Polypropylene copolymer blends and roofing membranes thereof

Abstract

The present disclosure generally relates to polymer blends containing polypropylene copolymers and roofing membranes thereof. In some embodiments, a composition includes a polypropylene copolymer including about 0.1 mol% to about 35 mole% ethylene units and about 99.9 mol% to about 65 mole% propylene units. The polypropylene copolymer has an mm triad tacticity of about 75% or greater, regio defects of about 0.01 mol% to about 1.2 mol%, an r1r2 of about 0.8 to about 3, a melt flow rate (230 °C / 2.16 kg) of about 4 g / 10 minutes or less, a phase angle at 10 kPa at 190 °C less than 69 degrees, and an [EEE] triad content of about 0.5 mol% to about 4 mol%. The composition includes an impact copolymer. The composition optionally includes a plastomer.

Description

Polypropylene Copolymer Blends and Roofing Membranes Thereof PRIORITY CLAIM

[0001] This application claims the benefit of U.S. Provisional Application Number 63 / 702,205, filed October 2, 2024, entitled “Polypropylene Copolymer Blends and Roofing Membranes Thereof”, the entirety of which is incorporated by reference herein. CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This invention is related to: 1) U.S. Provisional Application Number 63 / 702,209, filed October 2, 2024; 2) U.S. Provisional Application Number 63 / 702,214, filed October 2, 2024; 3) U.S. Provisional Application Number 63 / 702,219, filed October 2, 2024; 4) U.S. Provisional Application Number 63 / 702,223, filed October 2, 2024; 5) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “Polypropylene Copolymers and Processes for Production Thereof” (attorney docket number 2024EM122- WO); 6) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “High Melt Strength Propylene Based Elastomers Compositions for Elastic Blown or Cast Films” (attorney docket number 2024EM123-WO); 7) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “Polypropylene Copolymers and Processes For Production Thereof” (attorney docket number 2024EM124- WO); and 8) concurrently filed PCT Application Number PCT / US2025 / ___, entitled “Polypropylene Copolymer Compositions and Films Thereof” (attorney docket number 2024EM125-WO). FIELD

[0003] The present disclosure generally relates to polymer blends containing polypropylene copolymers and roofing membranes thereof. BACKGROUND

[0004] Thermoplastic polyolefin (TPO) polymers have been used in roofing applications for commercial buildings with flat and low slope roofs. Such roofing applications are typically a reflective roofing membrane made from blends of polypropylene and ethylene-propylene rubber and have a reflective white upper layer that gets exposed to sunlight and a pigmented layer underneath the reflective layer that is attached to a roof insulation material. TPO roofing sheets are installed using different methods including adhered, mechanically attached system, ballasted and plate bonded. The membrane is exposed throughout the life of the roof.

[0005] For roofing and other sheeting applications, the products are typically manufacturedas membrane sheets having a typical width of 10 feet (3 meters) or greater, although smaller widths can be available. The sheets are typically sold, transported, and stored in rolls. For roofing membrane applications, several sheets are unrolled at the installation site, placed adjacent to each other with an overlapping edge to cover the roof and are sealed together by a heat welding process. During transport and storage, the rolls can be exposed to extreme heat conditions, such as from 40 °C to 100 °C, which can lead to roll blocking of the rolls during storage in warehouse. In use, the membranes are exposed to a wide range of conditions that will deteriorate or destroy the integrity of the membrane after time. Generally speaking, roofing membranes should be able to withstand a wide variety of service temperatures, such as from −40° C to +40° C.

[0006] The current TPO roofing market has been led by a reactor thermoplastic polyolefin (“RTPO”) product from LyondellBasell called Hifax™ Ca10a. This RTPO product makes good quality, single ply TPO roofing sheets under high production rates. Propylene-based elastomers are thought to be useful for making TPO roofing sheets. For example, Vistamaxx™ polymers offer advantages in membrane flexibility and welding, and formulation flexibility. However, Vistamaxx™ performance polymer (e.g., VMX6102) may be defensive on both processing and mechanical performance. In addition, a blend containing 50 wt % Vistamaxx™ (VMX) 6102 (a polymer having isotactic propylene repeat units with random ethylene distribution that is produced using ExxonMobil's proprietary metallocene catalyst technology) and 50 wt % impact polypropylene (ICP) PP 7032E2 provide comparable flexibility relative to that of the RTPO Hifax™ Ca10a. However, this 50 / 50 blend may not have sufficient melt stability of extruded sheets under similar production conditions as the Hifax™ Ca10a. The melt strength of the 50 / 50 VMX / ICP blend is significantly lower than that of Hifax™ Ca10a, which is believed to be the cause of the melt instability problems.

[0007] There is a need for polymer compositions having improved melt strength as well as maintained or improved cold temperature performance, and capable of making quality single ply TPO roofing sheets under high production rates. SUMMARY

[0008] The present disclosure generally relates to polymer blends containing polypropylene copolymers and roofing membranes thereof.

[0009] In some embodiments, a composition includes a polypropylene copolymer including about 0.1 mol% to about 35 mole% ethylene units and about 99.9 mol% to about 65 mol% propylene units. The polypropylene copolymer has an mm triad tacticity of about 75% or greater, regio defects of about 0.01 mol% to about 1.2 mol%, an r1r2of about 0.8 to about 3,a melt flow rate (230oC / 2.16 kg) of about 4 g / 10 minutes or less, a phase angle at 10 kPa at 190oC less than 69 degrees, and an [EEE] triad content of about 0.5 mol% to about 4 mol%. The composition includes an impact copolymer. The composition optionally includes a plastomer.

[0010] In some embodiments, a composition includes a first polypropylene copolymer comprising about 0.1 mol% to about 35 mol% ethylene units and about 99.9 mol% to about 65 mol% propylene units. The first polypropylene copolymer has an mm triad tacticity of about 75% or greater, regio defects of about 0.01 mol% to about 1.2 mol%, an r1r2 of about 0.8 to about 3, and an [EEE] triad content of about 0.5 mol% to about 4 mol%. The composition includes a second copolymer comprising about 2 wt% to about 10 wt% ethylene content. The second copolymer has a weight average molecular weight (Mw) that is less than the weight average molecular weight of the first copolymer. The composition includes an impact copolymer and optionally a plastomer.

[0011] In some embodiments, a membrane sheet includes a scrim, a first membrane disposed on the scrim, and a second membrane. The scrim is disposed on the second membrane. At least one of the first membrane or the second membrane independently includes a composition of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG.1 is a multilayered roofing membrane that, when applied to a roof, is attached to insulation that is attached to the roof, according to an embodiment.

[0013] FIG. 2 is a graph depicting melt strength of compositions, according to an embodiment.

[0014] FIG.3A is a graph depicting extensional viscosity of compositions, according to an embodiment.

[0015] FIG.3B is a graph depicting extensional viscosity of compositions, according to an embodiment.

[0016] FIG.4A is a graph depicting melt flow instability of a composition, according to an embodiment.

[0017] FIG.4B is a graph depicting melt flow instability of a composition, according to an embodiment.

[0018] FIG.4C is a graph depicting melt flow instability of a composition, according to an embodiment.

[0019] FIG.4D is a graph depicting melt flow instability of a composition, according to an embodiment.

[0020] FIG. 5 is a graph illustrating melt strength (@ 190oC) of compositions, according to an embodiment.

[0021] FIG.6A is a graph depicting extensional viscosity of compositions, according to an embodiment.

[0022] FIG.6B is a graph depicting extensional viscosity of compositions, according to an embodiment.

[0023] FIG.6C is a graph depicting extensional viscosity of compositions, according to an embodiment.

[0024] FIG. 7 is a graph depicting SAOS data of compositions, according to an embodiment.

[0025] FIG. 8 is a graph illustrating tensile properties of compositions, according to an embodiment.

[0026] FIG.9 is a graph illustrating complex viscosity (@ 190oC) of TPO roofing sheets, according to an embodiment.

[0027] FIG. 10 is a graph depicting phase angle vs. complex modulus of TPO roofing sheets (at 190oC), according to an embodiment. DETAILED DESCRIPTION

[0028] The present disclosure generally relates to polymer blends containing polypropylene copolymers and roofing membranes thereof. In some embodiments, polymer blends (also referred to as compositions) can include (1) a polypropylene copolymer (e.g., propylene-based elastomer), (2) an impact copolymer, and (3) optionally, a plastomer.

[0029] Compositions of the present disclosure can provide improved melt strength as well as maintained or improved cold temperature performance, and capability of making quality single ply TPO roofing sheets under high production rates. Compositions of the present disclosure can provide maintained mechanical properties while providing the improved melt strength and improved rheological properties. For example, polypropylene copolymers of the present disclosure can have one or more of long chain branching, low melt flow rate, and / or high molecular weight. Long chain branching, for example, can provide shear thinning (high viscosity at low frequency and low viscosity at high frequency) which can provide higher melt strength for improved processability. Compositions of the present disclosure can be used in TPO roofing membranes to provide reduced or eliminated melt instability of the extruded TPO roofing membrane. Definitions

[0030] The term “multimodal,” when used to describe a polymer means “multimodalmolecular weight distribution,” which is understood to mean that the Gel Permeation Chromatography (GPC) trace, plotted as Absorbance versus Retention Time (seconds), has more than one peak or at least one inflection points. An “inflection point” is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versa). For example, a polyolefin composition that includes a first lower molecular weight polymer component and a second higher molecular weight polymer component can be considered to be a “bimodal” polyolefin composition if an inflection point is observed. For example, the Mw values of the high molecular weight polymer and low molecular weight polymer differ by at least 10%, relative to each other, such as by at least 20%, such as at least 50%, such as by at least 100%, such as by a least 200%.

[0031] As used herein, the term “copolymer” is meant to include polymers having two or more monomers, optionally, with other monomers, and can refer to interpolymers, terpolymers, etc. The term “polymer” as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc., and alloys and blends thereof. The term “polymer” as used herein also includes impact, block, graft, random, and alternating copolymers. The term “polymer” shall further include all possible geometrical configurations unless otherwise specifically stated. Such configurations can include isotactic, syndiotactic and atactic symmetries. The term “blend” as used herein refers to a mixture of two or more polymers.

[0032] “Reactor blend,” as used herein, means a highly dispersed and mechanically inseparable blend of two or more polymers produced in situ as the result of sequential or parallel polymerization of one or more monomers with the formation of one polymer in the presence of another, or by solution blending polymers made separately in parallel reactors. Reactor blends can be produced in a single reactor, a series of reactors, or parallel reactors and are reactor grade blends. Reactor blends can be produced by any polymerization method, including batch, semi-continuous, or continuous systems. Particularly excluded from “reactor blend” polymers are blends of two or more polymers in which the polymers are blended ex situ, such as by physically or mechanically blending in a mixer, extruder, or other similar device. As used herein, the terms “polypropylene,” “propylene polymer,” and “propylene- based polymer” refer to a polymer or copolymer comprising at least 50 mol% propylene units (such as at least 70 mol% propylene units, such as at least 80 mol% propylene units, such as at least 90 mol% propylene units, such as at least 95 mol% propylene units or 100 mol% propylene units (in the case of a homopolymer)).

[0033] As used herein, when a polymer is referred to as comprising a monomer, the monomer is present in the polymer in the polymerized form of the monomer or in the derivativeform of the monomer. The term “derived units” as used herein, refers to the polymerized form of the monomer from which the polymer was derived. For example, when a copolymer is said to have a “propylene” content of 35 wt % to 55 wt %, it is understood that the monomer unit in the copolymer is derived from propylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer.

[0034] As used herein, “wt%” means weight percent, “mol%” means mole percent, “vol %” means volume percent, and all molecular weights, e.g., Mw, Mn, Mz, are in units of g / mol, unless otherwise noted. Furthermore, all molecular weights are Mw unless otherwise noted.

[0035] As used herein, when a polymer is said to comprise a certain percentage, wt%, of a monomer, that percentage of monomer is based on the total amount of monomer units in the polymer. Polypropylene Copolymers copolymers can include copolymers of propylene with ethylene,C4-C20 olefins, or terpolymers of propylene and ethylene with C4-C20olefin, such as having an ethylene content of less than 35 mol%. In some embodiments, diene is absent from the copolymers produced herein. Polypropylene copolymers with long chain branching (LCB) architectures, bimodal distribution, and / or having a low melt flow rate have advantage in a number of applications.

[0037] Polypropylene copolymers can be produced using any suitable processes and utilizing any suitable catalyst systems (such as, for example, as described in WO 2021 / 162745). In addition to the catalyst, process conditions play important roles in enhancing production of polymers having LCB. In at least one embodiment, LCB in combination with low MFR can be provided by various process parameters, such as (1) catalyst used, (2) concentration of ethylene and propylene, (3) molar ratio of propylene to ethylene, (4) flow rate ratio of propylene feed to ethylene feed, and / or (5) reactor temperature.

[0038] The ethylene concentration can be 2 mole / liter or less, or 1.5 mole / liter or less, or 1.0 mole / liter or less, or 0.5 mole / liter or less, or 0.2 mole / liter or less, or 0.1 mole / liter or less, or 0.05 mole / liter or less, such as about 0.005 mole / liter to about 0.15 mole / liter, such as about 0.03 mole / liter to about 0.1 mole / liter, such as about 0.05 mole / liter to about 0.09 mole / liter, such as about 0.06 mole / liter to about 0.08 mole / liter, such as about 0.07 mole / liter. The propylene concentration can be 2 mole / liter or less, or 1.5 mole / liter or less, or 1.0 mole / liter or less, or 0.75 mole / liter or less, or 0.5 mole / liter or less, such as about 0.1 mole / liter to about 1 mole / liter, such as about 0.3 mole / liter to about 0.8 mole / liter, such as about 0.4 mole / liter to about 0.7 mole / liter, such as about 0.55 mole / liter to about 0.65 mole / liter, such as about 0.6mole / liter. In some embodiments, the molar ratio of propylene to ethylene is about 5 to about 12, such as about 6 to about 11, such as about 7 to about 10, such as about 7 to about 9, such as about 8.

[0039] In some embodiments, a flow rate ratio of propylene feed to ethylene feed (e.g., kg / hr / kg / hr) is about 4 to about 8, such as about 5 to about 7.5, such as about 6 to about 7.5, alternatively about 4 to about 5.

[0040] In some embodiments, a reactor temperature is maintained at about 75oC to about 85oC, such as about 77oC to about 83oC, such as about 79oC to about 81oC, such as about 80oC.

[0041] In some embodiments, polypropylene copolymers of the present disclosure, such as propylene-ethylene and / or propylene-C4to C20alphaolefin copolymers (such as propylene- hexene copolymers or propylene-octene copolymers) can have a Mw / Mn of between 1 to 10 (such as 2-8, such as 2-6, such as 2-5).

