Propylene-based elastomer compositions, articles thereof and methods

Abstract

The present specification provides compositions including propylene-based elastomers, articles thereof, and methods thereof. In at least one embodiment, the compositions include a propylene-based elastomer having a Mw of about 300,000 g / mol to about 600,000 g / mol and a melt flow rate of less than about 3 g / 10 min according to ASTM D-1238 (2.16 kg weight @ 230 °C). The compositions include a thermoplastic resin. In at least one embodiment, the roofing material includes a membrane. The membrane includes a composition. The composition includes a propylene-based elastomer having a Mw of about 300,000 g / mol to about 600,000 g / mol and a melt flow rate of less than about 3 g / 10 min according to ASTM D-1238 (2.16 kg weight @ 230 °C). The roofing material further includes a base material adhered to or secured to the membrane.

Description

[0001] Inventors: RU XIE, KRISHNAN IYER, SHANSHAN ZHANG, IVEREL GERARD E.TUMBAGA, YING YING SUN, ANTONIOS K.DOUFAS, PEIJUN JIANG, JUN SHI, NARAYANASWAMIDHARMARAJAN

[0002] Cross-reference to related applications

[0003] This application claims priority to USSN 62 / 947,937, filed December 13, 2019, which is incorporated herein by reference. Technical Field

[0004] This specification provides compositions comprising propylene-based elastomers, articles thereof, and methods thereof. Background Technology

[0005] Compositions and films containing thermoplastic olefin (TPO) polymers have been found to be widely used in the roofing industry of commercial buildings. TPO films are typically made into a composite structure comprising a reflective film (40 to 60 mils thick), a reinforcing polyester sparse fabric (1 to 2 mils thick), and a colored layer (40 to 60 mils thick). When the film is applied to a roof, the reflective film layer is exposed to sunlight while the colored layer (located below the reflective layer) is attached to the roof insulation material.

[0006] For roofing and other sheet applications, products are typically manufactured as membrane sheets with a width of 10 feet (3 meters) or more, but smaller widths are also possible. Sheets are usually sold, transported, and stored in rolls. For roofing membrane applications, several sheets are unrolled at the installation site, placed adjacent to each other with overlapping edges to cover the roof, and sealed together during installation using a thermal welding process. During transport and storage, rolls may be exposed to extreme heat conditions, such as 40°C to 100°C, which can cause roll blocking during warehouse storage. After installation, the membrane may be exposed to various conditions during use that could degrade or compromise its integrity. Therefore, membranes capable of withstanding a wide range of operating temperatures, such as from -40°C to 40°C, are required.

[0007] The polymer matrix commonly used in TPO roofing membranes is reactor-grade TPO with a high rubber content. This resin is used in applications requiring a combination of processability and flexibility. Compared to compositions containing conventional resins, the market demands TPO roofing membranes with further enhanced flexibility and the ability to maintain high-temperature performance. Compositions that can maintain performance and processability are also needed. For processability, melt strength may be important for providing dimensional stability; this will require the use of compositions containing commercially available resins (such as Hifax). TM The composition of the resin has a comparable melt strength. For example, compositions based on commercial resins may provide sufficient mechanical properties, but require increased melt strength for processability.

[0008] There is a need for compositions and roofing membranes that exhibit a balance of elastic modulus (flexibility) at temperatures from -40°C to 40°C, elastic modulus at high temperatures (e.g., 100°C) (reducing roll adhesion properties), and higher melt strength (providing improved dimensional stability during tableting).

[0009] This specification provides compositions comprising propylene-based elastomers, articles thereof, and methods thereof. Attached Figure Description

[0010] Figure 1 This is a non-limiting example of a multilayer roofing membrane that, when applied to a roof, is connected to an insulation material that is connected to the roof.

[0011] Figure 2 It is a graph illustrating the elastic modulus E of the composition according to one embodiment versus temperature.

[0012] Figure 3 It is a graph illustrating the melt strength of the composition according to one embodiment.

[0013] Figure 4 This is a graph comparing the tensile viscosity of graded MFR PBE with that of a control sample over time, according to one implementation scheme.

[0014] Figure 5 It is a graph comparing the tensile viscosity of PBE-VNB with that of a control sample over time according to one implementation scheme.

[0015] Figure 6 This is a graph comparing the tensile viscosity of branched PBE and unbranched PBE against time according to one embodiment of the present invention.

[0016] Figure 7 It is a Van Gurp-Palmen plot comparing the complex modulus (Pa) versus phase angle (deg) of branched PBE and unbranched PBE according to one implementation scheme.

[0017] Figure 8AThe GPC data of the polymer obtained from the diagram ( Figure 8B yes Figure 8A (Enlarged image).

[0018] Figure 9 The curve showing the relationship between elastic modulus (E′) and temperature is displayed.

[0019] Figure 10 The melt strength of the selected pure polymer is displayed.

[0020] Figure 11 The melt strength of the selected blend is displayed.

[0021] Figure 12 It shows a relatively pure Vista Max. TM 3588 and Vista Maxx TM DSC results of the thermal behavior of 3588-g-PS. Invention Details

[0023] This specification provides compositions comprising propylene-based elastomers, articles thereof, and methods thereof. For example, the compositions may include propylene-based elastomers suitable for roofing applications, such as films. The compositions of this specification are particularly suitable for roofing applications, such as for thermoplastic polyolefin roofing films. The compositions and films of this specification can exhibit a combination of properties, and particularly a balance of elastic modulus (flexibility) at temperatures from -40°C to 40°C, elastic modulus at high temperatures (e.g., 100°C) (properties that reduce roll adhesion), and higher melt strength (providing improved dimensional stability during tableting). The improved melt strength and processability provided by the compositions of this specification can provide uniform dispersion of fillers, which, if present in the composition, provides a more uniform layer (film) for roofing applications, thereby providing improved physical properties of the layer (film).

[0024] The improved compositions may include PBE polymers having at least one of the following properties: (i) low graded melt flow rate, (ii) long-chain branching, and (iii) grafting with polystyrene. Advantageously, such PBEs exhibit increased melt strength and tensile viscosity compared to conventional PBEs. Formulations suitable for roofing applications, particularly roofing membranes, comprising such PBEs are described herein. These formulations provide a balance of performance over a wide temperature range.

