in ICP2.

Tensile Strength and Elongation at Break

[0091] FIG. 3 is a bar graph depicting tensile strengths for polypropylene compositions for Samples 1-4 and 7-10. The tensile strengths were determined for Samples 1-4 to be 23.4 ± 0.08 MPa; 24.8 ± 0.11 MPa; 26.3 ± 0.05 MPa; and 25.3 ± 0.09 MPa, respectively, and for Samples 7-10 to be 21.5 ± 0.06 MPa; 23.4 ± 0.09 MPa; 24.2 ± 0.07 MPa; and 24.0 ± 0.11 MPa, respectively.

[0092] Tensile strength is also increased when adding two kinds of PPs. As shown in FIG. 3, both PP2 and PP3 show more effective than the control grade PP1. Specifically, in ICP1 case, adding PP2 (Sample3) results in a higher 12.8% improvement, while adding PP3 (Sample 4) shows 8.1% improvement over Sample 1. The control grade PP1 (Sample 2) shows 6.0% improvement over Sample 1. In ICP2 case, PP2 and PP3 (Samples 9 and 10) show 12.6% and 11.6% increases, respectively, over Sample 7. Both of them are higher than control grade PP1 (Sample 8) which shows 8.8% increase over Sample 7. Therefore, the results suggest that PP1, PP2, and PP3 improve the tensile strength to ICP1 and ICP2.

[0093] FIG. 4 is a bar graph depicting elongation at break for polypropylene compositions for Samples 1-4 and 7-10. The elongation at break values were determined for Samples 1-4 to be 17.4% ± 1.33%; 18.8% ± 1.60%; 14.5% ± 1.26%; and 20.1% ± 1.10%, respectively, and for Samples 7-10 to be 15.0% ± 0.97%; 29.2% ± 4.01%; 23.6% ± 1.25%; and 26.4% ± 1.91%, respectively.

[0094] Compared with the excellent performance in tensile strength improvement, the effects of PP1, PP2, and PP3 on elongation at break are more complex. In ICP1 case, PP3 (Sample 4) shows better results than the control grade PP1 (Sample 2), while PP2 (Sample 2) shows results in a decreased elongation over the control (Sample 1). In ICP2 case, the control grade PP1 (Sample 8) shows 81.6% improvement over the control (Sample 7). PP2 or PP3 (Samples 9 and 10) - although not as strong improvement as Sample 8 - still contribute to 49.4% and 65.5% increase, respectively, over the control (Sample 7). On the other hand, however, adding PP2 or PP3 does improve the consistency of elongation either for ICP1 and ICP2, as the stand deviations of their data are smaller than that of the control grade PP1.

[0095] FIGS. 5A and 5B are line graphs depicting normalized data distribution of elongation at break for ICP1 (FIG. 5A) and ICP2 (FIG. 5B) with PP1, PP2, and PP3. In FIG. 5 A, for ICP1, the distribution curve of PP3 (Sample 4) is sharper and narrower than the distribution curve of PP2 (Sample 3) which is sharper and narrower than the distribution curve of the control grade PP1 (Sample 2). In FIG. 5B, for ICP2, the distribution curve of PP2 (Sample 9) is sharper and narrower than the distribution curve of PP3 (Sample 10) which is sharper and narrower than the distribution curve of the control grade PP1 (Sample 8).

[0096] FIGS. 6A-6D are bar graphs depicting mechanical properties (e.g., Izod impact, flex modulus, tensile, and elongation at break) for polypropylene compositions containing a mixture of ICP1 and ICP2 containing PP1 (Sample 5) or PP3 (Sample 6). No test were conducted for the mixture of ICP1 and ICP2 containing PP2. The mixture of ICPs contains 40% of ICP1 and 20% of ICP2.