[0042] In at least one embodiment, a polypropylene copolymer of the present disclosure has an Mw / Mn (PDI) value about 1 to about 15, such as about 1 to about 5, such as about 1 to about 3, such as about 1.5 to about 2.5, alternatively a polypropylene copolymer is bimodal having a PDI of about at least 2, 2 to about 10, such as about 2 to about 6. It has been discovered that advantageous properties, such as bimodality, provide improved pellet stability, good high and low temperature properties, and softness as compared to conventional monomodal polypropylene polymers made by bis(phenolate) Lewis base catalysts and bimodal polymers made by metallocene catalysts.

[0043] In at least one embodiment, polypropylene copolymers are copolymers of propylene, such as those having from 0.1 to 30 wt% (alternately about 10 to about 25 wt%, alternately about 15 to about 25 wt%, such as about 18 to about 23 wt%, such as about 19 wt% to about 21 wt%, alternatively about 2 wt% to about 10 wt%, such as about 4 wt%) of one or more of ethylene and / or C4to C20olefin comonomer (such as ethylene and / or C4to C12alpha-olefin, such as ethylene, butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene).

[0044] In at least one embodiment, polypropylene copolymers are copolymers of propylene, such as those having from 99.9 to 70 wt% (alternately about 75 to about 90 wt%, alternately about 75 to about 85 wt%, such as about 77 to about 82 wt%, such as about 79 wt% to about 81 wt%, alternatively about 90 wt% to about 98 wt%, such as about 94 to 96 wt%) of propylene.

[0045] In some embodiments, polypropylene copolymers (formed from a single reactor or series of reactors, alternatively dual reactors in parallel) have a weight average molecularweight (Mw)(LS) of 150,000 g / mol or more, such as about 200,000 g / mol to about 500,000 g / mol, such as about 250,000 g / mol to about 400,000 g / mol, such as 275,000 g / mol to about 350,000 g / mol; a number average molecular weight (Mn)(LS) of 100,000 g / mol or more, such as about 100,000 g / mol to about 250,000 g / mol, such as about 100,000 g / mol to about 175,000 g / mol, such as about 120,000 g / mol to about 165,000 g / mol, a z-average molecular weight (Mz)(LS) of about 300,000 g / mol or more, such as about 400,000 g / mol to about 700,000 g / mol, such as about 400,000 g / mol 650,000 g / mol, such as about 450,000 g / mol to about 525,000 g / mol; and / or a g’ (vis) value of about 0.7 to about 1, such as about 0.75 to about 0.95, such as about 0.85 to about 0.92, alternatively about 0.92 to about 0.98, alternatively about 0.88 to about 0.94. Molecular weight and its moments are determined using GPC-4D.

[0046] In some embodiments, the polypropylene copolymer has a melt flow rate (MFR) of 10 g / 10 minutes or less, or 5 g / 10 minutes or less, or 4 g / 10 minutes or less, or 1 g / 10 minutes or less, such as about 0.1 g / 10 minutes to about 2 g / 10 minutes, such as about 0.2 g / 10 minutes to about 1 g / 10 minutes, such as about 0.3 g / 10 minutes to about 0.9 g / 10 minutes, such as about 0.4 g / 10 minutes to about 0.9 g / 10 minutes, alternatively about 0.3 g / 10 minutes to about 0.6 g / 10 minutes.

[0047] In some embodiments, the polypropylene copolymer has a melting temperature of 155°C or less, 140°C or less, 130°C or less, 110°C or less, 90°C or less. In another embodiment, the polymer produced herein can have a melting point of at least 10°C, or at least 20°C, or at least 30°C, or at least 50°C, or at least 60°C. For example, the polymer can have a melting point of at least 10°C to about 130°C. Alternatively, the polymer produced herein has a melting temperature of 10°C or less, such as 5°C or less. In another embodiment, the polymer produced herein is amorphous without measurable melting temperature in DSC.

[0048] In some embodiments, the polypropylene copolymer has a crystallization temperature of 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less. In another embodiment, the polymer produced herein can have a crystallization point of at least 0°C, or at least 10°C, or at least 15°C, or at least 20°C, or at least 30°C. For example, the polymer can have a crystallization point from at least 0°C to about 130°C. In another embodiment, the polymer produced herein is amorphous without measurable crystallization temperature in DSC.

[0049] In some embodiments, the polypropylene copolymer has a glass transition temperature of 0°C or less, -5°C or less, -10°C or less, -20°C or less, such about -20oC to about -45oC, such as about -30oC to about -36oC.

[0050] In some embodiments, the polypropylene copolymer has a heat of fusion of 100 J / gor less, 80 J / g or less, 70 J / g or less. In another embodiment, the polymer produced herein can have a heat of fusion of at least 1 J / g, at least 5 J / g, or at least 10 J / g, or at least 15 J / g, or at least 20 J / g. For example, the polymer can have a heat of fusion from at least 0.5 J / g to about 180 J / g. In another embodiment, the polymer produced herein is amorphous without measurable crystallization peak and melting peaks in DSC.

[0051] In at least one embodiment, a propylene copolymer of the present disclosure can have a melt temperature (Tm) (°C) of about 30°C to about 130°C and such as about 40°C to about 120°C. In another embodiment, the polymer produced herein is amorphous without measurable melting temperature in DSC

[0052] In some embodiments, the polypropylene copolymer has a Vicat softening temperature of about 30oC to about 90oC, such as about 35oC to about 55oC, alternatively about 50oC to about 60oC, such as about 55oC, as determined by ASTM D1525.

[0053] In some embodiments, the polypropylene copolymer has a Shore A hardness that is about 10 to about 90, such as about 40 to about 80, such as about 50 to about 70, as determined by ASTM D2240.

[0054] In some embodiments, the polypropylene copolymer has a Shore D hardness that is about 10 to about 25, such as about 10 to about 18, such as about 12 to about 20, as determined by ASTM D2240.

[0055] In some embodiments, the polypropylene copolymer has an elongation at break of about 500% to about 1,100%, such as about 600% to about 1,000%, such as about 800% to about 900%.

[0056] In some embodiments, a polypropylene copolymer has a density of about 0.8 to about 0.9 g / cm3, such as from a low of any one of about 0.815, 0.82, 0.83, 0.84, 0.85, or 0.86 g / cm3to a high of any one of 0.9, 0.89, 0.88, 0.87, 0.86, or 0.85 g / cm3, with combinations from any low to any high contemplated (provided the high end is greater than the low end), e.g., about 0.84 to about 0.87 g / cm3, such as about 0.85 to about 0.86 g / cm3. Density testing can follow ASTM D792.

[0057] In embodiments of bimodal polypropylene copolymers, a final polypropylene copolymer product (e.g., dried effluent from the second reactor) can have about 40 wt% or less (such as 20 wt% or less) polymer formed from the second reactor (of the parallel or series of reactors) and about 60 wt% or more (such as 80 wt% or more) polymer formed from the first reactor. In some embodiments, a polypropylene copolymer has about 5 wt% to about 50 wt%, such as about 2 wt% to about 20 wt% polymer formed from the second reactor, such as about 5 wt% to about 15 wt%, such as about 10 wt% to about 15 wt%, alternatively about 2 wt% toabout 10 wt%, such as about 2 wt% to about 5 wt%, alternatively about 20 wt% to about 40 wt%, such as about 25 wt% to about 35 wt%.

[0058] In embodiments of bimodal polypropylene copolymers, the weight average molecular weight of the first polymer component (of the first reactor) is greater than that of the second polymer component (of the second reactor). In embodiments, the weight average molecular weight of the second polymer component is about 400,000 g / mol or less, or about 300,000 g / mol or less, or about 250,000 g / mol or less, or about 200,000 g / mol or less, or about 150,000 g / mol or less, or about 100,000 g / mol or less.

[0059] In some embodiments, the second polymer (second polypropylene copolymer) has a glass transition temperature (Tg) of 0°C or less, -5°C or less, -10°C or less, -20°C or less, such about -20oC to about -45oC, such as about -30oC to about -36oC, such as about -33oC to about -35oC, according to ASTM D3418-03.

[0060] In some embodiments, the second polymer (second polypropylene copolymer) has a heat of fusion of 100 J / g or less, 80 J / g or less, 70 J / g or less. In another embodiment, the second polymer (second polypropylene copolymer) can have a heat of fusion of at least 1 J / g, or at least 5 J / g, or at least 10 J / g, or at least 15 J / g, or at least 20 J / g. For example, the second polymer (second polypropylene copolymer) can have a heat of fusion of about 1 J / g to about 25 J / g, such as about 3 J / g to about 8 J / g, alternatively about 18 J / g to about 25 J / g.

[0061] In at least one embodiment, the second polymer (second polypropylene copolymer) of the present disclosure can have a melt temperature (Tm) (°C) of about 110°C to about 150°C, such as about 110°C to about 140°C, such as about 115°C to about 130°C, such as about 115°C to about 120°C, alternatively about 120oC to about 125oC.

[0062] By definition, a blocky copolymer is one in which the product of the reactivity ratios (r1r2) is greater than 1. A copolymerization between monomers “E” and “P” in the presence of catalyst “M” can be represented by the following reaction schemes and rate equations where R11 is the rate of “E” insertion after “E”, R12 is the rate of “P” insertion after “E”, R21 is the rate of “E” insertion after “P”, R22is the rate of “P” insertion after “P”, and k11, k12, k21, and k22are the corresponding rate constants for each. The reactions scheme and rate equations are illustrated below.

[0063] The reactivity ratios r1and r2are:

[0064] The product of r1 x r2 provides information on how the different monomers distribute themselves along the polymer chain. Below, are illustrations of alternating, random and blocky copolymers and how the product of r1 x r2 relates to each: r1 and r2 also represent the reactivity of ethylene and propylene in the copolymer, respectively, which are used to describe the characteristic of the catalyst system. r1r2, the product of r1and r2, represents the distribution of monomers in the main chain of the copolymer. In at least one embodiment, the r1r2of the polypropylene copolymer is in range of 0.8 to 3.0, alternatively from 0.9 to 2.6, alternatively from 1.0 to 2.2, alternatively from 1.1 to 1.8. In some embodiments, the r1r2is greater than 1.0, such as greater than 1.1 and with an upper limit of 3.0, alternatively 2.8, alternatively 2.5, alternatively 2.2, alternatively 2.0. In some embodiments, the r1r2of the polypropylene copolymer is greater than 1.12-(0.0157x), where x is the wt% of ethylene, as measured by13C NMR.

[0065] In some embodiments, the polypropylene copolymer can have a complex shear viscosity (η*) @ 0.01 rad / sec and 190ºC of about 1,000 to about 100,000 Pa·s, such as from a low of any one of about 1,000, 5,000, 10,000, 15,000, 20,000, 30,000, 35,000, 40,000, 45,000, 50,000, or 55,000 Pa·s to a high of any one of about 20,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, or 70,000 Pa·s, with ranges from any low end to any high end contemplated (for example, about 25,000 to about 35,000 Pa·s or about 50,000 to about 65,000 Pa·s).

[0066] Complex shear viscosity (η*) @ 100 rad / sec and 190ºC may be about 300 to about 10,000 Pa·s, such as from a low of any one of about 300, 500, 1,000, 1,500, 2,000, 3,000, 3,500, 4,000, 4,500, 5,000, or 5,500 Pa·s to a high of any one of about 10,000, 8,800, 7,600, 7,000, 6,500, 6,000, or 5,800 Pa·s, with ranges from any foregoing low to any foregoing high also contemplated (for example, about 1,000 to 3,000 Pa·s or about 3,000 to about 7,000 Pa·s).

[0067] Polypropylene copolymers of various embodiments may also exhibit lower phaseangles at 10 kPA. Phase angle data measures the viscous and elastic properties of a material. Phase angle data of polypropylene copolymers of various embodiments may be about 35 degrees to about 65 degrees at 10kPa, such as about 40 degrees to about 65 degrees, such as about 40 degrees to about 50 degrees, alternatively about 55 degrees to about 65 degrees.

[0068] Polypropylene copolymers of various embodiments may also exhibit a shear thinning ratio (STI 0.1 / 100). Shear thinning ratio data measures the ratio of complex viscosities at 0.1 and 100 rad / s. STI 0.1 / 100 data of polypropylene copolymers of various embodiments may be less than about 70 radians per second (rad / s), or about 5 rad / s to about 70 rad / s, such as from a low of any one of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 rad / s to a high of any one of about 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10 rad / s, with ranges from any foregoing low to any foregoing high also contemplated (for example, about 10 rad / s to about 20 rad / s, or about 40 rad / s to about 50 rad / s, or about 50 rad / s to about 60 rad / s).

[0069] In some embodiments, a polypropylene copolymer has a plateau melt strength (at 190oC) of about 0.07 N or higher, such as about 0.08 N or higher, such as about 0.07 N to about 0.2 N, such as about 0.08 N to about 0.17 N, such as about 0.08 N to about 0.1 N, alternatively about 0.13 N to about 0.17 N. Plateau melt strength is defined as the average value of melt strength after it reaches a plateau in the melt strength testing.

[0070] Rheological data such as “Complex shear viscosity (η*),” reported in Pascal seconds, can be measured at 0.01 rad / sec and 100 rad / sec. Complex shear viscosity and other rheological measurements can be obtained from small angle oscillatory shear (SAOS) experiments.

[0071] For instance, complex shear viscosity can be measured with a rotational rheometer such as an Advanced Rheometrics Expansion System (ARES-G2 model) or Discovery Hybrid Rheometer (DHR-3 Model) using parallel plates (diameter=25 mm) in a dynamic mode under nitrogen atmosphere. The rheometer can be thermally stable at 190°C for at least 20 minutes before inserting compression-molded specimen onto the parallel plates. To determine the specimen’s viscoelastic behavior, a frequency sweep in the range from 0.01 to 628 rad / s can be carried out at a temperature of 190°C under constant strain that does not affect the measured viscoelastic properties. The sweep frequencies are equally spaced on a logarithmic scale, so that 5 frequencies are probed per decade. Depending on the molecular weight and temperature, strains of 3% can be used and linearity of the response is verified. A nitrogen stream is circulated through the oven to minimize chain extension or cross-linking during the experiments. The specimens can be compression molded at 190°C, without stabilizers. A sinusoidal shear strain can be applied. The shear thinning slope (STS) can be measured usingplots of the logarithm (base ten) of the dynamic viscosity versus logarithm (base ten) of the frequency. The slope is the difference in the log(dynamic viscosity) at a frequency of 100 s−1and the log(dynamic viscosity) at a frequency of 0.01 s−1divided by 4. The complex shear viscosity (η*) versus frequency (ω) curves can be fitted using the Carreau-Yasuda model: η*- η∞ = (η0 - η∞)*(1 + (λω)a)(n–1) / a.