[0025] All numerical values ​​in the detailed description and claims herein are corrected to “about” or “approximately” values ​​and take into account experimental errors and variations expected by one of ordinary skill in the art.

[0026] As used herein, the term "polymer" is intended to include polymers having two or more monomers, optionally together with other monomers, and may refer to interpolymers, terpolymers, etc. As used herein, the term "polymer" includes homopolymers, copolymers, terpolymers, etc., and alloys and blends thereof. As used herein, the term "polymer" also includes impact, block, graft, random, and alternating copolymers. Unless otherwise specified, the term "polymer" should further include all possible geometries. Such geometries can include isotactic, syndiotactic, and atactic symmetries. As used herein, the term "blend" refers to a mixture of two or more polymers. The term "elastomer" should refer to any polymer exhibiting a degree of elasticity, where elasticity is the ability of a material deformed by a force (e.g., by stretching) to at least partially return to its original dimensions after the force is removed.

[0027] As used herein, the term "monomer" or "comonomer" can refer to the monomer used to form the polymer, i.e., the unreacted compound in its pre-polymerization form, or to the monomer after it has been incorporated into the polymer, also referred to herein as "[monomer]-derived unit". This article discusses various monomers, including propylene monomers, ethylene monomers, and diene monomers.

[0028] As used herein, “reactor-grade” means a polymer that has not undergone chemical or mechanical treatment or blending after polymerization in an attempt to alter its average molecular weight, molecular weight distribution, or viscosity. Specifically excluded from those polymers described as reactor-grade are those that have undergone de-thickening cracking or other treatments, or have been coated with peroxides or other degradation aids. However, for the purposes of this specification, reactor-grade polymers include those polymers used as reactor blends.

[0029] As used herein, "reactor blend" refers to a highly dispersed and mechanically inseparable blend of two or more polymers produced by the sequential or parallel polymerization of one or more monomers and the in-situ formation of a polymer in the presence of another polymer, or by solution blending of polymers prepared individually 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. Polymers specifically excluded from "reactor blends" are blends of two or more polymers where the polymers are not blended in situ, for example, by physical or mechanical blending in a mixer, extruder, or other similar apparatus.

[0030] Composition

[0031] The compositions described herein comprise polymer blends of one or more propylene-based elastomers and one or more thermoplastic resins. In at least one embodiment, the composition has a propylene-based elastomer content of about 1 wt% to about 60 wt%, for example, about 5 wt% to about 40 wt%, for example, about 20 wt% to about 40 wt%, for example, about 25 wt% to about 35 wt%, for example, about 30 wt%, based on the weight of the composition. In at least one embodiment, the composition has a thermoplastic resin content of about 1 wt% to about 60 wt%, for example, about 5 wt% to about 40 wt%, for example, about 20 wt% to about 40 wt%, for example, about 25 wt% to about 35 wt%, for example, about 30 wt%, based on the weight of the composition. In one embodiment, the polymer blend comprises less than 15 wt% ethylene.

[0032] The compositions described herein may include one or more additives. Additives may include reinforcing and non-reinforcing fillers, antioxidants, stabilizers, processing oils, compatibilizers, lubricants (e.g., oleamide), antiblocking agents, antistatic agents, waxes, coupling agents for fillers and / or pigments, pigments, flame retardants, antioxidants, or other processing aids. In some embodiments, the composition may contain about 1 wt% to about 60 wt% of additives, for example, about 5 wt% to about 40 wt%, about 20 wt% to about 40 wt%, about 25 wt% to about 35 wt%, or about 30 wt%, based on the weight of the composition.

[0033] The melt flow rate (MFR) of the composition described in this specification is at least 0.01 dg / min (e.g., 0.1 to 50 dg / min, 0.2 to 30 dg / min, 0.1 to 1.5 dg / min, 0.15 to 1.4 dg / min, e.g., 0.9 to 1.3 dg / min) (ASTM 1238, 2.16 kg, 230 °C). Alternatively, the melt flow rate (MFR) of the composition is at least 0.01 dg / min (e.g., 0.1 to 50 dg / min, e.g., 1 to 10 dg / min).

[0034] The composition may be elastic in the molten phase. “Tanδ” is the ratio of viscous modulus (E') to elastic modulus (E') and is a useful quantifier of the presence and degree of elasticity in the melt. In some embodiments, the composition has a Tanδ greater than 4, or 6, or 8, or 10, or in the range of 4, or 6, or 8, or 10 to 20, or 24, or 28, or 32, or 36.

[0035] In at least one embodiment, the composition of this specification may have a viscous modulus (E) of about 2.0E+10 to about 7.0E+10 at -40°C, as determined by the method described below.

[0036] In at least one embodiment, the composition of this specification may have a viscous modulus (E) of about 3.0E+08 to about 3.0E+09 at 100°C, as determined by the method described below.

[0037] In at least one embodiment, the composition of this specification may have an elastic modulus (E′) of about 4.0E+09 to about 7.0E+09 at -40°C, as determined by the method described below.

[0038] In at least one embodiment, the composition of this specification may have an elastic modulus (E′) of about 8.0E+07 to about 2.0E+08 at 100°C, as determined by the method described below.

[0039] The membranes made from the compositions of this specification may have a stiffness (1% flexural modulus) greater than 200 MPa or greater than 225 MPa in the longitudinal (MD) and transverse (TD) directions, for example, from about 250 MPa to about 1,000 MPa, for example, from about 300 MPa to about 500 MPa.

[0040] In one or more embodiments, the monolayer comprising the polyolefin composition independently has a relatively high stiffness value (1% flexural modulus) in each of MD and TD. The 1% flexural modulus MD (in the longitudinal direction) of the polyolefin composition is greater than 200 MPa, greater than 225 MPa, greater than 250 MPa, or greater than 275 MPa, for example about 200 MPa, 300 MPa, about 400 MPa, about 500 MPa, or about 600 MPa to about 700 MPa, about 800 MPa, about 900 MPa, about 1,000 MPa, about 1,200 MPa, about 1,500 MPa or greater, determined under conditions where the thickness of the layer (e.g., monolayer) of the polyolefin composition is about 50 μm. For example, the 1% flexural modulus (MD) of the polyolefin composition is greater than or equal to about 200 MPa to about 1,500 MPa, greater than or equal to about 225 MPa to about 1,500 MPa, greater than or equal to about 250 MPa to about 1,500 MPa, greater than or equal to about 275 MPa to about 1,500 MPa, about 300 MPa to about 1,500 MPa, about 300 MPa to about 1,200 MPa, about 300 MPa to about 1,000 MPa, and about 250 MPa to about 1,000 MPa. The pressure is measured at approximately 0 MPa to 1,000 MPa, approximately 300 MPa to 800 MPa, approximately 300 MPa to 600 MPa, approximately 300 MPa to 500 MPa, approximately 400 MPa to 1,200 MPa, approximately 400 MPa to 1,000 MPa, approximately 400 MPa to 800 MPa, or approximately 400 MPa to 600 MPa, at a thickness of approximately 50 μm in the layer (e.g., monolayer) containing the polyolefin composition. The 1% flexural modulus is determined according to the method provided below.