[0097] FIG. 6A depicts the Izod impact strength which was determined to be 97.0 ± 5.28

J/m for Sample 5 and 93.5 ± 8.05 J/m for Sample 6. FIG. 6B depicts the flex modulus strength which was determined to be 1,841 ± 48 MPa for Sample 5 and 1,845 ± 34 MPa for Sample 6. FIG. 6C depicts the tensile strength which was determined to be 24.1 ± 0.09 MPa for Sample 5 and 24.9 ± 1.39 MPa for Sample 6. FIG. 6D depicts the elongation at break which was determined to be 18.7% ± 1.28% for Sample 5 and 20.9% ± 1.39% for Sample 6. Overall, Samples 5 and 6 had quite similar mechanical properties. Sample 5 was slightly higher in impact strength than Sample 6, while Sample 6 was slightly higher in elongation at break than Sample 5. Samples 5 and 6 have similar in flex modulus and tensile strengths.

[0098] In conclusion, the polypropylene compositions (Samples 2-6 and 8-10) containing mixtures of one or more impact copolymers (ICP1 and/or ICP2) and one or more polypropylene resins (PP1, PP2, and/or PP3) have improved impact strength, flex modulus, tensile strength, and elongation compared to the same impact copolymers without the polypropylene resin (Samples 1 and 7). Moreover, the polypropylene compositions (Samples 3-4 and 9-10) have improved consistency of elongation at break compared to the control grade, polypropylene resin (Samples 2 and 8).

[0099] Overall, polypropylene compositions of the present disclosure provide consistent elongation at break properties with high melt strength and/or broad molecular weight distribution. [00100] 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. Likewise, the term“comprising” is considered synonymous with the term“including” for purposes of United States law. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase“comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases“consisting essentially of,”“consisting of’,“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.

[00101] 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 polypropylene composition comprising:

20 wt% to 95 wt%, by weight of the polypropylene composition, of an impact copolymer comprising propylene and ethylene and having a melt flow rate

(MFR) of greater than 4 g/lO min (230°C/2. l6 kg), as determined according to ASTM D1238; and

0.5 wt% to 20 wt%, by weight of the polypropylene composition, of a polypropylene resin having an MFR of less than 5 g/lO min (230°C/2. l6 kg), as determined according to ASTM D1238, and an MWD (Mw/Mn) of greater than 5;

wherein the polypropylene composition has:

an Izod impact strength of greater than 20 J/m (22.8°C), as determined according to ASTM D256A;

a tensile strength of greater than 10 MPa (2.0 in/min), as determined according to ASTM D638; and

an elongation at break of greater than 3%, as determined according to ASTM D638.

2 The polypropylene composition of claim 1, wherein the polypropylene resin has an Mz/Mw of greater than 3.

3. The polypropylene composition of claim 1 or 2, comprising:

50 wt% to 70 wt% of the impact copolymer; and

5 wt% to 15 wt% of the polypropylene resin.

4. The polypropylene composition according to any one of claims 1- 3, further comprising a plastomer.

5. The polypropylene composition of claim 4, comprising 0.5 wt% to 20 wt% of the plastomer.

6. The polypropylene composition of claim 4 or 5, wherein the plastomer comprises ethylene-propylene, ethylene-butene, ethylene-hexene, ethylene-octene, or any combination thereof.

7. The polypropylene composition according to any one of claims 1-6, wherein the impact copolymer has an MFR of 10 g/lO min to 200 g/lO min.

8. The polypropylene composition according to any one of claims 1-7, wherein the impact copolymer comprises an ethylene-propylene copolymer.

9. The polypropylene composition of claim 8, wherein the impact copolymer further comprises a propylene homopolymer.

10. The polypropylene composition according to any one of claims 1-9, wherein the polypropylene resin has an MFR of less than 5 g/lO min.

11. The polypropylene composition according to any one of claims 1-10, wherein the polypropylene resin has an MFR of 0.1 g/lO min to 3 g/lO min.

12. The polypropylene composition according to any one of claims 1-11, wherein the polypropylene resin comprises a propylene homopolymer.