[0072] The five parameters in this model are: η0, the zero-shear viscosity; λ, the relaxation time; and n, the power-law index; η∞, the infinite rate viscosity; and a, the transition index. The zero-shear viscosity is the value at a plateau in the Newtonian region of the flow curve at a low frequency, where the dynamic viscosity is independent of frequency. The relaxation time corresponds to the inverse of the frequency at which shear-thinning starts. The power-law exponent describes the extent of shear-thinning, in that the magnitude of the slope of the flow curve at high frequencies approaches n-1 on a log(η*)-log(ω) plot. For Newtonian fluids, n=1 and the dynamic complex viscosity is independent of frequency.

[0073] In addition to dynamic and complex viscosity (each in Pascal seconds), at each frequency sweep in the SAOS experiment, various other parameters are collected, including storage modulus (Pa), Loss modulus (Pa), Complex Modulus (Pa), tan(delta), and phase angle. Charting the phase angle versus the complex shear modulus from the rheological experiment yields Van Gurp Palmen plots useful to extract some information on the molecular characteristics, for example, linear vs. long chain branched chains, type of long chain branching, polydispersity (Dealy, M. J., Larson, R. G., “Structure and Rheology of Molten Polymers”, Carl Hanser Verlag, Munich 182-183 (2006). It has been also suggested that Van Gurp Palmen plots can be used to reveal the presence of long chain branching in polymers. See Trinkle, S., Walter, P., Friedrich, C. “Van Gurp-Palmen plot II—Classification of long chain branched polymers by their topology”, in 41 Rheol. Acta 103-113 (2002).

[0074] “Shear thinning ratio”, which is reported as a unitless number, is characterized by the decrease of the complex viscosity with increasing shear rate. Herein, shear thinning can be determined as a ratio of complex viscosity at a frequency of 0.01 rad / s to the complex viscosity at a frequency of 100 rad / s.13C-NMR Spectroscopy of Polypropylene copolymers

[0075] Polypropylene microstructure is determined by13C-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 d2-1,1,2,2-tetrachloroethane, and spectra recorded at 120°C using a 125 MHz (orhigher) NMR spectrometer. Polymer resonance peaks are referenced to mmmm = 21.83 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).

[0076] Example copolymers produced herein have a ratio of m to r (m / r) of more than 1. The propylene tacticity index, expressed herein as "m / r", is determined by 13C nuclear magnetic resonance (NMR). The propylene tacticity index m / r is calculated as defined in H.N. Cheng, (1984) Macromolecules, v.17, pg. 1950. The designation “m” or “r” describes the stereochemistry of pairs of contiguous propylene groups, “m” referring to meso and “r” to racemic. An m / r ratio of 0 to less than 1.0 generally describes a syndiotactic polymer, and an m / r ratio of 1.0 an atactic material, and an m / r ratio of greater than 1.0 an isotactic material. An isotactic material theoretically may have a ratio approaching infinity, and many by-product atactic polymers have sufficient isotactic content to result in ratios of greater than 50.

[0077] In at least one embodiment, the propylene polymers have isotactic stereo-regular propylene crystallinity. The term "stereo-regular" as used herein means that the predominant number, i.e. greater than 80%, of the propylene residues in the polypropylene exclusive of any other monomer such as ethylene, has the same 1,2 insertion and the stereo-chemical orientation of the pendant methyl groups is the same, either meso or racemic.

[0078] The crystallinity of a polypropylene polymer can be derived from isotactic polypropylene sequences. The isotacticity of the polypropylene polymer can be illustrated by the presence of a preponderance of the propylene residues in the polymer in mm triads. Example propylene polymers produced herein have an mm triad tacticity of three propylene units, as measured by13C NMR, of 75% or greater, 80% or greater, 82% or greater, 85% or greater, or 90% or greater. In one or more embodiments, the mm triad tacticity may range from about 75 to about 99%, from about 80 to about 99%, from about 85 to about 99%, from about 90 to about 99.9%, from about 95 to about 99.9%, from about 97 to about 99.9%, or from about 80 to about 97%.

[0079] The “mm triad tacticity index” of a polymer is a measure of the relative isotacticity of a sequence of three adjacent propylene units connected in a head-to-tail configuration. More specifically, the mm triad tacticity index (also referred to as the “mm Fraction”) of a polypropylene homopolymer or copolymer is expressed as the ratio of the number of units of meso tacticity to all of the propylene triads in the copolymer:mm Fraction=PPP(mm) PPP(mm) + PPP(mr) + PPP(rr) where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from the methyl groups of the second units in the possible triad configurations for three head-to-tail propylene units, shown below in Fischer projection diagrams: CH3CH3CH3PPP(mm):CH CH.

[0080] The is described in U.S.Patent copolymer: column 28, line 38 to column 29, line 67). For further information on how the mm triad tacticity can be determined from a13C-NMR spectrum, see 1) J. A. Ewen, Catalytic Polymerization of Olefins: Proceedings of the International Symposium on Future Aspects of Olefin Polymerization, T. Keii and K. Soga, Eds. (Elsevier, 1986), pp. 271-292; and 2) U.S. Patent Application Publication No. US2004 / 054086 (paragraphs

[0043] to

[0054] ).

[0081] Similarly m diads and r diads can be calculated as follows where mm, mr and mr are defined above. m = mm + ½ mr r = rr + ½ mr

[0082] 13C NMR can be used to determine monomer content and sequence distribution for the ethylene-propylene copolymers using the procedure from J.C. Randall’s paper: Polymer Reviews, 1989, v.29(2), pp. 201-317. The calculations of mole % C3, run number, average sequence length, and diad / triad distributions were all calculated per the method established in the above paper. Calculations for r1r2 can be based on the equation r1r2= 4*[EE]*[PP] / [EP]2; where [EE], [EP], [PP] are the diad molar concentrations; E is ethylene, P is propylene. For other copolymers of ethylene, a similar methodology is used. In another embodiment, the polymers produced herein have regiodefects (as determined by13C NMR), based upon the total propylene monomer. Three types of defects are defined to be the regio defects: 2,1-erythro, 2,1-threo, and 3,1-isomerization as well as a defect followed byethylene insertion. The structures and peak assignments for these are given in [L. Resconi, et al. (2000), Chem. Rev., v.100, pp. 1253-1345]. The regio defects each give rise to multiple peaks in the carbon NMR spectrum, and these are all integrated and averaged (to the extent that they are resolved from other peaks in the spectrum), to improve the measurement accuracy. The chemical shift offsets of the resolvable resonances used in the analysis are tabulated below. The precise peak positions may shift as a function of NMR solvent choice. Regio defect (2,1 defects) Chemical shift range (ppm) αβ + 21-threo +21-er thro (21-P) 3570 - 3409

[0083] The ag g y g ea (CH3, CH, CH2), and multiplied by 10,000 to determine the defect concentration per 10,000 monomers. This value can be converted to mol% regio errors by dividing by 100.

[0084] In some embodiments, a polypropylene polymer has regio defects (also called regio errors) from 0.01 to 1.2 mol%, such as from 0.05 to 1.0 mol%, alternatively from 0.08 to 0.8 mol%, alternatively from 0.1 to about 0.7 mol%.

[0085] As used herein, a “triad content” refers to a three monomer repeat unit: e.g. AAA, AAB, BAA, BAB, ABA, BBA, ABB, BBB summed and normalized to 1. A = propylene; B = ethylene. Triad analysis by13C-NMR gives insight into the sequence distribution and the blockiness of the material. In some embodiments, a polypropylene copolymer has an [PPP] triad content of about 40 mol% to about 60 mol%, such as about 45 mol% to about 55 mol%, such as about 45 mol% to about 50 mol%, as determined by13C nuclear magnetic resonance (13C NMR). (“P” is propylene). In some embodiments, a polypropylene copolymer has an [EEE] triad content of about 0.5 mol% to about 4 mol%, such as about 1 mol% to about 3 mol%, such as about 2 mol% to about 3 mol%, as determined by13C NMR). (“E” is ethylene). In some embodiments, a polypropylene copolymer has an [EEP] triad content of about 7 mol% to about 12 mol%, such as about 8 mol% to about 11 mol%, such as about 8 mol% to about 10 mol%, as determined by13C NMR). In some embodiments, a polypropylene copolymer has an [PEP] triad content of about 8 mol% to about 13 mol%, such as about 10 mol% to about 12 mol%, such as about 10.5 mol% to about 11.5 mol%, as determined by13C NMR). In some embodiments, a polypropylene copolymer has an [EPE] triad content of about 3 mol% to about8 mol%, such as about 3 mol% to about 7 mol%, such as about 4 mol% to about 6 mol%, as determined by13C NMR). In some embodiments, a polypropylene copolymer has an [EPP] triad content of about 18 mol% to about 26 mol%, such as about 20 mol% to about 25 mol%, such as about 22 mol% to about 24 mol%, as determined by13C NMR).

[0086] In some embodiments, the polypropylene copolymer has an [EEE] triad content of greater than (3*10-5)x2+ 0.0005x – 0.0039, where x is the wt% of ethylene, as determined by13C NMR. Impact Copolymers copolymers (ICPs) of the present disclosure can be made by physicallyhomopolymer component(s) and propylene-copolymer component(s) or made in a single reactor process using dual catalysts to produce the different components, or are produced in a series reactor process to produce individual components that are further combined in situ, or in one or more of the reactors. The ICPs can be produced in series reactors wherein the polypropylene homopolymer can be first produced in one or more slurry reactors by contacting a catalyst and monomers, such as propylene, such as in slurry-loop reactors well known in the art, followed by combining the same catalyst and formed homopolymer in a single gas-phase reactor with monomers, such as propylene and ethylene and / or C4to C10α-olefins, to produce the propylene copolymer such that the copolymer imbeds itself in the homopolymer as discrete domains with the homopolymer as a matrix or “continuous” phase. The MFR of the individual components can be controlled by, for example, the addition and / or removal of hydrogen from the reactors. In some embodiments, the homopolymer can be produced in two loop-slurry reactors in series and each as a similar or same amount of hydrogen, producing homopolymer of nearly the same or the same MFR. The amount of hydrogen in the gas phase reactor can be the same or different from the loop slurry reactor, such level controlled by removing the hydrogen from the homopolymer stream entering the gas phase reactor or at some other stage. A suitable process and apparatus can be described in U.S. Pat. No.9,000,106 and U.S. Pat. No. 8,076,419 (column 6, line 6 to column 7, line l6). The systems and processes disclosed therein can be used in a “balanced” reactor scheme where two slurry loop reactors in series forming the polypropylene homopolymer are under the same or similar conditions, followed by transfer of the crystalline polymer (polypropylene homopolymer) to a single gas phase reactor to form the semi-crystalline polymer (propylene copolymer).

[0088] Suitable ICPs can be or can include a polypropylene homopolymer having from about 10 or 15 or 20, or 22, or 24 wt% to about 26, or 28, or 30, or 35, or 40, or 45 wt% of propylene copolymer based on the total weight of the ICP, wherein the copolymer has about 7,or 10, or 15, or 20, or 25, or 30, or 35 wt% to about 40 or 45, or 50, or 55 or 60 wt% ethylene, 1-butene, 1-hexene, and / or 1-octene derived units and about 80 wt% to about 40 wt% propylene-derived units based on the weight of the propylene copolymer, the propylene-based impact copolymer having a MFR of about 10, or 15, or 20, or 26 g / 10 min to about 30, or 36, or 40, or 50 g / 10 min and an Elongation at Break of greater than 60, or 70, or 80, or 90, or 100% (or about 60% or 80% or 100% or 200% to about 120%, or 150%, or 300%, or 400%). Such an ICP tends to have an improved toughness (T-ICP) compared to other ICPs. The propylene copolymer can be an ethylene-propylene copolymer.

[0089] Suitable ICPs also can be or include a polypropylene homopolymer having about 6, or 8, or 10 wt% to about 14, or 16, or 20 wt% of propylene copolymer based on the weight of the ICP, wherein the propylene copolymer has about 20, or 25, or 30, or 35 wt% to about 40, or 45, or 50, or 55, or 60 wt% ethylene, 1-butene, 1-hexene and / or 1-octene derived units and about 80, or 75, or 70, or 65 wt% to about 60, or 55, or 50, 45, or 40 wt% propylene-derived units based on the weight of the propylene copolymer, the ICP having a MFR wiof about 5, or 8, or 12 g / 10 min to about 20, or 30, or 40, or 50 g / 10 min and a surface gloss at 60° of about 40, or 50 to about 80, or 90. Such an ICP tends to have an improved gloss (G-ICP) compared to other ICPs. The propylene copolymer can be an ethylene-propylene copolymer.

[0090] The ICP can have a molecular weight distribution (Mw / Mn) of about 4, or 5 to about 7, or 8. In some embodiments, the ICP is unimodal.

[0091] In some embodiments, the total comonomer derived unit content, such as ethylene derived units of the ICP, can be about 2 or 2.5 wt % to about 4, or 6, or 10, or 16 wt % by weight of the ICP.

[0092] In some embodiments, the melting point temperature of the ICP can be greater than 155, or 160, or 162° C., or a range of about 155, or 160, or 162 °C to about 170 or 180 °C.

[0093] In some embodiments, the polypropylene homopolymer portion of the ICP has an Mw / Mn of about 3, or 3.5, or 4 to about 4.5, or 5, or 6, or 7, or 8, or 9; and the polypropylene homopolymer portion can also have an Mz / Mw of less than 4, or 3.4, or 3.2, or 3.0, or 2.8, or 2.6, or 2.4, or within a range from 2 to 2.5, or 2.6, or 2.8, or 3, or 3.2, or 3.4, or 4. By “polypropylene homopolymer” it is meant a polymer having a range of about 0, or 0.01, or 0.1, or 0.5 to about 2, or 3 wt%, by weight of the polymer, of ethylene, or C4to C10α-olefin-derived units, such as a polymer consisting of propylene-derived units.

[0094] In some embodiments, the “propylene copolymer” or “copolymer” can be a polymer having ethylene, 1-butene, 1-hexene and / or 1-octene derived units, such as ethylene derived units.

[0095] In some embodiments, the isopentad value for the polypropylene homopolymer can be greater than 92, or 94, or 96%, and less than or equal to about 99%.

[0096] In some embodiments, in particular for an ICP with high gloss, the MFR of the polypropylene homopolymer can be about 5, or 10, or 15 g / 10 min to about 20, or 25, or 30, or 40 g / 10 min. In embodiments for an impact copolymer with high toughness, the polypropylene homopolymer has a MFR of about 80 or 100 g / 10 min to about 120, or 140, or 160, or 180, or 200, or 220 g / 10 min.

[0097] In some embodiments, the xylene cold soluble fraction of the ICP described herein, which corresponds to the propylene copolymer portion of the ICP, has a number average molecular weight (Mn) of about 50,000 or 60,000 g / mol to about 80,000 or 100,000 g / mol. In some embodiments, the propylene copolymer has a weight average molecular weight (Mw) of about 150,000, or 180,000, or 200,000 g / mol to about 300,000, or 350,000, or 400,000 g / mol. And further, the propylene copolymer component can have a z-average molecular weight (Mz) of about 400,000, or 450,000, or 500,000, or 550,000 g / mol to about 650,000, or 700,000, or 800,000, or 900,000 g / mol. The propylene copolymer component can have an Mz / Mw of less than 3, or 2.8, or 2.6, or 2.4, or a range of about 2 to about 2.5, or 2.6, or 2.8.