[0041] In one or more embodiments, the 1% flexural modulus TD (in the transverse direction) of the monolayer comprising the polyolefin composition is greater than 200 MPa, greater than 225 MPa, greater than 250 MPa, greater than 275 MPa, or greater than 300 MPa, for example from about 320 MPa, about 340 MPa, about 350 MPa, about 400 MPa, about 500 MPa, or about 600 MPa to about 700 MPa, about 800 MPa, about 900 MPa, about 1,000 MPa, about 1,200 MPa, about 1,500 MPa or greater, measured under conditions where the layer (e.g., monolayer) of the polyolefin composition has a thickness of about 50 μm. For example, the 1% flexural modulus TD of the polyolefin composition is about 250 MPa to about 1,500 MPa, about 250 MPa to about 1,200 MPa, about 250 MPa to about 1,000 MPa, about 250 MPa to about 800 MPa, about 250 MPa to about 600 MPa, about 250 MPa to about 500 MPa, about 340 MPa to about 1,500 MPa, about 340 MPa to about 1,200 MPa, and about 340 MPa. The pressure was measured at 0 MPa to about 1,000 MPa, about 340 MPa to about 800 MPa, about 340 MPa to about 600 MPa, about 340 MPa to about 500 MPa, about 400 MPa to about 1,200 MPa, about 400 MPa to about 1,000 MPa, about 400 MPa to about 800 MPa, or about 400 MPa to about 600 MPa, at a thickness of about 50 μm in the layer containing the polyolefin composition.

[0042] The 1% flexural modulus can be determined by the following equipment: a United Six (6) station, a 60-degree machine containing the following: a load frame test console containing an electrically driven crosshead mounted to provide horizontal movement. Six (6) individual load sensors are mounted opposite the crosshead. These load sensors are tension load sensors.

[0043] Units #1 and #3 have load cells ranging from 0 to 35 pounds. Unit #2 has a load cell ranging from 0 to 110 pounds. Each load cell is equipped with a set of pneumatic jaws. Each jaw has a face designed to form a linegrip. The jaw combines a standard flat rubber face with an opposing face that protrudes from it in a semi-circular metal shape. Units #1 and #3 have 1 1 / 4" wide jaws, and Unit #2 has 2 1 / 4" wide jaws.

[0044] In one or more embodiments, the 1% secant modulus MD (longitudinal) of the monolayer comprising the polyolefin composition is greater than 200 MPa, greater than 225 MPa, greater than 250 MPa, or greater than 275 MPa, for example about 200 MPa, 300 MPa, about 400 MPa, about 500 MPa, or about 600 MPa to about 700 MPa, about 800 MPa, about 900 MPa, about 1,000 MPa, about 1,200 MPa, about 1,500 MPa, or greater, measured under conditions where the layer (e.g., monolayer) of the polyolefin composition has a thickness of about 50 μm. For example, the 1% secant modulus (MD) of the polyolefin composition is greater than or equal to about 200 MPa to about 1,500 MPa, greater than or equal to about 225 MPa to about 1,500 MPa, greater than or equal to about 250 MPa to about 1,500 MPa, greater than or equal to about 275 MPa to about 1,500 MPa, about 300 MPa to about 1,500 MPa, about 300 MPa to about 1,200 MPa, about 300 MPa to about 1,000 MPa, and about 250 MPa. The pressure was measured at approximately 1,000 MPa, approximately 300 MPa to approximately 800 MPa, approximately 300 MPa to approximately 600 MPa, approximately 300 MPa to approximately 500 MPa, approximately 400 MPa to approximately 1,200 MPa, approximately 400 MPa to approximately 1,000 MPa, approximately 400 MPa to approximately 800 MPa, or approximately 400 MPa to approximately 600 MPa, at a thickness of approximately 50 μm in a layer (e.g., a monolayer) containing a polyolefin composition.

[0045] In one or more embodiments, the 1% secant modulus TD (transverse) of the monolayer comprising the polyolefin composition is greater than 200 MPa, greater than 225 MPa, greater than 250 MPa, greater than 275 MPa, or greater than 300 MPa, for example from about 320 MPa, about 340 MPa, about 350 MPa, about 400 MPa, about 500 MPa, or about 600 MPa to about 700 MPa, about 800 MPa, about 900 MPa, about 1,000 MPa, about 1,200 MPa, about 1,500 MPa or greater, measured under conditions where the layer (e.g., monolayer) of the polyolefin composition has a thickness of about 50 μm. For example, the 1% secant modulus TD of the polyolefin composition is about 250 MPa to about 1,500 MPa, about 250 MPa to about 1,200 MPa, about 250 MPa to about 1,000 MPa, about 250 MPa to about 800 MPa, about 250 MPa to about 600 MPa, about 250 MPa to about 500 MPa, about 340 MPa to about 1,500 MPa, about 340 MPa to about 1,200 MPa, about 340 MPa to about 1,200 MPa, about 340 MPa to about 1,5 ... The secant modulus (M), measured at approximately 50 μm, is determined at approximately 1,000 MPa, approximately 340 MPa to approximately 800 MPa, approximately 340 MPa to approximately 600 MPa, approximately 340 MPa to approximately 500 MPa, approximately 400 MPa to approximately 1,200 MPa, approximately 400 MPa to approximately 1,000 MPa, approximately 400 MPa to approximately 800 MPa, or approximately 400 MPa to approximately 600 MPa, in layers (e.g., monolayers) of the polyolefin composition. The 1% secant modulus (M), reported in MPa, can be measured according to ASTM D-882-10.