13. The polypropylene composition according to any one of claims 1-12, wherein the polypropylene resin comprises a broad molecular weight distribution (BMWD) polypropylene, and wherein the BMWD polypropylene comprises at least 50 mol% propylene and has a melt strength of greater than 15 cN determined using an extensional rheometer at l90°C.

14. The polypropylene composition of claim 13, wherein the MWD of the BMWD polypropylene is from 6 to 15.

15. The polypropylene composition of claim 13 or 14, wherein the melt strength of the BMWD polypropylene is from 50 cN to 200 cN.

16. The polypropylene composition according to any one of claims 1-15, wherein the polypropylene resin comprises a high melt strength (HMS) polypropylene, and wherein the HMS polypropylene comprises 0.1 wt% to 5 wt% of ethylene derived units and has:

a flexural modulus of at least 1,200 MPa (0.05 in/min), as measured according to ASTM D790A; and

an Mz/Mw of at least 4.

17. The polypropylene composition of claim 16, wherein the flexural modulus of the

HMS polypropylene is ranging from 1,500 MPa to 3,500 MPa.

18. The polypropylene composition of claim 16 or 17, wherein the HMS polypropylene has an MWD (Mw/Mn) value ranging from 8 to 18.

19. The polypropylene composition according to any one of claims 16-18, wherein the HMS polypropylene has an MFR ranging from 1 g/lO min to 30 g/lO min, (230°C/2T6 kg), as determined according to ASTM D1238.

20. The polypropylene composition according to any one of claims 1-19, wherein the polypropylene composition has an Izod impact strength of 20 J/m to 480 J/m.

21. The polypropylene composition according to any one of claims 1-20, wherein the polypropylene composition has a tensile strength of greater than 25 MPa to 30 MPa.

22. The polypropylene composition according to any one of claims 1-21, wherein the polypropylene composition has an elongation at break of 14% to 40%.

23. The polypropylene composition according to any one of claims 1-22, wherein the polypropylene composition has an elongation at break of 15% to 32%.

24. The polypropylene composition according to any one of claims 1-23, wherein the polypropylene composition has a flex modulus of greater than 1,500 MPa (1% Secant), as determined according to ASTM D790.

25. The polypropylene composition according to any one of claims 1-24, wherein the polypropylene composition has a flex modulus of 1,600 MPa to 2,200 MPa.

26. The polypropylene composition according to any one of claims 1-25, further comprising a filler.

27. The polypropylene composition of claim 26, comprising 5 wt% to 30 wt% of the filler.

28. The polypropylene composition of claim 26 or 27, wherein the filler comprises talc, titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, clay, carbon nanotubes, or any combination thereof.

29. A polypropylene composition comprising:

40 wt% to 80 wt% of an impact copolymer comprising propylene and ethylene and having a melt flow rate (MFR) of greater than 20 g/lO min (230°C/2.16 kg), as determined according to ASTM D1238;

2 wt% to 20 wt% of a polypropylene resin having an MFR of less than 5 g/lO min (230°C/2. l6 kg), as determined according to ASTM D1238; and 2 wt% to 20 wt% of a plastomer,

wherein the polypropylene composition has:

an Izod impact strength of greater than 90 J/m (22.8°C), as determined according to ASTM D256A; and

an elongation at break of greater than 12%, as determined according to ASTM D638.

30. A polypropylene composition comprising:

an impact copolymer comprising propylene and ethylene and having a melt flow rate (MFR) of greater than 20 g/lO min to 200 g/lO min (230°C/2. l6 kg), as determined according to ASTM D1238; and a polypropylene resin having an MFR of 0.1 g/lO min to less than 5 g/lO min (230°C/2. l6 kg), as determined according to ASTM D1238;

wherein the polypropylene composition has:

a tensile strength of greater than 20 MPa to 30 MPa (2.0 in/min), as determined according to ASTM D638; and

an elongation at break of greater than 12% to 40%, as determined according to ASTM

D638.