[0098] In some embodiments, the propylene copolymer portion of the ICP described herein has an Mw / Mn of about 3, or 3.5, or 4 to about 4.5, or 5, or 6, or 7, or 8, or 9. The propylene copolymer component has an Mz / Mw of less than 4, or 3.4, or 3.2, or 3.0, or 2.8, or 2.6, or 2.4, or a range of about 2 to about 2.5, or 2.6, or 2.8, or 3, or 3.2, or 3.4, or 4.

[0099] In some embodiments, the propylene copolymer portion of the ICP described herein has a melt flow rate of about 0.1 or 0.2 g / 10 min to about 0.6, or 0.8, or 1, or 2 g / 10 min.

[0100] Also, in some embodiments, the propylene copolymer has an intrinsic viscosity (IV) of about 2 or 2.2 dL / g to about 4, or 4.4, or 5, or 6 dL / g.

[0101] The ICP described herein can be heterogeneous, meaning that there are domains of copolymer within a continuous phase of polypropylene homopolymer. Advantageously, the copolymer domains are relatively small, and the two domains are miscible (instead of large heterogeneous domains). Thus, in some embodiments, the polypropylene homopolymer forms a continuous phase and the copolymer, such as an ethylene-propylene copolymer, forms copolymer domains having an average size (diameter) of less than 10, or 8, or 5, or 4, or 2 or 1 um, or within a range of from 0.40, or 0.45, or 0.50 um to 0.80, or 0.85, or 0.90, or 1, or 2, or 4, or 5, or 8, or 10 um. Due to this nature of the ICP described herein, the surface of the ICP can have high gloss, and thus, the surface gloss can be greater than 80, or 85, or 90 (ASTM D523), or greater than 70, or 75, or 80, or 85 measured at any one of 20, 60, or 85 degrees.

[0102] The ICP described herein can be made in a reactor in granules without further processing if desired. Thus, the impact copolymer includes reactor grade granules having an average particle size of about 1200, or 1300, or 1400, or 1500 um to about 2000, or 2400, or 2800 um and produced at a rate greater than 30,000, or 35,000 or 40,000, or 45,000 lbs / hr (13,620 kg / hr or 15,890 kg / hr, or 18,160 kg / hr, or 20,430 kg / hr). There are any number of ways of making the ICP described herein, but can be manufactured in a two-step, sequential processes that utilizes a solution or slurry-type polymerization process in the presence of a polymerization catalyst, followed by transfer of the homopolymer-active catalyst to a gas phase reactor where it can be further contacted with α-olefin comonomer and propylene to form the copolymer domains within the continuous phase of polypropylene homopolymer. Such processes, individually, are well known in the art, and described for instance in U.S. Pat. No. 8,076,419.

[0103] When manufacturing either the homopolymer or copolymer, the properties of each can be tailored to meet certain desired needs to impart desirable final properties in the ICP described herein, and there can be a range of desirable properties that the ICP described herein can possess. For instance, the level of hydrogen in the reactor(s) can be adjusted, as can the polymerization temperature, residence time, identity of solvent (if any), as well as other factors.

[0104] In some embodiments, the “tough” ICP (T-ICP) has a Heat Deflection Temperature (HDT) within a range of about 70, or 75, or 80, or 85 °C to about 95, or 100, or 115, or 125 °C; or greater than 80, or 84, or 86, or 80, or 92 °C at 66 psi (ASTM D648). In some embodiments, the G-ICP has a HDT of about 100, or 110 °C to about 130, or 135, or 140, or 150 °C; or greater than 100 or 110 °C at 66 psi (ASTM D648).

[0105] Also, in some embodiments, the ICP has a flexural modulus (1% Secant, ASTM D790A) of greater than 200, or 220, or 250, or 300 kpsi, or a range of about 120, or 130, or 140 kpsi to about 200, or 225, or 250, or 300, or 400 kpsi. The tensile strength at yield (ASTM D638) of the ICP described herein can be about 2500 or 2600 or 2800 psi to about 3000, 3500, or 4500, or 5500 psi; or greater than 2800, or 2900, or 3000, or 3200 psi.

[0106] One advantage of the T-ICP can be its desirable impact properties. For instance, the notched Izod impact at 23 °C as measured by ASTM D256A of the ICP described herein can be greater than 4, or 5, or 6, or 8 ft-lb / in (213 J / m, or 267 J / m, or 320 J / m, or 426 J / m) (or a range of about 4 or 5, or 6, or 8 ft-lb / in to about 10, or 12, or 14 ft-lb / in; about 213 or 426 J / m to about 533, or 640, or 693 J / m). Also, the notched Izod impact at 23 °C as measured by ISO 180 / A can be greater than 8, or 10, or 12, or 14, or 20, or 30, or 40 kJ / m2 (or a range of about 8 or 10 kJ / m2to about 16, or 20, or 30, or 40, or 50, or 60 kJ / m2).

[0107] The disclosure described herein can include compositions of the ICP with other polymeric materials and common additives. Desirable polymeric materials include polypropylene homopolymers (as defined above), propylene-based elastomers (such as Vistamaxx™ performance polymers), ethylene-based plastomers, elastomers such as EP rubber, EPDM, butyl rubber, styrenic copolymers and block copolymers, and other impact copolymers, especially so called “high-comonomer” impact copolymers, which are defined as propylene-based impact copolymers having greater than 44 wt % comonomer-derived units in the copolymer portion. Common “additives” include fillers such as talc, carbon black, clay, silica, fatty acids, and other well-known materials, as well as antioxidants, anti-slip agents, pigments, cavitating agents (e.g., calcium carbonate), nucleating agents, curatives for added polymers that are curable, and any other of one or more well-known additives. These polymeric materials and additives can be compounded with the ICP described herein by traditional blending such as in a Brabender mixer, or extruded in a single or double screw extruder, and can possibly be formed into a thermoplastic vulcanizate as can be well known in the art.

[0108] In some embodiments, the ICP can include a polypropylene homopolymer and a range of about 10 to about 45 wt% of propylene copolymer based on the weight of the ICP, wherein the propylene copolymer has about 7 to about 60 wt% ethylene and / or C4to C10α- olefin derived units and the remainder propylene-derived units based on the weight of the propylene copolymer, the ICP having an MFR (230 °C / 2.16 kg) of a range of about 10 to about 50 g / 10 min and an Elongation at Break of greater than 60%. In various embodiments, the ICP can further have one or more of the following properties: (a) a density (as measured at room temperature based on ASTM D1505) of about 0.860 to about 0.920 g / cm3, or about 0.890 to about 0.910 g / cm3; (b) a total propylene-derived unit content of about 88 to about 92 wt%, such as about 90 to about 91 wt%, based on the weight of the ICP; (c) a flexural modulus (1% Secant, as measured based on ASTM D790A) of a range of about 130 to about 200 kpsi, or about 130 to about 160 kpsi, or about 140 to about 150 kpsi; (d) a tensile strength at yield (as measured based on ASTM D638) of about 2500 to about 4500 psi, or about 2600 to about 3500 psi, or about 2800 to about 3000 psi; (e) a notched Izod impact at 23° C. (as measured based on ISO 180 / A) of greater than about 20, or about 30, or about 40 kJ / m2; and (f) a heat deflection temperature (HDT) at 66 psi (as measured based on ASTM D648) of about 75 °C to about 115 °C, or about 80 °C to about 100 °C, or about 85 °C to about 95 °C.

[0109] For the ICPs, tensile properties of the ICP are determined according to ASTM D638, including Young's modulus (also called modulus of elasticity), yield stress (also called tensile strength at yield), yield strain (also called elongation at yield), break stress (also called tensile strength at break), and break strain (also called elongation at break). The energy to yield can be defined as the area under the stress-strain curve from zero strain to the yield strain. The energy to break can be defined as the area under the stress-strain from zero strain to the break strain. Injection-molded tensile bars are of either ASTM D638 Type I or Type IV geometry, tested at a speed of 2 inch / min. Compression-molded tensile bars were of ASTM D412 Type C geometry, tested at a speed of 20 inch / min. For compression-molded specimens only: the yield stress and yield strain were determined as the 10% offset values as defined in ASTM D638. Break properties were reported only if a majority of test specimens broke before a strain of about 2000%, which can be the maximum strain possible on the load frame used for testing.

[0110] Flexure properties of the ICP are determined according to ASTM D790A, including the 1% secant modulus. Test specimen geometry can be as specified under “Molding Materials (Thermoplastics and Thermosets)”, and the support span can be 2 inches.

[0111] Heat deflection temperature of the ICP can be determined according to ASTM D648, at 66 psi, on injection-molded specimens.

[0112] A suitable ICP can include “PP7722KN” (EXXONMOBIL™ PP 7722KN polypropylene, a polypropylene impact copolymer having a density of 0.9 g / cc and a melt mass-flow rate (MFR) (230°C; 2.16 kg) of 1.8 g / 10 min (ASTM D1238), available from ExxonMobil Chemical Company), “PP7011L1” (EXXONMOBIL™ PP 7011L1 polypropylene, a polypropylene impact copolymer having a density of 0.9 g / cc and a melt mass-flow rate (MFR) (230°C; 2.16 kg) of 1 g / 10 min (ASTM D1238), available from ExxonMobil Chemical Company), “PP8244” (EXXONMOBIL™ PP 8244E1 polypropylene, a polypropylene impact copolymer having a density of 0.9 g / cc and a melt mass-flow rate (MFR) (230°C; 2.16 kg) of 29.0 g / 10 min (ASTM D1238), available from ExxonMobil Chemical Company); and “PP7143” (EXXONMOBIL™ PP 7143KNE1 polypropylene, a polypropylene impact copolymer having a density of 0.9 g / cc and a melt mass-flow rate (MFR) (230°C; 2.16 kg) of 24.5 g / 10 min (ASTM D1238), available from ExxonMobil Chemical Company).

[0113] As another example thermoplastic resin, ExxonMobil™ PP 7032E2 is a polypropylene available from ExxonMobil Chemical Company. PP 7032E2 is a polypropylene impact copolymer having the following properties: (1) a density of 0.9 g / cm3;(2) a melt mass-flow rate (MFR) (230 °C; 2.16 kg) of 4.0 g / 10 min (ASTM D1238); (3) a tensile strength at yield 2.0 in / min (51 mm / min) of 3,480 psi (24.0 MPa) (ASTM D638); (4) a tensile stress at yield of 3390 psi (23.4 MPa) (ISO 527-2 / 50); (5) elongation at yield (2.0 in / min (51 mm / min)) of 6.4 % (ASTM D638); (6) tensile strain at yield of 6.2% (ISO 527-2 / 50); (7) flexural modulus – 1% secant (0.51 in / min) of 188,000 psi (1300 MPa) (ASTM D790B); (8) notched Izod impact strength at 23oC of 45 kJ / m2(ISO 180 / 1A); (9) charpy notched impact strength at 23oC of 48 kJ / m2(ISO 179 / 1eA); and (10) heat deflection temperature (1.80 MPa) of 48.7oC (ISO 75-2 / Af).

[0114] ExxonMobil™ PP 7032E3 is a polypropylene available from ExxonMobil Chemical Company. PP 7032E3 is a polypropylene impact copolymer having the following properties: (1) a density of 0.9 g / cm3; (2) a melt mass-flow rate (MFR) (230 °C; 2.16 kg) of 4.0 g / 10 min (ASTM D1238); (3) a tensile strength at yield 2.0 in / min (51 mm / min) of 3,470 psi (23.9 MPa) (ASTM D638); (4) a tensile stress at yield of 3390 psi (23.4 MPa) (ISO 527-2 / 50); (5) elongation at yield (2.0 in / min (51 mm / min)) of 7.3 % (ASTM D638); (6) tensile strain at yield of 6.3% (ISO 527-2 / 50); (7) flexural modulus – 1% secant (0.50 in / min) of 180,000 psi (1240 MPa) (ASTM D790B); (8) notched Izod impact strength at 23oC of 28 kJ / m2(ISO 180 / 1A); (9) charpy notched impact strength at 23oC of 18 kJ / m2(ISO 179 / 1eA); and (10) heat deflection temperature (1.80 MPa) of 51.4oC (ISO 75-2 / A).

[0115] ExxonMobil™ PP 7032KN is a polypropylene available from ExxonMobil Chemical Company. PP 7032KN is a polypropylene impact copolymer having the following properties: (1) a density of 0.9 g / cm3; (2) a melt mass-flow rate (MFR) (230 °C; 2.16 kg) of 4.0 g / 10 min (ASTM D1238); (3) a tensile strength at yield 2.0 in / min (51 mm / min) of 26.1 MPa (ASTM D638); (4) a tensile stress at yield of 26.3 MPa (ISO 527-2 / 50); (5) elongation at yield (2.0 in / min (51 mm / min)) of 5.5 % (ASTM D638);(6) tensile strain at yield of 4.2 % (ISO 527-2 / 50); (7) flexural modulus – 1% secant (1.3 mm / min) of 1,340 MPa (ASTM D790A); (8) notched Izod impact strength at 23oC of 42 kJ / m2(ISO 180 / 1A); (9) charpy notched impact strength at 23oC of 14 kJ / m2(ISO 179 / 1eA); and (10) heat deflection temperature (1.80 MPa) of 52.5oC (ISO 75-2 / A).

[0116] ExxonMobil™ PP 7033E2 is a polypropylene available from ExxonMobil Chemical Company. PP 7033E2 is a polypropylene impact copolymer having the following properties: (1) a density of 0.9 g / cm3; (2) a melt mass-flow rate (MFR) (230 °C; 2.16 kg) of 8.0 g / 10 min (ASTM D1238); (3) a tensile strength at yield 2.0 in / min (51 mm / min) of 3,420 psi (ASTM D638); (4) a tensile stress at yield of 3340 psi (ISO 527-2 / 50); (5) elongation at yield (2.0 in / min (51 mm / min)) of 6.2 % (ASTM D638); (6) tensile strain at yield of 6.3 % (ISO 527-2 / 50); and (7) flexural modulus – 1% secant (0.51 in / min) of 176,000 psi (ASTM D790B).