[0046] Figure 1 This is a non-limiting example of a multilayer roofing membrane 102, which, when applied to a roof 106, is connected to an insulation 104. The illustrated roofing membrane 102 comprises three layers: a first TPO film 108, a scrim 110, and a second TPO film 112. The scrim 110 provides mechanical strength to the multilayer roofing membrane 102. In the illustrated example, the first TPO film 108 faces outwards and preferably includes additives to make it reflective to reduce heat absorption. Furthermore, the second TPO film 112 is located at or closest to the insulation 104 and preferably includes additives to make it darker to improve insulation. In this non-limiting example, the first TPO film 108 and / or the second TPO film 112 can be the TPO film described herein, comprising a propylene-based polymer, a thermoplastic resin, at least one flame retardant, and at least one UV stabilizer.

[0047] The roofing membranes (single or multiple layers) described herein can be secured to the base roof by any means known in the art, such as by adhesive materials, ballast materials, spot bonding, or mechanical spot fastening. For example, the membrane can be installed and fastened through the membrane and into the roof panel using mechanical fasteners and plates placed along the edge sheets. Adjacent sheets of the flexible membrane are overlapped to cover the fasteners and plates, and are preferably joined together, for example by hot air welding. The membrane can also be completely adhered to or self-adheded to the insulation or deck material using adhesives. The insulation is typically secured to the deck with mechanical fasteners, while the flexible membrane is adhered to the insulation.

[0048] The roof membrane can be reinforced with any type of sparse fabric, including but not limited to polyester, glass fiber, glass fiber reinforced polyester, polypropylene, woven or nonwoven fabrics (e.g., nylon), or combinations thereof. Preferred sparse fabrics are glass fiber and / or polyester.

[0049] Furthermore, the surface layers of the top and / or bottom of the membrane can have textures with various patterns. Textures increase the surface area of ​​the membrane, reduce glare, and make the membrane surface less slippery. Examples of texture designs include, but are not limited to, polyhedra with polygonal bases and triangular faces intersecting at common vertices, such as the base of a pyramid; conical structures with circular or elliptical configurations; and random patterned configurations.

[0050] The TPO membrane described herein 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). The multilayer roofing membrane 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).

[0051] Propylene-based elastomers

[0052] The compositions described herein comprise one or more propylene-based elastomers (“PBE”). PBE contains propylene and about 5 to about 30 wt% of one or more ingredients selected from ethylene and / or C4-C4. 12 A comonomer of an α-olefin and optionally one or more dienes. For example, the comonomer unit may be derived from ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, or decene. In some embodiments, the comonomer is ethylene. In some embodiments, the propylene-based elastomer component consists essentially of propylene and ethylene-derived units, or only of propylene and ethylene-derived units. Some embodiments disclosed below are discussed with reference to ethylene as the comonomer, but these embodiments are equally applicable to other copolymers having other higher α-olefin comonomers. In this respect, the copolymer may be simply referred to as PBE, with ethylene as the α-olefin.

[0053] Although the molecular weight of PBE is affected by reactor conditions including temperature, monomer concentration and pressure, catalyst system, and the presence of chain terminators or chain transfer agents, the Mw of homopolymer and copolymer products can be approximately 1,000 to approximately 2,000,000 g / mol, or approximately 30,000 to approximately 600,000 g / mol, or approximately 100,000 to approximately 600,000 g / mol, for example approximately 200,000 g / mol to approximately 600,000 g / mol, for example approximately 300,000 g / mol to approximately 600,000 g / mol, for example approximately 400,000 g / mol to approximately 600,000 g / mol, for example approximately 500,000 g / mol to approximately 600,000 g / mol, for example approximately 500,000 g / mol to approximately 550,000 g / mol, as determined by GPC (described below).

[0054] The melt flow rate (MFR) of PBE can be at least 0.01 dg / min (e.g., 0.1 to 50 dg / min, 0.2 to 30 dg / min, 0.1 to 1.5 dg / min, 0.15 to 1.0 dg / min, 0.15 to 0.8 dg / min, 0.15 to 0.5 dg / min) (ASTM 1238, 2.16 kg, 230 °C). Alternatively, the melt flow rate (MFR) of PBE can be at least 0.01 dg / min (e.g., 0.1 to 50 dg / min, 1 to 10 dg / min). Alternatively, PBE can have a melt flow rate (MFR) of less than 0.5 dg / min.

[0055] PBE can be a homopolymer or a copolymer. In at least one embodiment, the content of one or more comonomers of PBE is up to 50 mol%, for example, 0.01 to 40 mol%, for example, 1 to 30 mol%, for example, 5 to 20 mol%.

[0056] In some embodiments, PBE is a propylene-ethylene copolymer having 1 to 35 wt% ethylene (e.g., 5 wt% to 30 wt%, e.g., 5 wt% to 25 wt%) and 99 wt% to 65 wt% propylene (e.g., 95 wt% to 70 wt%, e.g., 95 wt% to 75 wt%), with optionally up to 10 wt% (e.g., 0.00001 wt% to 6.0 wt%, e.g., from 0.002 wt% to 5.0 wt%, e.g., 0.003 wt% to 0.2 wt%) of one or more dienes, based on the weight of the copolymer. Non-limiting examples of useful dienes include cyclopentadiene, norbornene, dicyclopentadiene, 5-ethide-2-norbornene (“ENB”), 5-vinyl-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, 1-methyl-1,9-decadiene, and 9-methyl-1,9-decadiene.

[0057] In some embodiments described herein, a multi-peaked polyolefin composition is produced, comprising a first polyolefin component and at least one other polyolefin component that is molecularly different from the first polyolefin component, for example, such that the GPC trace has more than one peak or inflection point.

[0058] When used to describe polymers or polymer compositions, the term "multimodal" refers to a "multimodal molecular weight distribution," which is understood to mean that a gel permeation chromatography (GPC) trace, plotted as the relationship between absorbance and retention time (seconds), has more than one peak or at least one inflection point. An "inflection point" is the point where the sign of the second derivative of the curve changes (e.g., from negative to positive or vice versa). For example, a polyolefin composition comprising a first low molecular weight polymer component (e.g., a polymer having a Mw of 100,000 g / mol) and a second high molecular weight polymer component (e.g., a polymer having a Mw of 300,000 g / mol) is considered a "bimodal" polyolefin composition. For example, the Mw of the polymers or polymer compositions differs from each other by at least 10%, for example, at least 20%, for example, at least 50%, for example, at least 100%, for example, at least 200%. Similarly, in at least one embodiment, the Mw of the polymer or polymer composition differs from each other by 10% to 10,000%, for example by 20% to 1,000%, for example by 50% to 500%, for example by at least 100% to 400%, for example by 200% to 300%.

[0059] Unless otherwise stated, the molecular weight moments, i.e., weight-average molecular weight (Mw), number-average molecular weight (Mn), and z-average molecular weight (Mz), were determined by gel permeation chromatography (GPC), as described in Macromolecules, 2001, Vol. 34, No. 19, p. 6812, which is incorporated herein by reference in its entirety. This included the use of a high-temperature size exclusion chromatograph (SEC, Waters Alliance 2000) equipped with a differential refractive index detector (DRI) featuring three PolymerLaboratories PLgel 10 mm Mixed-B columns. The instrument used a 1.0 cm... 3 The operation was conducted at a flow rate of [flow rate] / min and an injection volume of 300 μL. Various transfer lines, columns, and differential refractometers (DRI detectors) were installed in an oven maintained at 145 °C. Polymer solutions were prepared by heating 0.75 to 1.5 mg / mL of polymer in filtered 1,2,4-trichlorobenzene (TCB) containing ~1000 ppm butylated hydroxytoluene (BHT) at 160 °C for 2 hours with continuous stirring. The polymer-containing solution sample was injected into the GPC and eluted with filtered 1,2,4-trichlorobenzene (TCB) containing ~1000 ppm BHT. The separation efficiency of the column set was calibrated using a series of narrow MWD polystyrene standards reflecting the expected Mw range of the analyte and the exclusion limits of the column set. Calibration curves were generated using seventeen individual polystyrene standards with peak molecular weights (Mp) ranging from ~580 to 10,000,000, obtained from Polymer Laboratories (Amherst, Mass.). Before determining the retention volume of each polystyrene standard, the flow rate for each run was calibrated to provide a common peak position for the flow marker (as the positive injection peak). The flow marker peak position was used to correct the flow rate when analyzing samples. The calibration curve (log(Mp) versus retention volume) was generated by recording the retention volume at the peak in the DRI signal for each PS standard and fitting this dataset to a second-order polynomial. The equivalent polyethylene molecular weight was determined using the Mark-Howwink coefficient shown in Table A.

[0060]

[0061] In at least one embodiment, the homopolymer and copolymer PBE can have multiple peaks, such as bimodal, Mw / Mn.

[0062] In some embodiments, PBE is a regular polymer, such as an isotactic or highly isotactic polymer. In some embodiments, PBE is isotactic polypropylene, such as highly isotactic polypropylene.

[0063] The term "isotactic polypropylene" (iPP) is defined as having at least 10% or more isotactic pentads. The term "highly isotactic polypropylene" is defined as having 50% or more isotactic pentads. The term "syndiotactic polypropylene" is defined as having 10% or more syndiotactic pentads. The term "random copolymer polypropylene" (RCP), also known as propylene random copolymer, is defined as a copolymer of propylene with 1 to 10 wt% of an olefin selected from ethylene and C4 to C8 α-olefins. For example, an isotactic polymer (e.g., iPP) has at least 20% (e.g., at least 30%, e.g., at least 40%) isotactic pentads. If a polyolefin has less than 10% isotactic and syndiotactic pentads, the polyolefin is "random," also known as "amorphous."

[0064] The microstructure of polypropylene is achieved through 13 C-NMR spectroscopy determination, including the concentrations of isotactic and syndiotactic binary groups ([m] and [r]), tripartite groups ([mm] and [rr]), and pentatomic groups ([mmmm] and [rrrr]). The names "m" or "r" describe the stereochemistry of the consecutive propene group pairs; "m" indicates meso, and "r" indicates racemic. The sample was dissolved in d2-1,1,2,2-tetrachloroethane, and the spectra were recorded at 125 °C using an NMR spectrometer at 100 MHz (or higher). The polymer resonance peak is referred to as mmmm = 21.8 ppm. (FA Bovey in *Polymer Conformation and Conformation* (Academic Press, New York, 1969) and J. Randall in *Polymer Sequence Determination*,) 13 The calculations involved in characterizing polymers by NMR were disclosed in the C-NMR METHOD (Academic Press, New York, 1977).

[0065] PBE may contain at least about 5 wt%, at least about 7 wt%, at least about 9 wt%, at least about 10 wt%, at least about 12 wt%, at least about 13 wt%, at least about 14 wt%, at least about 15 wt%, or at least about 16 wt% of α-olefin derivatizing units, based on the total weight of PBE. PBE may include up to about 30 wt%, up to about 25 wt%, up to about 22 wt%, up to about 20 wt%, up to about 19 wt%, up to about 18 wt%, or up to about 17 wt% of α-olefin derivatizing units, based on the total weight of PBE. In some embodiments, PBE may contain about 5 to about 30 wt%, about 6 to about 25 wt%, about 7 wt% to about 20 wt%, about 10 to about 19 wt%, about 12 wt% to about 19 wt%, or about 15 wt% to about 18 wt%, or about 16 wt% to about 18 wt% of α-olefin derivatizing units, based on the total weight of PBE.

[0066] PBE may contain at least about 70 wt%, at least about 75 wt%, at least about 78 wt%, at least about 80 wt%, at least about 81 wt%, at least about 82 wt%, or at least 83 wt% of propylene-derived units, based on the total weight of PBE. PBE may contain at most about 95 wt%, at most about 93 wt%, at most about 91 wt%, at most about 90 wt%, at most about 88 wt%, at most about 87 wt%, at most about 86 wt%, at most about 85 wt%, or at most about 84 wt% of propylene-derived units, based on the total weight of PBE.

[0067] PBE can be characterized by its melting point (Tm), which can be determined by differential scanning calorimetry (DSC). Using the DSC method described herein, the melting point is the temperature recorded corresponding to the maximum endothermic reaction within the sample's melting temperature range when the sample is continuously heated at a programmed rate. When a single melting peak is observed, that peak is considered the "melting point." When multiple peaks (e.g., a main peak and secondary peaks) are observed, the melting point is considered to be the highest of these peaks. It is worth noting that due to the low crystallinity of many PBEs, the melting point peak may be at low temperatures and relatively flat, making it difficult to determine the precise peak location. In this specification, a "peak" is defined as the point on which the general slope of a DSC curve (heat flow versus temperature) changes from positive to negative, forming a maximum value without baseline shift, where the DSC curve is plotted such that an endothermic reaction will appear as a positive peak.