[0117] ExxonMobil™ PP 7033N is a polypropylene available from ExxonMobil Chemical Company. PP 7033N is a polypropylene impact copolymer having the following properties: (1) a density of 0.9 g / cm3; (2) a melt mass-flow rate (MFR) (230 °C; 2.16 kg) of 8.0 g / 10 min (ASTM D1238); (3) a tensile strength at yield 2.0 in / min (51 mm / min) of 3,760 psi (ASTM D638); (4) a tensile stress at yield of 3,740 psi (ISO 527-2 / 50); (5) elongation at yield (2.0 in / min (51 mm / min)) of 5.2 % (ASTM D638); (6) tensile strain at yield of 4.0 % (ISO 527-2 / 50); and (7) flexural modulus – 1% secant (0.51 in / min) of 224,000 psi (ASTM D790B). Plastomers

[0118] A plastomer comprises ethylene-derived units and one or more of C3to C8α-olefin derived units from about 1 wt % to about 40 wt % of the plastomer, such as from about 5 wt% to about 35 wt % of the plastomer in another embodiment, and from about 5 wt% to about 30 wt% of the plastomer in yet another embodiment. More particularly, a plastomer is a copolymer of ethylene-derived units and one or more of non-cyclic mono-olefins such as propylene, 1- butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene. However, cyclic mono-olefins and both linear and cyclic dienes can also be used in copolymerization with ethylene to form the plastomer. In some embodiments, a plastomer is an ethylene-α-olefin-diene terpolymer.

[0119] In some embodiments, the plastomer is a copolymer of ethylene derived units and1-hexene or 1-octene derived units, wherein the 1-hexene or 1-octene derived units are present in an amount of about 5 wt% to about 50 wt% of the plastomer in one embodiment, about 15 wt% to about 50 wt% of the plastomer in another embodiment, and from about 20 wt% to about 50 wt% in another embodiment, and about 30 wt% to about 50 wt% in yet another embodiment.

[0120] In some embodiments, the plastomer has a density (ASTM D-1505) of about 0.855 g / cm3to 0.915 g / cm3, and a density of about 0.860 g / cm3to about 0.915 g / cm3in another embodiment, and about 0.865 g / cm3to about 0.915 g / cm3in one embodiment, and of about 0.860 g / cm3to about 0.900 g / cm3in another embodiment, and of about 0.855 g / cm3to about 0.908 g / cm3in another embodiment.

[0121] The I2 (2.16 kg / 190° C.) of the plastomer is about 0.10 dg / min to about 40 dg / min in one embodiment, and about 0.5 dg / min to about 10 dg / min in another embodiment, and about 1 dg / min to about 6 dg / min in another embodiment, and about 1.5 dg / min to about 5 dg / min in another embodiment.

[0122] Example plastomers are sold, for example, under the trademark Exact™ (ExxonMobil Chemical Company, Houston, Tex.), such as Exact™ 5171. Other example polymers may include Engage™ polymers (also Affinity™ and Versify™; Dow Chemical Company, Midland, Mich.) and Tafiner™ (Mitsui Petrochemical Co.).

[0123] ExxonMobil™ Exact™ 5171 is an ethylene 1-octene copolymer available from ExxonMobil Chemical Company. Exact™ 5171 has the following properties: of 0.868 g / cm3(ASTM D1505); index (190oC / 2.16 kg) of 1.0 g / 10 min (ASTM D1238); and mass-flow rate (MFR) (230 °C; 2.16 kg) of 2.3 g / 10 min (ASTM D1238).blends (compositions) of the present disclosure can include at least one polypropylene copolymer, at least one impact copolymer, and at least one plastomer.

[0125] In some embodiments, polypropylene copolymers can be present in a composition of the present disclosure in an amount of about 10 wt% to about 95 wt%, such as about30 wt% to about 80 wt%, such as about 50 wt% to about 75 wt%, such as about 55 wt% to about 65 wt%, such as about 60 wt%, based on total amount of polypropylene copolymers, ICPs, and plastomers.

[0126] In some embodiments, ICPs can be present in a composition of the present disclosure in an amount of about 10 wt% to about 99 wt %, such as about 10 wt% to about 60wt %, such as about 20 wt% to about 40 wt%, such as about 25 wt% to about 35 wt%, such as about 30 wt%, based on total amount of polypropylene copolymers, ICPs, and plastomers.

[0127] In some embodiments, plastomers can be present in a composition of the present disclosure in an amount of about 0.1 wt% to about 30 wt %, such as about 1 wt% to about 20 wt%, such as about 5 wt% to about 15 wt%, such as about 8 wt% to about 12 wt%, such as about 10 wt%, based on total amount of polypropylene copolymers, ICPs, and plastomers.

[0128] In some embodiments, a composition has a melt strength (at 190oC) of about 0.02 N or higher, such as about 0.04 N or higher, such as about 0.02 N to about 1 N, such as about 0.02 N to about 0.2 N, such as about 0.02 N to about 0.1 N, alternatively about 0.05 N to about 0.1 N, such as about 0.06 N to about 0.1 N, alternatively about 0.1 N to about 1 N, such as about 0.1 N to about 0.3 N, such as about 0.15 N to about 0.25 N.

[0129] In embodiments, a composition has a melt flow rate (MFR) of 10 g / 10 minutes or less, or 5 g / 10 minutes or less, or 4 g / 10 minutes or less, or 1 g / 10 minutes or less, such as about 0.1 g / 10 minutes to about 2 g / 10 minutes, such as about 0.2 g / 10 minutes to about 1 g / 10 minutes, such as about 0.3 g / 10 minutes to about 0.9 g / 10 minutes, such as about 0.4 g / 10 minutes to about 0.9 g / 10 minutes, alternatively about 0.3 g / 10 minutes to about 0.6 g / 10 minutes.

[0130] In embodiments, a composition has a glass transition temperature of 0°C or less, - 5°C or less, -10°C or less, -20°C or less, such about -20oC to about -45oC, such as about -20oC to about -35oC.

[0131] In some embodiments, a composition has an elongation at break of about 500% to about 1,100%, such as about 600% to about 1,000%, such as about 700% to about 900%, such as about 800% to about 900%, alternatively about 700% to about 800%.

[0132] In some embodiments, a composition has an extensional viscosity (also referred to as elongation viscosity) (measured at 204 °C, shear rate of 1 and 10 s-1) of about 10 Pa•s to about 10,000,000 Pa•s, such as from about 1,000 Pa•s to about 100,0000 Pa•s, such as from about 3,000 Pa•s to about 100,000 Pa•s.

[0133] In some embodiments, a composition has a complex viscosity (at 628 rad / s, 190°C) of 1,000, 900, 800, 700, 600, 500, or 450 Pa*s or less; such as a range of about 200, 250, 300, 350, 400, 450, 500, or 550 Pa*s to about 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1,000 Pa*s.

[0134] In some embodiments, a composition has a complex viscosity (at 100 rad / s, 190°C) of 5,000 Pa*s or less; such as 4,000 Pa*s or less, 3,000 Pa*s or less, 2,000 Pa*s or less; 1,900 Pa*s or less; 1,800 Pa*s or less; or 1,500 Pa*s or less; such as a range of about 600; 700; 800;900; 1,000; 1,200; 1,300; or 1,350 to about 1,000; 1,100; 1,200; 1,300; 1,400; 1,500; 1,750; 2,000; 2,250; 2,500; 2,750; or 3,000 Pa*s.

[0135] In some embodiments, a composition has a complex viscosity (at 0.01 rad / s, 190°C) of 100,000 Pa*s or less; such as 50,000 Pa*s or less; or 30,000 Pa*s or less; 10,000 Pa*s, or 5,000 Pa*s or less; such as a range of about 1,000; 3,000; 4,000; 5,000; 10,000; 12,000; or 15,000 Pa*s to about 40,000; 30,000; 20,000; 18,000; 16,000; 12,000; 10,000; 8,000; or 6,000 Pa*s.

[0136] In some embodiments, a composition of the present disclosure (e.g., as a roofing formulation) has a tensile strength at break of about 10 MPa to about 30 MPa, such as about 15 MPa to about 25 MPa, such as about 15 to about 25. Tensile strength at break can be measured according to ASTM D638 (Type IV, t=0.075" specimen, at 20 in / min).

[0137] Compositions of various embodiments may also exhibit lower phase angles at 10 kPa. Phase angle data measures the viscous and elastic properties of a material. Phase angle data of compositions of various embodiments may be about 35 degrees to about 69 degrees at 10kPa, such as about 40 degrees to about 69 degrees, such as about 40 degrees to about 50 degrees, alternatively about 55 degrees to about 69 degrees. Additives

[0138] The polymer blends provided herein can also contain one or more additives, depending on the intended purpose(s). The additives can be incorporated into the polymer blend directly or as part of a masterbatch, i.e., an additive package containing several additives to be added at one time in predetermined proportions. The additive package or masterbatch can be added in any suitable amount to accomplish the desired result.

[0139] Suitable additives can include reinforcing and non-reinforcing fillers, antioxidants, stabilizers, processing oils, compatibilizing agents, lubricants (e.g., oleamide), antiblocking agents, antistatic agents, waxes, coupling agents for the fillers and / or pigment, pigments, flame retardants, antioxidants, and other processing aids known to the art. In some embodiments, the additives can comprise up to about 65 wt%, or up to about 60 wt%, or up to about 55 wt%, or up to about 50 wt% of the composition. In some embodiments, the additives can comprise at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 35 wt%, or at least 40 wt% of the composition.

[0140] In some embodiments, the composition can include fillers and coloring agents. Exemplary materials include inorganic fillers such as calcium carbonate, clays, silica, talc, titanium dioxide or carbon black. Any type of carbon black can be used, such as channel blacks, furnace blacks, thermal blacks, acetylene black, lamp black and the like.

[0141] In some embodiments, the composition can include flame retardants, such as calcium carbonate, inorganic clays containing water of hydration such as aluminum trihydroxides (“ATH”) or magnesium hydroxide. For example, calcium carbonate or magnesium hydroxide can be pre-blended into a masterbatch with a thermoplastic resin, such as polypropylene, or a polyethylene, such as linear low density polyethylene. For example, the flame retardant can be pre-blended with a polypropylene, an impact polypropylene-ethylene copolymer, or polyethylene, where the masterbatch comprises at least 40 wt%, or at least 45 wt%, or at least 50 wt%, or at least 55 wt%, or at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 75 wt%, of flame retardant, based on the weight of the masterbatch. The flame retardant masterbatch can then form at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, of the composition. In some embodiments, the composition comprises from 5 wt% to 40 wt%, or from 10 wt% to 35 wt%, or from 15 wt% to 30 wt% flame retardant masterbatch, where desirable ranges can include ranges from any lower limit to any upper limit.

[0142] In some embodiments, the composition can include UV stabilizers, such as titanium dioxide or Tinuvin™ XT-850. The UV stabilizers can be introduced into the composition as part of a masterbatch. For example, one or more UV stabilizers can be pre-blended into a masterbatch with a polypropylene or a polyethylene. The one or more UV stabilizers also can be pre-blended with a polypropylene, an impact polypropylene-ethylene copolymer, or polyethylene, where the masterbatch comprises at least 5 wt%, or at least 7 wt%, or at least 10 wt%, or at least 12 wt%, or at least 15 wt%, of UV stabilizer, based on the weight of the masterbatch. The UV stabilizer masterbatch can then form at least 5 wt%, or at least 7 wt%, or at least 10 wt%, or at least 15 wt%, of the composition. In some embodiments, the composition comprises from 5 wt% to 30 wt%, or from 7 wt% to 25 wt%, or from 10 wt% to 20 wt% flame retardant masterbatch, where desirable ranges can include ranges from any lower limit to any upper limit.

[0143] Still other additives can include antioxidant and / or thermal stabilizers. In an exemplary embodiment, processing and / or field thermal stabilizers can include IRGANOX™ B-225 and / or IRGANOX™ 1010 available from BASF.

[0144] In some embodiments, the one or more additive(s) can be present in a composition in an amount of about 0.01 wt% to about 50 wt%, or about 0.1 wt% to about 15 wt%, or from 1 wt% to 10 wt%, based on a total weight of the composition. In some embodiments, a composition includes at least one of an anti-ultraviolet agent and a color masterbatch, such as in an amount of about 7 to about 10 wt%, for example, about 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%,9 wt%, 9.5 wt%, or 10 wt%, based on total weight of the polymer blend. In another embodiment, a polymer blend includes at least one of an anti-ultraviolet agent, a flame retardant, and a color masterbatch, particularly in an amount of about 7 to about 10 wt%, for example, about 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, or 10 wt%, based on total weight of the polymer blend

[0145] In another embodiment, a composition of the present disclosure includes one or more additional polymers prior to being formed into a film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and / or butene, and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and / or polyisobutylene.

[0146] The blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in parallel or series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.

[0147] 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. Films

[0148] Specifically, any of the foregoing compositions, may be used in a variety of end- use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and / or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique,wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented in the transverse and / or longitudinal directions to the same or different extents. The uniaxial orientation can be accomplished using typical cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or double bubble processes and may occur before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. Typically, the films are oriented in the Machine Direction (MD) at a ratio of up to 15, such as between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as 7 to 9. However, in another embodiment the film is oriented to the same extent in both the MD and TD directions.

[0149] The films may vary in thickness depending on the intended application; however, films of a thickness from 1 to 50 µm are usually suitable. Films intended for packaging are usually from 10 to 50 µm thick. The thickness of the sealing layer is typically 0.2 to 50 µm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.

[0150] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In some embodiments, one or both of the surface layers is modified by corona treatment. End Uses

[0151] Any of the foregoing polymers and compositions in combination with optional additives (see, for example, U.S. Patent Application Publication No.2016 / 0060430, paragraphs

[0082] -

[0093] ) may be used in a variety of end-use applications. Such end uses may be produced by methods known in the art. End uses include polymer products and products having exemplary end-uses. Exemplary end uses are films, film-based products, diaper backsheets, housewrap, wire and cable coating compositions, articles formed by molding techniques, e.g., injection or blow molding, extrusion coating, foaming, casting, and combinations thereof. End uses also include products made from films, e.g., bags, packaging, and personal care films,pouches, medical products, such as for example, medical films and intravenous (IV) bags. Exemplary end uses also include thermoplastic polyolefin (TPO) roof sheeting, foam, nonwovens, 3D printing, and recycling solutions.

[0152] For thermoplastic polyolefin roof sheeting, compositions and membranes comprising thermoplastic olefin (TPO) polymers have found widespread use in the roofing industry for commercial buildings. TPO membranes can include a composition of the present disclosure and can be fabricated as a part of a composite structure containing a reflective membrane (40 to 60 mils thick), a reinforcing polyester scrim fabric (1 to 2 mils thick), and a pigmented layer (40 to 60 mils thick). When the membrane is applied to the roof, the reflective membrane layer is exposed to sunlight while the pigmented layer (which is underneath the reflective layer) is attached to the roof insulation material.

[0153] For roofing and other sheeting applications, products can be manufactured as membrane sheets having a typical width of 10 feet (3 meters) or greater, although smaller widths are contemplated. The sheets can be sold, transported, and stored in rolls. For roofing membrane applications, several sheets can be unrolled at the installation site, placed adjacent to each other with an overlapping edge to cover the roof and can be sealed together by a heat welding process during installation. During transport and storage of conventional TPO membrane sheets (not TPO membrane sheets of the present disclosure), the rolls can be exposed to extreme heat conditions, such as from 40 °C to 100 °C, which can lead to roll blocking of the rolls during storage in a warehouse. After installation of the conventional TPO membrane sheets, the membranes can be exposed during service to a wide range of conditions that may deteriorate or destroy the integrity of the membrane. As such, a membrane is desired that can withstand a wide variety of service temperatures, such as from −40 °C to 90 °C. It has been discovered that polypropylene copolymers of the present disclosure can provide compositions used for TPO membrane sheets that can withstand a wide variety of service temperatures, such as from −40 °C to 90 °C, due to improved properties of the polypropylene copolymers of the compositions, such as one or more of MFR, LCB, and / or high molecular weight. In addition, for processability, melt strength can be important for providing dimensional stability, which would need melt strength comparable to that of compositions containing a commercial resin, such as HifaxTMresin to enable high production rate. Polypropylene copolymers of the present disclosure can provide such melt strength.

[0154] Compositions of the present disclosure may exhibit a combination of properties, and in particular exhibit a balance of elastic modulus (flexibility) at temperatures from −40 °C to 40 °C, elastic modulus at elevated temperatures (e.g., 100oC) (an attribute that mitigates rollblocking), and higher melt strength (that provides improved dimensional stability in a sheeting process). The improved melt strength and processability provided by compositions of the present disclosure can provide uniform dispersion of fillers, if present in a composition, which provides more uniform layers (films) for roofing applications, providing improved physical properties of the layers (films).

[0155] FIG.1 is a nonlimiting example of a multilayered roofing membrane 102 that, when applied to a roof 106, is attached to insulation 104 that is attached to a roof 106. The illustrated roofing membrane 102 includes three layers: a first TPO membrane 108, a scrim 110, and a second TPO membrane 112. The scrim 110 provides mechanical strength to the multilayered roofing membrane 102. In the illustrated example, the first TPO membrane 108 is outward facing and can include an additive to make the first TPO membrane 108 reflective to mitigate heat absorption. Further, the second TPO membrane 112 is at or nearest the insulation 104 and can include an additive to make the second TPO membrane 112 dark to improve insulation. In this example, the first TPO membrane 108 and / or the second TPO membrane 112 may be a TPO membrane described herein that includes a composition of the present disclosure which includes one or more of the additional additives such as a thermoplastic resin, a fire retardant, and / or an ultraviolet stabilizer.

[0156] Fire retardants, such as calcium carbonate, can include inorganic clays containing water of hydration such as aluminum trihydroxides (“ATH”) or magnesium hydroxide. UV stabilizers, such as titanium dioxide or Tinuvin® XT-850.

[0157] The roofing membranes described herein (single layer or multilayer) may be fixed over the base roofing by any suitable means, such as via adhesive material, ballasted material, spot bonding, or mechanical spot fastening. For example, the membranes may be installed using mechanical fasteners and plates placed along the edge sheet and fastened through the membrane and into the roof decking. Adjoining sheets of the flexible membranes are overlapped, covering the fasteners and plates, and can be joined together, for example with a hot air weld. The membrane may also be fully adhered or self-adhered to an insulation or deck material using an adhesive. Insulation is typically secured to the deck with mechanical fasteners and the flexible membrane is adhered to the insulation.

[0158] The roofing membranes may be reinforced with any type of scrim including, but not limited to, polyester, fiberglass, fiberglass reinforced polyester, polypropylene, woven or non-woven fabrics (e.g., nylon) or combinations thereof. Example scrims are fiberglass and / or polyester.

[0159] Further, a surface layer of the top and / or bottom of the membrane may be texturedwith various patterns. Texture increases the surface area of the membrane, reduces glare and makes the membrane surface less slippery. Examples of texture designs include, but are not limited to, a polyhedron with a polygonal base and triangular faces meeting in a common vertex, such as a pyramidal base; a cone configuration having a circular or ellipsoidal configurations; and random pattern configurations.

[0160] TPO membranes of the present disclosure may have a thickness of about 0.1 mm to about 3 mm (or about 0.1 mm to about 1 mm, or about 0.5 mm to about 2 mm, or about 2 mm to about 3 mm). Multilayer roofing membranes described herein may have a thickness of about 0.5 mm to about 5 mm (or about 0.5 mm to about 2 mm, or about 1 mm to about 3 mm, or about 2 mm to about 5 mm). TEST METHODS

[0161] Dynamic shear melt rheology test: Dynamic shear melt rheological data was measured using with the Advanced Rheometrics Expansion System (ARES-G2) from TA Instruments. A sample of approximately 1.0 gm weight is compression molded in a disk (diameter = 25 mm, thickness = 2 mm) at 190°C and no stabilizers were added. Then the sample is mounted between the parallel plates (diameter = 25 mm) of the ARES-G2. The test temperature is 190°C, the applied strain is 10%, and the angular frequency was varied from 0.1 rad / s to 200 rad / s. A nitrogen stream was purged through a force convection oven to minimize cross-linking or degradation during the experiments. A sinusoidal shear strain is applied to the material. A small strain amplitude is applied within the linear visco-elastic regime. The complex modulus (G*), complex viscosity (η*) and the phase angle (δ) are measured at each frequency. As those of ordinary skill in the art will be aware, the resulting steady-state stress will also oscillate sinusoidally at the same frequency but will be shifted by a phase angle δ with respect to the strain wave. For purely elastic materials δ=0° (stress is in phase with strain) and for purely viscous materials, δ=90°. For viscoelastic materials, 0 < δ < 90. Phase angle at 10 k Pa G* was used as a measure of long chain branching degree. Complex viscosity, loss modulus (G”) and storage modulus (G’) as function of frequency are provided by the small amplitude oscillatory shear test. Dynamic viscosity is also referred to as complex viscosity or dynamic shear viscosity. The phase or the loss angle (δ), is the inverse tangent of the ratio of G'' (shear loss modulus) to G' (shear storage modulus).

[0162] Shear Thinning Ratio: Shear-thinning is a rheological response of polymer melts, where the resistance to flow (viscosity) decreases with increasing shear rate. The complex shear viscosity is generally constant at low shear rates (Newtonian region) and decreases with increasing shear rate. In the low shear-rate region, the viscosity is termed the zero shearviscosity, which is often difficult to measure for polydisperse and / or LCB polymer melts. At the higher shear rate, the polymer chains are oriented in the shear direction, which reduces the number of chain entanglements relative to their un-deformed state. This reduction in chain entanglement results in lower viscosity. Shear thinning is characterized by the decrease of complex dynamic viscosity with increasing frequency of the sinusoidally applied shear. Shear thinning ratio is defined as a ratio of the complex shear viscosity at frequency of 0.1 rad / sec to that at frequency of 100 rad / sec.

[0163] Solvent Gradient Interactive Chromatography (SGIC) analysis (to measure composition of RCP and polymer in bimodal grades) was done using an SGIC-2D instrument from Polymer Char, S.A., Valencia, Spain. The principles of SGIC-2D analysis are explained in the article Bhati, S. et al. Polyolefins J. 2016, 3, 119. In particular, the schematic configuration shown in Fig.1(a) of this article is an appropriate depiction of the schematic for the apparatus used in the present case. Pertinent features of the apparatus and relevant details of the analysis method, as they apply to the present case, are as follows.

[0164] The IR5 infrared detector (Polymer Char) was used to generate an absorbance signal that is proportional to the concentration of polymer in the eluting flow. The composition signal, in terms of methyl content, was measured as described in the article Ortin, A. et al. Chromatogr. A 2012, 1257, 66. A Hypercarb™ (Thermo Fisher™) column of dimensions 4.6 x 100 mm (I.D. x L.) and a stationary phase of porous graphitic carbon (PGC) particles (5 µm, particle size; 138.2 m2 / gm, surface area) was used in the first dimension. A PL Rapide H (Agilent Technologies) SEC column of dimensions 7.5 x 150 mm (I.D. x L.) packed with 10-µm particles was used in the second dimension.

[0165] The solvents used for preparing the sample solution and for elution were 98+% 1decanol (decanol) and ≥99% 1,2,4-trichlorobenzene (TCB) as the adsorption- and desorption- promoting mobile phases, respectively; the decanol was used as received whereas the TCB was filtered using a membrane filter (0.1 μm JV, Omnipore-™). At the beginning of the analysis, the PGC column was flushed and filled with 100vol% decanol. Temperatures of the PGC and SEC columns were kept at 160 and 170 °C, respectively, throughout the analysis. The sample to be analyzed (1–13 mg) was dissolved in 8 ml of decanol (metered at ambient temperature) by shaking (Medium setting) at 160 °C for 90 min. The solution was then used to completely fill a 100-μl injection-valve loop. Then the injection valve was switched to let the flow from the gradient pump carry the volume in the loop towards the PGC column, and the switching of the valve coincided with the start of a solvent-gradient profile, shown here as a sequence of time (min), TCB (vol%): 0, 0; 150, 30; 170, 30; 190, 50; 200, 100; 312, 100. Flow rates usedfor the PGC and SEC columns were set to 0.025 ml / min of mixed solvent (gradient pump) and 1.5 ml / min of TCB (isocratic pump), respectively, from start to finish of the gradient profile. The transfer-valve loop volume was 100 μl and the valve-switching time was 3 min, thereby filling the loop to 75 μl- for each SEC injection and generating 104 SEC chromatograms per sample analyzed.

[0166] The data generated was processed using an in-house MATLAB application for setting baselines (for subtraction) and integration limits, calibrating the IR5 detector and SEC column, and calculating all relevant metrics from the processed data. For calibrating the CH3 / CH2 band ratio of the IR5 detector to obtain the CH3 / 1000TC signal, up to 39 polyolefin samples with CH3 / 1000TC in the range of 0–333.3 were used. For calibrating the elution volume from the SEC column to obtain the molecular weight of the eluting polymer, nine narrow polystyrene standards (Agilent Technologies) having a peak molecular weight in the range of 1–6035 kg / mol were used. RCP composition of bimodal grades was measured by SGIC.

[0167] GPC-4D: Unless otherwise indicated, for purposes of the Claims, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), the comonomer content are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering about 2700 cm-1to about 3000 cm-1(representing saturated C-H stretching vibration) , an 18- angle light scattering detector and a viscometer. Three Agilent PLgel 10-µm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) comprising ~300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of ~1.0 mL / min and a nominal injection volume of ~200 μL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with ~10 μL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ~8 mL added TCB solvent at ~160°C with continuous shaking. The sample solution concentration can be from ~0.2 to ~2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The concentration, c, at each point in the chromatogram can be calculated from the baseline- subtracted IR5 broadband signal, I, using the equation: c=αI, where α is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography overelution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm / mole. The MW at each elution volume is calculated with following equation: ^+ 1log ^ =log^^^^ / ^^^^^ + 1+^ + 1 log ^^^where the variables with those without a subscript are for the test samples.α and K for other materials are as calculated by GPC ONE™ software (Polymer Characterization, S.A., Valencia, Spain). Concentrations are expressed in g / cm3, molecular weight is expressed in g / mole, and intrinsic viscosity (hence K in the Mark–Houwink equation) is expressed in dL / g unless otherwise noted.

[0168] The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2and CH3channel calibrated with a series of PE and PP homo / copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short- chain branch (SCB) content per 1000TC (SCB / 1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3 / 1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which ^ is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, C6, C8, and so on co-monomers, respectively: ^2 = ^ ∗ SCB / 1000TCThe bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained Bulk IR ratio =Area of CH3signal within integration limits Area of CH2signal within integration limits Then the same calibration of the CH3 and CH2 signal ratio, as mentioned previously in obtaining the CH3 / 1000TC as a function of molecular weight, is applied to obtain the bulk CH3 / 1000TC. A bulk methyl chain ends per 1000TC (bulk CH3end / 1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then ^2^ = ^ ∗ bulk CH3 / 1000TCbulk SCB / 1000TC = bulk CH3 / 1000TC − bulk CH3end / 1000TCand bulk SCB / 1000TC is converted to bulk ^2 in the same manner as described above.

[0169] The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.): Koc 1 = +2A∆ R(θ) MPθ)2c(Here, ΔR(θ) is the measured excess at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil, and Ko is the optical constant for the system: 2 2 2index increment for the system, n = 1.500 for TCB at 145 °C and λ = 665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for analyzing ethylene-butene copolymers, dn / dc = 0.1048*(1-0.00126*w2) ml / mg and A2 = 0.0015 where w2 is weight percent butene comonomer.

[0170] A high temperature Agilent (or 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, ηs, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]= ηs / c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M= K Mα + 1PS[η] where is 0.67 and Kpsis 0.000175.(g'vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]avg, of the sample is calculated by: ^ ci[ η ]i where the summations are over thei, between the integration limits.

[0172] The branching index g'visis defined as '=[ η ] g avg vis KM α , v where Mvis the viscosity-average based on molecular weights determinedby LS analysis and the K and α are for linear polymer, which are, for purposes of the present disclosure, α = 0.705 and K = 0.0002288 for linear propylene polymers. Concentrations are expressed in g / cm3, molecular weight is expressed in g / mole, and intrinsic viscosity (hence K in the Mark–Houwink equation) is expressed in dL / g unless otherwise noted. Calculation of the w2b values is as discussed above.

[0173] Experimental and analysis details not described above, including how the detectors are calibrated and how to calculate the composition dependence of Mark-Houwink parameters and the second-virial coefficient, are described by T. Sun, et al. (2001) Macromolecules, v.34(19), pp.6812-6820.

[0174] Ethylene content is determined using13C NMR by methods well known to those in the art. The content of other comonomers can be obtained using FTIR according the ASTM D3900.

[0175] The comonomer content and sequence distribution of the polymers can be measured using13C nuclear magnetic resonance (NMR) by methods well known to those skilled in the art. Reference is made to U.S. Patent No. 6,525,157 which contains more details of the determination of ethylene content by NMR. Calculations involved in the characterization of polymers by NMR follow the work of J. Randall in Polymer Sequence Determination, 13C- NMR Method, Academic Press, New York, 1977 and Frank Bovey et.al. (1976) Macromolecules, v.9, pp.76-80.

[0176] Comonomer content of discrete molecular weight ranges can be measured using methods well known to those skilled in the art, including Fourier Transform Infrared Spectroscopy (FTIR) in conjunction with samples by GPC, as described in Wheeler and Willis (1993) Applied Spectroscopy, v.47, pp.1128-1130.