[0068] The Tm (first melting point) of PBE (determined by DSC) can be less than about 120°C, less than about 115°C, less than about 110°C, less than about 105°C, less than about 100°C, less than about 90°C, less than about 80°C, less than about 70°C, less than about 65°C, or less than about 60°C. In some embodiments, PBE can have a Tm of about 20°C to about 110°C, about 30°C to about 110°C, about 40°C to about 110°C, or about 50°C to about 105°C. In some embodiments, PBE can have a Tm of about 40°C to about 70°C, or about 45°C to about 65°C, or about 50°C to about 60°C. In some embodiments, PBE can have a Tm of about 80°C to about 110°C, or about 85°C to about 110°C, or about 90°C to about 105°C.

[0069] As used in this application, the DSC procedure for determining Tm is as follows: The polymer is pressed in a hot press at a temperature of about 200°C to about 230°C, and the resulting polymer sheet is annealed in air at an ambient temperature of about 23.5°C to cool. About 6 to 10 mg of polymer sheet is cut off using a die. This 6 to 10 mg sample is annealed at room temperature (about 23.5°C) for about 80 to 100 hours. At the end of this stage, the sample is placed in a DSC (Perkin Elmer Pyris One thermal analysis system) and cooled to about -30°C to about -50°C and held at -50°C for 10 minutes. The sample is then heated at a rate of 10°C / min to reach a final temperature of about 200°C. The sample is held at 200°C for 5 minutes. This is the first melting. A second thermal cycle is then performed (to obtain a second melting), in which the sample is cooled to about -30°C to about -50°C and held at -50°C for 10 minutes, and then heated at a rate of 10°C / min to reach a final temperature of about 200°C. Unless otherwise stated, Tm as used in this article refers to the first melting point.

[0070] PBE can be characterized by its crystallinity percentage, determined by X-ray diffraction, also known as wide-angle X-ray scattering (WAXS). PBE can have a crystallinity percentage of at least about 0.5, at least about 1.0, or at least about 1.5. PBE can also be characterized by a crystallinity percentage of less than about 2.0, less than about 2.5, or less than about 3.0. For polyethylene and polyethylene copolymers, WAXS can be used to probe the semi-crystalline nature of these materials. Polyethylene forms inherently orthorhombic crystals with specific unit cell sizes. And α = β = γ = 90°. Polyethylene crystal cells are then stacked together to form microcrystals, the planes of which then diffract the incident X-rays. The crystal planes that diffract the X-rays are characterized by their Miller indices (hkl), and for polyethylene, the three main diffraction planes that appear as peaks in the WAXS pattern are (110), (200), and (020). The overall degree of crystallinity of these materials is calculated by dividing the area under each (hkl) value by the area of ​​the total WAXS trace. The minimum degree of crystallinity required to observe crystals using WAXS technology is approximately 0.5 vol%.

[0071] The comonomer content and sequence distribution of polymers can be used 13 C-NMR measurements. Comonomer content in discrete molecular weight ranges can be measured using methods well-known to those skilled in the art, including Fourier transform infrared spectroscopy (FTIR) combined with GPC, as described in Wheeler and Willis, Applied Spectroscopy, 1993, Vol. 47, pp. 1128-1130. For propylene-ethylene copolymers containing more than 75 wt% propylene, the comonomer content (ethylene content) of this polymer can be measured as follows: a thin, uniform film is pressed at approximately 150°C or higher and mounted on a PerkinElmer PE 1760 infrared spectrophotometer. The sample is recorded from 600 cm⁻¹. -1 Up to 4000cm -1 The complete spectrum of ethylene and the monomer weight percentage can be calculated using the following formula: Ethylene wt% = 82.585 - 111.987X + 30.045X 2 Where X is 1155cm -1 Peak height is 722cm -1 Or 732cm -1 The ratio of peak heights (whichever is higher). For propylene-ethylene copolymers with 75 wt% or less propylene content, the comonomer (ethylene) content can be measured using the procedure described in Wheeler and Willis. Refer to US Patent 6,525,157, which contains further details regarding GPC measurements, determination of ethylene content by NMR, and DSC measurements.

[0072] PBE can have approximately 0.84 g / cm³. 3 Approximately 0.92 g / cm³ 3 Approximately 0.85 g / cm³ 3 Approximately 0.91 g / cm³ 3 For example, approximately 0.85 g / cm³ 3 Approximately 0.87 g / cm³ 3 or approximately 0.87 g / cm³ 3 Approximately 0.9 g / cm³3 The density, measured at room temperature according to ASTM D-1505 test method, where the desired range may include any lower limit to any upper limit.

[0073] PBE may have a melt index (MI) of less than or equal to about 10 g / 10 min, less than or equal to about 8.0 g / 10 min (ASTM D-1238, 2.16 kg @ 190 °C), less than or equal to about 5.0 g / 10 min, or less than or equal to about 3.0 g / 10 min, or less than or equal to about 2.0 g / 10 min. In some embodiments, PBE may have an MI of about 0.5 to about 3.0 g / 10 min, or 0.75 to about 2.0 g / 10 min, wherein the desired range may include a range from any lower limit to any upper limit.

[0074] The melt flow rate (MFR) of PBE, measured according to ASTM D-1238 (2.16 kg weight @ 230 °C), is greater than approximately 0.05 g / 10 min, greater than approximately 0.1 g / 10 min, greater than approximately 0.15 g / 10 min, greater than approximately 0.2 g / 10 min, greater than approximately 0.25 g / 10 min, greater than approximately 0.3 g / 10 min, greater than approximately 0.35 g / 10 min, or greater than approximately 0.4 g / 10 min. PBE can have an MFR less than approximately 10 g / 10 min, less than approximately 4 g / 10 min, less than approximately 3 g / 10 min, less than approximately 2.5 g / 10 min, less than approximately 2 g / 10 min, less than approximately 1.5 g / 10 min, less than approximately 1 g / 10 min, or less than approximately 0.5 g / 10 min. In some embodiments, the PBE may have an MFR of about 0.05 to about 10 g / 10 min, about 0.1 to about 3 g / 10 min, about 0.1 to about 2.5 g / 10 min, about 0.15 to about 2 g / 10 min, about 0.2 to about 1 g / 10 min, or about 0.4 to about 0.6 g / 10 min, wherein the desired range may include a range from any lower limit to any upper limit.