[0177] 1H-NMR data of the polymer was collected at 120°C using a 10 mm cryoprobe with a field of at least 600 MHz Bruker instrument with 1,1,2,2-tetrachloroethane-d2 (tce-d2). Samples were prepped with a concentration of 30mg / mL at 140°C. Data was recorded with a 30°pulse, 5 second delay, 512 transients. Signals were integrated and the numbers of unsaturation types per 1,000 carbons per 1,000 carbons were reported. The shift regions for unsaturations were in the following table.Species Shift Region Number of (ppm) hydrogens Calculationtemperature, Tc, (also referred to as crystallization temperature), glass transition temperature (Tg), heat of fusion (∆Hf or Hf), and percent crystallinity were determined using the following DSC procedure according to ASTM D3418-03. Differential scanning calorimetric (DSC) data were obtained using a TA Instruments model Q200 machine. Samples weighing approximately 5-10 mg were sealed in an aluminum hermetic sample pan. The DSC data were recorded by first gradually heating the sample to 200°C at a rate of 10°C / minute. The sample was kept at 200°C for 2 minutes, then cooled to -90°C at a rate of 10°C / minute, followed by an isothermal for 2 minutes and heating to 200°C at 10°C / minute. Both the first and second cycle thermal events were recorded. Areas under the endothermic peaks were measured and used to determine the heat of fusion and the percent of crystallinity. The percent crystallinity is calculated using the formula, [area under the melting peak (Joules / gram) / B (Joules / gram)] * 100, where B is the heat of fusion for the 100% crystalline homopolymer of the major monomer component. These values for B are to be obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, provided; however, that a value of 189 J / g (B) is used as the heat of fusion for 100% crystalline polypropylene, a value of 290 J / g is used for the heat of fusion for 100% crystalline polyethylene. The melting and crystallization temperatures reported here were obtained during the second heating / cooling cycle unless otherwise noted.

[0179] For polymers displaying multiple endothermic and exothermic peaks, all the peak crystallization temperatures and peak melting temperatures were reported. The heat of fusion for each endothermic peak was calculated individually. The percent crystallinity is calculated using the sum of heat of fusions from all endothermic peaks. Some of the polymer blends produced show a secondary melting / cooling peak overlapping with the principal peak, which peaks are considered together as a single melting / cooling peak. The highest of these peaks is considered the peak melting temperature / crystallization point. For the amorphous polymers,having comparatively low levels of crystallinity, the melting temperature is typically measured and reported during the first heating cycle. Prior to the DSC measurement, the sample was aged (typically by holding it at ambient temperature for a period of 2 days) or annealed to maximize the level of crystallinity.

[0180] Melt Strength Data: Melt strength data was measured by using the Rheotester 1000 capillary rheometer in combination with the Rheotens 71.97 (Göttfert) with 72s-1 extrusion rate. A. Test conditions: 1. Rheotester 1000: Temperature: 190°C; Die: 30 / 2; Entrance angle: 180°; time: 300 sec; Piston speed: 0.5 mm / s; Shear rate: 72 sec-1 Strand: Length: 122 mm; Vo: 18 mm / s 3. Rheotens: Gap: 0.7 mm (depending on die swell); Wheels: grooved / Combined Smooth and rough; Acceleration: 12 mm / s² B. Testing: For each material several measurements are performed. In fact, the complete of material present in the barrel of the Rheotester is extruded through the die and is being picked up by the rolls of the Rheotens. Once the strand is placed between the rolls, the roll speed is adjusted till a force 0 is measured. This beginning speed Vs is the speed of the strand through the nip of the wheels at the start of the test. Once the test is started, the speed of the rolls is increased with a 12.0 mm / s² acceleration and the force is measured for each given speed. After each strand break, or strand slip between the rotors, the measurement is stopped and the material is placed back between the rolls for a new measurement. A new curve is recorded. Measuring continues until all material in the barrel is used. C. Data treatment: After testing, all the obtained curves are saved. Curves, which are out of line, are deactivated. The remaining curves, are cut at the same point at break or slip (maximum force measured), and are used for the calculation of a mean curve. The numerical data of this calculated mean curves are reported.

[0181] Linear Capillary Rheometer (LCR): LCR data was collected by using the Ceast “Smart Rheo” Rheometer (SmartRheo 2000), with 30 / 1 L / D ratio capillary die having a round, 1 mm (0.040") diameter orifice, at 204 ºC.

[0182] Delft Tear: Delft tear data was collected by using Zwick Z010. Thickness of the specimen was measured by Mitutoyo Digimatic micrometer No. 543-450B (0-25 mm). ISO23529 was followed to prepare samples with a width of 4 mm and a thickness of 2 mm and following sample conditioning. The samples were tested with a distance of 30 mm between the clamps and with a speed of 500 mm / min.

[0183] Flexural modulus: Flexural modulus data was collected using Zwick 1445.03 with 500 N load cell. The test specimens were produced by injection molding following ISO294-1 using Engel ES500125T injection molding machine. Thickness of the specimen was measured by Mitutoyo Digimatic micro meter. The specimens were conditioned based on ISO291. The specimens have a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. The specimens were tested based on ISO178 with a gauge length of 10 min, a pre-load speed of 1 mm / min, a test speed of 2 mm / min, a span at 64 mm, and a pre-load of 1.4 N. Experimental

[0184] In US Patent Publication No. 2023 / 0097049, which is herein incorporated by reference, a VMX with 0.88 MFR, 16% C2, and no LCB (a phase angle at 10 kPa at 190 ºC of 73 degrees by SAOS) made by bis(phenolate) Lewis base catalysts were disclosed as an example (Exp. 4) in TPO roofing compositions. In U.S. Patent Pub. No. 2021 / 0024733, VMX6102 was blended with LDPE for higher melt strength and extensional viscosity. Herein, the inventors have discovered innovative polypropylene copolymers with a higher LCB degree and / or bimodal design in blends with ICPs (optionally with plastomers). The blends showed improved melt strength and rheological properties arising from LCB and better low temperature performance arising from the higher C2% VMX stabilized by RCP for pellet stability. The blends were also used in TPO roofing compositions and demonstrated improved melt strength and rheological properties.

[0185] “Vistamaxx™ 6102” is a propylene-based elastomer containing 16 wt % ethylene- derived units and has a density of 0.862 g / cm3(ASTM D1505), a melt index (190 °C; 2.16 kg) of 1.4 g / 10 min (ASTM D1238), a melt mass-flow rate (MFR) (230 °C; 2.16 kg) of 3 g / 10 min (ASTM D1238), a Shore A durometer hardness of 66 (ASTM D2240), and a Vicat softening temperature of 52.2 °C (ASTM D1525).

[0186] “ICP 7032E2” is an impact copolymer with a density of 0.90 g / cc (ASTM D1505), a melt mass-flow rate (MFR) (230° C.; 2.16 kg) of 4.0 g / 10 min (ASTM D1238), a Rockwell hardness of 87 (ASTM D785), and a deflection temperature of 82.1° C. (ASTM D648, under load of 66 psi unannealed).

[0187] The VMX6102 polymer is a commercial grade provided by ExxonMobil Chemical Company, Baytown, TX. The other VMX polymers were produced by dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'- biphenyl]-2-olate)], whose preparation was described in US 11,254,763. Their polymer characteristics can be found in Table 1.

[0188] Polymerizations of ethylene and propylene were carried out using a suitablesolution process. For example, in a 28 liter continuous stirred-tank reactor (autoclave reactor), the autoclave reactor was equipped with an agitator, a pressure controller, and insulation to prevent heat loss. The reactor temperature was controlled by controlling the catalyst feed rates and heat removal was provided by feed chilling. All solvents and monomers were purified over beds of alumina and molecular sieves. The reactor was operated liquid full and at a pressure of 1600 psi. Isohexane was used as a solvent. It was fed into the reactor using a turbine pump and its flow rate was controlled by a mass flow controller downstream. The compressed, liquefied propylene feed was controlled by a mass flow controller. Hydrogen was fed to the reactor by a thermal mass flow controller. Ethylene feed was also contolled by a mass flow controller. The ethylene, propylene and hydrogen (if used) were mixed into the isohexane at separate addition points via a manifold. A 3 wt.% mixture of tri-n-octylaluminum in isohexane was also added to the manifold through a separate line (used as a scavenger) and the combined mixture of monomers, scavenger, and solvent was fed into the reactor through a single tube.

[0189] An activated Catalyst A (dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3- adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)]) solution was prepared in a 4 L Erlenmeyer flask in a nitrogen-filled glove box. The flask was charged with 4 L of air-free anhydrous toluene, 0.25 to 0.5 g (~260 to 512*10-6mole) of Catalyst A and 0.21 to 0.42 g Activator A-1 (N,N-dimethylanilinium tetrakis(perfluorophenyl)borate), or 2 g (~2122*10-6mole) of comparative Catalyst B (rac-dimethylsilylene bis(inden-1-yl)hafnium dimethyl) and 1.7 g Activator A-2 (N,N-dimethylanilinium tetrakis(pentafluoronaphth-2-yl)borate) in a ~1:1 molar ratio to make the solution. After the solids dissolved, with stirring, the solution was charged into an ISCO pump and metered into the reactor.

[0190] The catalyst feed rate was controlled along with the monomer feed rates and reaction temperature to produce the polymers described in Table 1. The reactor product stream was treated with trace amounts of methanol to halt the polymerization. The mixture was then freed from solvent via a low-pressure flash separation, treated with Irganox™ 1076 then subjected to a devolatilizing extruder process. The dried polymer was then pelletized.

[0191] Some of the comparative and inventive examples are blends of individual materials with similar process conditions and polymer properties.

[0192] In general, the process conditions targeted for the main Vistamaxx reactor making copolymer with 19 to 21% ethylene are as follows: Reactor temperature was 79-81oC; C2 conversion of 60-90%; C3 conversion of 30-75%; C3 concentration of ~ 0.59 mol / L; C2 concentration of 0.07 mol / L; Hydrogen amount of zero.

[0193] For dual reactor processes, the process conditions targeted for the second reactor making random copolymer product with about 4 to 7% ethylene are as follows: Reactor temperature was about 89-91oC; C2 conversion of about 60-90%; C3 conversion of about 30- 75%; C3 concentration of about 0.65 mol / L; C2 concentration of about 0.012 mol / L; Various amounts of hydrogen. Table 1: Polymer characteristics ID Example Pellet ndut 22% and an MFR of about 0.4 to about 1.#the bimodal grades comprise about 8 to 12% RCP with a C2% of about 5 to 9% and an MFR of about 1 to about 3 and about 88 to 92% VMX with a C2% of about 18.5 to 21.5% and an MFR of about 0.4 to about 1.

[0194] For dual reactor products, reactor samples of the first copolymer from the first reactor and the second copolymer from the second reactor were collected and characterized by FTIR and MFR to determine composition and viscosity. The reactor samples were collected in a solution state followed by solvent removal. The composition of the first polymer and the second polymer can be characterized by SGIC or calculated by the balance of ethylene content using the measured ethylene content of the first polymer, the second polymer and the finished pellets, the later of which is preferred.

[0195] The polymer blends of VMX and ICP, VMX, ICP and ExactTM, and VMX and Hifax CA10A were prepared by using Coperion Twin Screw extruder with screw design optimized for polymer blending with temperature profile from 160oC to 210oC and use of strand cutting setup. Polymer blend pellets were used for rheology behavior. Rheologybehavior was tested per melt flow index condition 230oC and 2.16kg load based on ASTM D1238, Linear capillary rheology was conducted with barrel temperature at 204oC and die 30 / 1 for shear rate 100 to 1000 s-1based on ASTM D3835, melt strength measurement was conducted by Rheotens using the following conditions: "Model curves" are Wagner's model fit to the data. Rheotester 1000 (Göttfert) Temperature: 190 °C Die: 30 / 2 mm Entrance angle: 180 ° Melting time: 300 s Piston speed: 0.5 mm / s Shear rate: 72 s⁻¹ Strand Length: 122 mm Initial speed: 18 mm / s Rheotens 71.97 (Göttfert) Gap: 0.7 mm (depending on die swell) Wheels: grooved Acceleration: 12 mm / s²

[0196] Polymer blend pellets were used in single screw for 1 mm thickness, 25m width strip and set barrel temperature 160oC to 200oC. Tensile properties were measured based on ISO37S2 with a pull rate of 500 mm / min, low temperature performance was measured using a Dynamic Mechanical Thermal Analysis at 10 hertz and 0.2% strain on extruded strip. Melt flow instability test was done using the following test conditions: Equipment: Göttfert Rheograph 2003 equipped with sharkskin tool; Die: slit die 30 / 4 / 0.4 mm; Temperatures: 190 °C; Shear rates run: 150 to 1000 sec-1; Prior to each measurement, the die was flushed 3 times at 1000 s-1 with the sample to be tested; Filling of the barrel in 2 steps: first filling + compression till ± 50 bar. Second filling + compression till ± 50 bar; Melting time: 600 s.

[0197] Moreover, a dual reactor grade with a higher ethylene content and an RCP component for pellet stability can improve low temperature performance. As shown in table 2A, the Tg of the inventive dual reactor grade blends is lower than that of commercial Vistamaxx™ 6102 grade blend, which suggests better low temperature performance of the inventive dual reactor grade blends. In addition, the tan delta at Tg of the inventive dual reactor grade blends is also lower than commercially available Vistamaxx™ 6102 grade blend, whichsuggests better elastic properties of the dual reactor grade blends. The polymer blend properties can be adjusted by replacing the 10% Exact 5171 with PP7032E3 or an innovative VMX such as D(18.5-1.1-L) and D(18.7-0.61). Table 2B shows more examples of polymer blends comprising D(17.2-0.9-L) and various ICP grades (PP7032KN, PP7722KN, PP7011L1) with and without Exact5061 vs Hifax CA10A, Hifax CA10A / VMX6102 and Hifax CA10A / D(17.2- 0.9-L) blends. Table 2A: tensile, thermal, and rheological properties of polymer blends In wt% MAC-211578 B2110- B2110- B2110- B2110- B2110- B2110- (Comparative) 29243 29244 29245 29248 29250 29251 5Table 2A (continued): tensile, thermal, and rheological properties of polymer blends In wt% MAC-211579 MAC- MAC-211581 B2109- B2109- ti 211 2 ti 27227 27228Tg (degC) -22.3 -22.4 -22.2 -24.5 -24.3 Tan d at Tg 0.452 0.415 0.531 0.45 0.48Formulations by 100% Hifax 70% Hifax 70% Hifax 60% D(17.2- 60% D(17.2- wt% CA10A CA10A CA10A 0.9-L) 0.9-L) 2 7Table 2B (continued): mechanical, thermal, and rheological properties of polymer blends Formulations by wt% 60% D(17.2-0.9- 50% D(17.2- 70% D(17.2-0.9- 50% D(17.2-0.9- L) 0.9-L) L) L)

[0198] As shown in FIG.2, the melt strength of the polymer blends comprising VMX with LCB (i.e., S(16.5-0.84-L) and S(16.5-3.0-L)) is higher than that of the polymer blends comprising VMX without LCB and with comparable MFR and C2% (i.e., S(16.4-0.79) and S(16.5-3.9), respectively).