[0075] PBE may have a g′ index value of 0.95 or greater, or at least 0.97, or at least 0.99, where g′ is measured at the polymer's Mw using the intrinsic viscosity of isotactic polypropylene as a baseline. For the purposes of this application, the g′ index is defined as:

[0076] g′=η b η l

[0077] Where η bη is the intrinsic viscosity of the polymer, and ηl is the intrinsic viscosity of a linear polymer having the same viscosity-average molecular weight (Mv) as the polymer. ηl = KMvα, where K and α are measurements of the linear polymer and should be obtained on the same instrument used for measuring the g′ index.

[0078] Optionally, PBE may include long-chain branching. The g′vis or branching index value of branched PBE is less than 1. The g′vis or branching index can be measured using gel permeation chromatography.

[0079] Mw, Mn, Mz, number of carbon atoms and g′ vis Determination was performed using volumetric exclusion chromatography (from Waters Corporation or Polymer Laboratories) equipped with three online detectors: a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R.R. Chance, and W.W. Graessley, Macromolecules, Vol. 34, No. 19, pp. 6812-6820, (2001) and its references. Three Polymer Laboratories PLgel 10 mm Mixed-B LS columns were used. The nominal flow rate was 0.5 cm⁻¹. 3 The injection rate was 300 μL / min. Various transfer lines, columns, and differential refractometers (DRI detectors) were contained in an oven maintained at 145 °C. The experimental solvent was prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 L of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. The TCB was then degassed using an online degasser before entering the size exclusion chromatograph. The polymer solution was prepared by placing the dried polymer in a glass container, adding the required amount of TCB, and then heating the mixture at 160 °C with continuous stirring for approximately 2 hours. All quantities were measured by gravimetric analysis. The TCB density, expressed as mass / volume for polymer concentration, was 1.463 g / ml at room temperature and 1.324 g / ml at 145 °C. Injection concentrations ranged from 0.75 to 2.0 mg / ml, with lower concentrations used for higher molecular weight samples. Before testing each sample, the DRI detector and syringe were purged. The flow rate in the device was then increased to 0.5 mL / min, and the DRI was allowed to stabilize for 8 to 9 hours before injecting the first sample. The LS laser was turned on 1 to 1.5 hours before testing the sample. The concentration c at each point in the chromatogram was calculated by subtracting the baseline DRI signal I. DRI The following formula is used to calculate:

[0080] c = K DRI I DRI / (dn / dc)

[0081] Where K DRI This is a constant determined by DRI calibration, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145°C and λ = 690 nm is n = 1.500. For the purposes of this invention and its claims, (dn / dc) = 0.104 for propylene polymers, 0.098 for butene polymers, and otherwise 0.1. Throughout the description of the SEC method, the units of the parameters are concentrations expressed in g / cm³. 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity is expressed in dL / g.

[0082] The LS detector is a Wyatt Technology High Temperature Micro-DAWN. The molecular weight M at each point in the chromatogram was determined by analyzing the LS output using the Zimm static light scattering model (MB Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971).

[0083]

[0084] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration determined by DRI analysis, A2 is the second virial coefficient [for the purposes of this invention, A2 = 0.0006 for propylene polymers, 0.0015 for butene polymers, and 0.001 otherwise], (dn / dc) = 0.104 for propylene polymers, 0.098 for butene polymers, and 0.1 otherwise, P(θ) is the shape factor of the monodisperse random coil, and K... o These are the system's optical constants:

[0085]

[0086] Where N A dn / dc is the Avogadro number, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145℃ and λ=690nm is n=1.500.

[0087] The high-temperature Viscotek Corporation viscometer features four capillaries arranged in a Wheatstone bridge configuration, with two pressure sensors for determining specific viscosity. One sensor measures the total pressure drop across the entire detector, while the other, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is... s The intrinsic viscosity [η] at each point in the chromatogram is calculated from their outputs.

[0088] □ηs=c[η]+0.3(c[η]) 2

[0089] Where c is the concentration and is determined by the DRI output.

[0090] Branching index (g′) vis The output calculated using the SEC-DRI-LS-VIS method is as follows. The average intrinsic viscosity of the sample [η] avg Calculated using the following formula:

[0091]

[0092] In chromatographic segment i, the values ​​are accumulated between the integration limits. Branching index g′ vis Defined as:

[0093]

[0094] Specifically, for the present invention and its claims, α = 0.695 and k = 0.000579 for linear ethylene polymers, α = 0.705 and k = 0.000262 for linear propylene polymers, and α = 0.695 and k = 0.000181 for linear butene polymers. v It is the viscosity-average molecular weight based on the molecular weight determined by LS analysis.

[0095] In one embodiment, branched PBE can be prepared using a method for long-chain branching of propylene-based polymers, whereby the polymer is made to undergo peroxide macroradical chain scission by using a radical scavenger containing a functional nitryl group. It is believed, without being bound by theory, that peroxides initiate the grafting of C=C functional groups onto the propylene backbone, followed by oligomerization of the polymer-bound monomers. The nitryl-based radical scavenger can participate in the abstraction of hydrogen atoms from the propylene backbone, followed by oligomerization to produce the branched propylene-based polymer. Formulations containing a peroxide and a small amount of radical scavenger (characterized by at least one nitro oxygen radical or capable of generating at least one nitro oxygen radical) can produce a significant level of long-chain branching while minimizing the reduction in molecular weight when melt-mixed with the propylene-based polymer and with at least one unsaturated bond capable of withstanding radical addition reactions.

[0096] This method can be implemented by mixing PBE with a radical generator and an auxiliary agent via a melt blending process. Optionally, the method may also include a radical scavenger. The branched PBE formulation is prepared in a 70cc capacity brabender batch mixer at 100 rpm and a metal equipment temperature of 150°C. At time zero, the PBE is loaded into the mixer. After mixing for approximately 2–3 minutes, the radical scavenger is optionally added, followed by the auxiliary agent and the radical initiator. In some embodiments, the radical initiator is added before the auxiliary agent. In another embodiment, the radical initiator and the auxiliary agent are added simultaneously. The mixture is then mixed for another 4 minutes.