[0199] As shown in FIGs. 3A-3B, the extensional viscosity of the polymer blends comprising VMX with LCB (i.e., S(16.5-3.0-L)) is higher than that of the polymer blends comprising VMX without LCB and with comparable MFR and C2% (i.e., S(16.5-3.9)).

[0200] As shown in FIGs.4A-4D, the melt flow stability of the polymer blends comprising VMX with LCB (i.e., S(16.5-0.84-L) and D(18.5-1.1-L)) is higher than that of the polymer blends comprising VMX without LCB and with comparable MFR and C2% (i.e., S(17.3-0.58) and D(18.3-0.99), respectively). The melt flow stability of the polymer blends comprising bimodal VMX (i.e., D(18.5-1.1-L)) is higher than that of the polymer blends comprising monomodal VMX with comparable MFR (i.e., S(16.5-0.84-L)). Melt flow instability of polypropylene copolymer-based polymer blends (60% Vistamaxx™ + 30% PP7032 + 10% Exact 5171) was collected at 190 ⁰C with pressure fluctuation from 0.001 to 0.5 bar in Y axisvs frequency from 0 to 35 Hz in X axis.

[0201] The TPO roofing compositions were prepared by twin screw extruder (screw functionary length 40D, from Coperion) with melt temperature from 140oC to 210oC, with underwater pelletizer equipment. The Melt Strength test was conducted at 190oC using a RHEOTENS rheometer jointed with an extruder to measure the tensile force presenting melt strength by elongating the melt at a given condition. The TPO roofing compositions were extruded through a round die at constant melt temperature and output. Melt strength force was measured at different strain rates. Extensional viscosity test was conducted using a ARES-G2 rheometer as follows:

[0202] The ARES-G2 rheometer has a motor with maximum torque range of 800 mN·m and a transducer with torque range from 0.05 μN·m to 200mN·m. The temperature is controlled by an air / N2 gas convection oven which is capable of rapid heating or cooling from 150°C to 600 °C. A range of geometries are available for the rheometer, including parallel plate, cone and plate, torsion rectangular, extensional viscosity fixture.

[0203] Extensional Viscosity Fixture: Sample test sheets (0.8mm thick) can be pressed by using the hot press with water-cooling machine.

[0204] 0.8 mm thick mold with 20 rectangles (10mm width and 18mm length) is stored in ARES drawer and used for this method.

[0205] Typical cycle for compression molding the test samples:

[0206] 1 min without additional pressure

[0207] 1.5 min with 50bar pressure

[0208] Cooling between cold watercooled plates.

[0209] Temperature settings press: 190°C

[0210] SAOS test was conducted using the ARES-G2 rheometer under 190oC, nitrogen atmosphere, 398~0.1 rad / s range. Sample test discs can be pressed using the Schwabenthan laboratory press (200T). When polymers have to be tested, special molds are available (4 or 5 discs, 25 mm, thickness 1 mm).

[0211] Typical cycle for compression molding the test samples: • 1 min without additional pressure • 1.5 min with 50bar pressure • Cooling between cold water-cooled plates. Temperature settings press: 190°C.

[0212] Tensile test was conducted with ISO 37 type 1 tensile bar, 500mm / min speed.Specimens are cut from flat plaques. Each plaque can cut one tensile specimen. Minimum three specimens are needed for one test. There are two directions of punching: flow direction or cross flow direction. Specimens must be conditioned at 23±2°C and 50±10% humidity for not less than 16 hours prior to testing. At least 3 specimens need to be tested for 1 test. Table 3A: composition of TPO roofing compositions Material Wt% S(15.7-0.93-L) 40[ ] s s own n . , e me s reng o e roo ng compos ons compr sing VMX with LCB (i.e., S(16.5-0.84-L) and S(15.7-0.93-L)) is higher than that of the TPO roofing compositions comprising VMX without LCB and with comparable C2% but lower MFR (i.e., S(16.6-0.43) and S(17.3-0.58)).

[0214] As shown in FIGs. 6A-6C, the extensional viscosity of the TPO roofing compositions comprising VMX with LCB (i.e., S(16.5-0.84-L) and S(15.7-0.93-L)) is generally higher than that of the TPO roofing compositions comprising VMX without LCB and with comparable C2% but lower MFR (i.e., S(16.6-0.43) and S(17.3-0.58)).

[0215] As shown in FIG. 7, the complex viscosity of the TPO roofing compositions comprising Vistamaxx™ with LCB (i.e., S(16.5-0.84-L) and S(15.7-0.93-L)) is higher than that of the TPO roofing compositions comprising VMX without LCB and with comparable C2% but lower MFR (i.e., S(16.6-0.43) and S(17.3-0.58)) at the lower frequency regime.

[0216] As shown in Figure 8, the tensile and elongation of the TPO roofing compositions comprising VMX with LCB (i.e., S(16.5-0.84-L) and S(15.7-0.93-L)) are generally comparable as those of the TPO roofing compositions comprising VMX without LCB and with comparable C2% but lower MFR (i.e., S(16.6-0.43) and S(17.3-0.58)), which suggests the mechanical properties are retained while improving the melt strength and rheological properties by using polypropylene copolymer with LCB.

[0217] D(17.2-0.9-L) based TPO roofing compounds, Hifax CA10A and HifaxCA10A / VMX6102 based TPO roofing compounds (as shown in Table 3B) were also prepared using the same method of the polymer blend preparation with the Coperion Twin Screw extruder (as shown in Table 2A and 2B above). MDH is a masterbatch of magnesium hydroxide, Mg(OH)2, which contains 79% of natural Mg(OH)2, and a blend of Vistamaxx™ 6202 and Vistamaxx™ 8880 as carrier. Provided in masterbatch form via twin screw compounding. Table 3B: mechanical, thermal, and rheological properties of TPO roofing compounds Formulations by wt%62.5% Hifax43.75% Hifax 43.75% Hifax 43.75% CA10A CA10A CA10A D(172-09-L)Table 3B (continued): mechanical, thermal, and rheological properties of TPO roofing compounds Formulations by 43.75% D(17.2- 43.75% 18.75% 31.25% wt% 0.9-L) D(17.2-0.9-L) D(17.2-0.9-L) D(17.2-0.9-L) 2 TTable 4: Formulations Extruded Into Membranes with Davis Standard line Material F1 F2 F3 F4 F5 F6 F7 F8 6102(149- 30 30Ampacet 112482 is masterbatch of TiO2in polyethylene.Table 5: Barrel Profile Zone 1 Zone 2 Zone 3 Zone 4 Zone 5 400 °F 420 °F 430 °F 430 °F 430 °F ’’Roll Temperature (°F) Top 130roll temperature profiles. The membranes were extruded using a 3.5’’ single screw Davis Standard extruder. The extruder was vacuum vented and all of the formulations were pre-dried to eliminate moisture, voids, and other surface defects on the membrane that stem from moisture and VOCs. All membranes were extruded at a line speed of ~19 ft / min with a 30 mil thickness.

[0219] As shown in FIG.9, TPO roofing sheet F2 containing D(18.5-1.1-L) showed higher shear thinning than comparative TPO roofing sheet F1 containing 6102(14.9-3.1). The viscosity of the TPO roofing sheet can be further increased by replacing the 4 MFR PP7032 (F2) with the 2 MFR PDI082 (F6).

[0220] As shown in FIG. 10, TPO roofing sheet F2 and F6 containing D(18.5-1.1-L) showed lower phase angle at complex modulus lower than ~30000 Pa than TPO roofing sheet F1, which comes from the LCB of D(18.5-1.1-L).

[0221] Overall, compositions of the present disclosure can provide improved melt strength as well as maintained or improved cold temperature performance, and capability of making quality single ply TPO roofing sheets under high production rates. Compositions of the present disclosure can provide maintained mechanical properties while providing the improved melt strength and improved rheological properties. For example, polypropylene copolymers of the present disclosure can have one or more of long chain branching, low melt flow rate, and / or high molecular weight. Long chain branching, for example, can provide shear thinning (high viscosity at low frequency and low viscosity at high frequency) which can provide higher melt strength for improved processability. Compositions of the present disclosure can be used in TPO roofing membranes to provide reduced or eliminated melt instability the extruded TPO roofing membrane.

[0222] The phrases, unless otherwise specified, "consists essentially of" and "consistingessentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0223] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0224] 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.

[0225] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

CLAIMS What is claimed is:

1. A composition comprising: a polypropylene copolymer comprising about 0.1 mol% to about 35 mol% ethylene units and about 99.9 mol% to about 65 mol% propylene units, the polypropylene copolymer having: an mm triad tacticity of about 75% or greater, regio defects of about 0.01 mol% to about 1.2 mol%, an r1r2 of about 0.8 to about 3, a melt flow rate (230oC / 2.16 kg) of about 4 g / 10 minutes or less, a phase angle at 10 kPa at 190oC less than 69 degrees, and an [EEE] triad content of about 0.5 mol% to about 4 mol%; an impact copolymer; and optionally a plastomer.

2. The composition of claim 1, further comprising a fire retardant and at least one of an ultraviolet light stabilizer or an antioxidant.

3. The composition of any of claims 1 to 2, wherein the polypropylene copolymer has a melt flow rate of about 0.3 g / 10 minutes to about 4 g / 10 minutes.

4. The composition of any of claims 1 to 3, wherein the polypropylene copolymer has: a weight average molecular weight (Mw)(LS) of about 250,000 g / mol to about 400,000 g / mol, a number average molecular weight (Mn)(LS) of about 100,000 g / mol to about 175,000 g / mol, and a z-average molecular weight (Mz)(LS) of about 300,000 g / mol to about 650,000 g / mol.

5. The composition of any of claims 1 to 4, wherein the polypropylene copolymer has a complex shear viscosity (η*) @ 0.01 rad / sec and 190ºC of about 15,000 Pa·s to about 70,000 Pa·s.

6. The composition of any of claims 1 to 5, wherein the phase angle at 10 kPa at 190oC is less than 69 degrees.

7. The composition of claim 6, wherein the phase angle at 10 kPa at 190oC is about 55 degrees to about 65 degrees.

8. The composition of any of claims 1 to 7, wherein the mm triad tacticity is about 97% to about 99.9%.

9. The composition of any of claims 1 to 8, wherein the polypropylene copolymer has: [PPP] triad content of about 45 mol% to about 55 mol%, [EEE] triad content of about 1 mol% to about 3 mol%, [EEP] triad content of about 8 mol% to about 11 mol%, [PEP] triad content of about 10 mol% to about 12 mol%, [EPE] triad content of about 3 mol% to about 7 mol%, and [EPP] triad content of about 20 mol% to about 25 mol%.

10. The composition of any of claims 1 to 9, further comprising a second polypropylene copolymer comprising about 2 wt% to about 10 wt% ethylene content and about 90 wt% to about 98 wt% propylene content, wherein the second polypropylene copolymer has a weight average molecular weight (Mw) that is less than the weight average molecular weight of the first polypropylene copolymer.

11. The composition of claim 10, wherein the second polypropylene copolymer is present in an amount of about 1 wt% to about 20 wt%, based on total weight of the first polypropylene copolymer and the second polypropylene copolymer.

12. A composition comprising: a first polypropylene copolymer comprising about 0.1 mol% to about 35 mol% ethylene units and about 99.9 mol% to about 65 mol% propylene units, the first polypropylene copolymer having: an mm triad tacticity of about 75% or greater, regio defects of about 0.01 mol% to about 1.2 mol%, an r1r2of about 0.8 to about 3, andan [EEE] triad content of about 0.5 mol% to about 4 mol%; and a second copolymer comprising about 2 wt% to about 10 wt% ethylene content, wherein the second copolymer has a weight average molecular weight (Mw) that is less than the weight average molecular weight of the first copolymer; an impact copolymer; and optionally a plastomer.

13. The composition of claim 12, further comprising a fire retardant and at least one of an ultraviolet light stabilizer or an antioxidant.

14. The composition of claim 13, wherein the first polypropylene copolymer has about 16 wt% to about 23 wt% ethylene units and about 77 wt% to about 84 wt% propylene units.

15. The composition of claims 13 or 14, wherein the second polypropylene copolymer comprises about 2 wt% to about 8 wt% ethylene content and about 92 wt% to about 98 wt% propylene content, wherein the second polypropylene copolymer has a weight average molecular weight (Mw) that is less than the weight average molecular weight of the first polypropylene copolymer.

16. The composition of any of claims 13 to 15, wherein the combination of the first polypropylene copolymer and the second polypropylene copolymer has an Mw / Mn value of about 2 to about 4.

17. The composition of any of claims 13 to 16, wherein the first polypropylene copolymer has: a weight average molecular weight (Mw)(LS) of about 250,000 g / mol to about 400,000 g / mol, and a number average molecular weight (Mn)(LS) of about 100,000 g / mol to about 175,000 g / mol.

18. The composition of any of claims 13 to 17, wherein the mm triad tacticity is about 97% to about 99.9%.

19. The composition of any of claims 13 to 18, wherein the first polypropylene copolymer has: [PPP] triad content of about 45 mol% to about 55 mol%, [EEE] triad content of about 1 mol% to about 3 mol%, [EEP] triad content of about 8 mol% to about 11 mol%, [PEP] triad content of about 10 mol% to about 12 mol%, [EPE] triad content of about 3 mol% to about 7 mol%, and [EPP] triad content of about 20 mol% to about 25 mol%.

20. The composition of any of claims 1 to 19, wherein the impact copolymer has a melt index @ 230oC / 2.16 kg of about 0.3 g / 10 min to about 4 g / 10 min and a density of about 0.87 g / cm3to about 0.902 g / cm3.

21. The composition of any of claims 1 to 20, wherein the composition comprises: the first polypropylene copolymer in an amount of about 10 wt% to about 95 wt%, and the impact copolymer in an amount of about 5 wt% to about 90 wt%, based on total amount of the polypropylene copolymer, the impact copolymer.

22. The composition of claim 21, wherein the composition comprises the plastomer in an amount of about 5 wt% to about 25 wt%, based on total amount of the polypropylene copolymer, the impact copolymer, and the plastomer.

23. The composition of any of claims 1 to 22, wherein the composition comprises the plastomer, and the plastomer has a density of about 0.855 g / cm3to about 0.900 g / cm3and a melt index of about 0.1 g / 10 min to about 20 g / 10 min.

24. The composition of any claims 21 to 23, wherein the composition has a melt strength (at 190oC) of about 0.1 N to about 1 N.

25. The composition of any of claims 21 to 24, wherein the composition has an elongation at break of about 700% to about 900%.

26. The composition of any of claims 21 to 25, wherein the composition has a phase angle at 10 kPa at 190oC of about 55 degrees to about 65 degrees.

27. A membrane sheet comprising: a scrim; a first TPO membrane disposed on the scrim; and a second TPO membrane, wherein the scrim is disposed on the second TPO membrane, wherein at least one of the first TPO membrane or the second TPO membrane independently comprises the composition of any of claims 1 to 26.

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