[0097] In one embodiment, about 95 to 99 wt% of PBE is mixed with about 0.3 to 0.6 wt% of an adjuvant and about 0.5 to 1.5 wt% of a free radical initiator. In embodiments using a free radical scavenger, about 0.5 to 1 wt% of the free radical scavenger may be added to the mixture.

[0098] Suitable radical scavengers comprise at least one nitro oxygen radical and at least one unsaturated bond capable of radical reaction. Such radical scavengers include 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxy, (AOTEMPO).

[0099] Suitable free radical initiators can be selected from organic peroxides, organic peresters, and azo compounds. Examples of such compounds include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyn-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butylperphenylacetate, tert-butyl perisobutyrate, tert-butyl peroctanoate, tert-butyl perpentanoate, cumyl perpentanoate, and tert-butyl perethylacetate, azoisobutyronitrile, and dimethyl azoisobutyrate. Suitable organic peroxides for crosslinking the polyethylene / NFP blends according to the invention are commercially available under the trade name LUPEROX (preferably 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, produced by Arkema under the trade name...). (101 for sale).

[0100] Examples of adjuvants include triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, sulfur, N-phenylbismaleimide, zinc diacrylate, zinc dimethacrylate, divinylbenzene, 1,2-polybutadiene, trimethylolpropane trimethacrylate, butanediol diacrylate, trifunctional acrylates, dipentaerythritol pentaacrylate, polyfunctional acrylates, retarded cyclohexanedimethyl diacrylate, polyfunctional methacrylates, metal salts of acrylic acid and methacrylate, and oximes for, for example, quinone dioximes.

[0101] In another embodiment, branched PBE can be prepared by copolymerizing propylene with a limited amount of one or more comonomers selected from ethylene, C4-C20 α-olefins, and polyenes. For example, propylene, ethylene, and 5-vinyl-2-norbornene (VNB) can be copolymerized to form a PBE-VNB terpolymer. The formation of the PBE-VNB polymer is disclosed in U.S. Patent Application No. US2005 / 0107534.

[0102] PBE can have a Shore D hardness (ASTM D2240) of less than about 50, less than about 45, less than about 40, less than about 35, or less than about 20.

[0103] PBE may have a Shore A hardness (ASTM D2240) of less than about 100, less than about 95, less than about 90, less than about 85, less than about 80, less than about 75, or less than 70. In some embodiments, PBE may have a Shore A hardness of about 10 to about 100, about 15 to about 90, about 20 to about 80, or about 30 to about 70, wherein the desired range may include a range from any lower limit to any upper limit.

[0104] In some embodiments, PBE is a propylene-ethylene copolymer having at least four, or at least five, or at least six, or at least seven, or at least eight, or all nine of the following properties: (i) about 9 to about 25 wt%, or about 12 to about 20 wt% ethylene-derived units, based on the weight of PBE; (ii) Tm of 80 to about 110 °C, or about 85 to about 110 °C, or about 90 to about 105 °C; (iii) Hf less than about 75 J / g, or less than 50 J / g, or less than 30 J / g, or about 1.0 to about 15 J / g, or about 3.0 to about 10 J / g; (iv) MI of about 0.5 to about 3.0 g / 10 min or about 0.75 to about 2.0 g / 10 min; (v) about 0.05 to about 10 g / 10 min, or 0.1 to about 3 g / 10 min. (vi) Mw is about 500,000 to about 600,000 g / mol, or about 500,000 to about 550,000 g / mol, or about 510,000 to about 600,000 g / mol, or about 525,000 to about 550,000 g / mol; (vii) Mn is about 50,000 to about 500,000 g / mol, or about 150,000 to about 350,000 g / mol, or about 200,000 to about 250,000 g / mol; (viii) MWD is about 1.0 to about 5, or about 1.5 to about 4, or about 1.8 to about 3; and / or (ix) Shore D hardness is less than 30, or less than 25, or less than 20.

[0105] Optionally, one or more graft monomers may be used to graft (i.e., “functionalize”) PBE. As used herein, the term “grafting” refers to the covalent bonding of the graft monomer to the polymer chain of the propylene-based polymer. The graft monomer may be or include at least one olefinically unsaturated carboxylic acid or acid derivative, such as anhydrides, esters, salts, amides, imides, acrylates, etc. Exemplary graft monomers include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesocarboxylic acid, maleic anhydride, 4-methylcyclohexene-1,2-dicarboxylic anhydride, bicyclo(2.2.2)octene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-oxa-1,3-diketospiro(4.4)nonene, bicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, norbornene-2,3-dicarboxylic anhydride, nadic anhydride, methylnadic anhydride, himic anhydride, methyl norbornene, and 5-methylbicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride. Other suitable graft monomers include methyl acrylate and higher alkyl acrylates, methyl methacrylate and higher alkyl methacrylates, acrylic acid, methacrylic acid, hydroxymethyl methacrylate, hydroxyethyl methacrylate and higher hydroxyalkyl methacrylates, and glycidyl methacrylate. Maleic anhydride is an example graft monomer. In embodiments where the graft monomer is maleic anhydride, the concentration of maleic anhydride in the graft polymer can be from about 1 wt% to about 6 wt%, at least about 0.5 wt%, or at least about 1.5 wt%.

[0106] Other suitable graft monomers include polystyrene. The PBE-g-PS described herein can be prepared via in-situ reactive extrusion (e.g., polymerization of styrene monomers and grafting of PBE macromolecular chains in a twin-screw extruder). Polystyrene is grafted onto PBE (e.g., VISTAMAXX). TM The main chain. A schematic diagram of the grafting reaction and polymerization of styrene monomers during the reaction process is shown below:

[0107]

[0108] Typically, in-situ reactive extrusion involves heating and extruding propylene-based elastomers (e.g., VISTAMAXX). TMThe polymerization is carried out using a mixture of styrene monomer and initiator (e.g., dicumyl peroxide (DCP)). To improve the distribution of styrene monomer throughout the propylene-based polymer, the propylene-based elastomer (typically in granular or flake form) is immersed in a mixture containing styrene monomer and initiator. Immersion can be carried out for about 1 hour to about 24 hours or longer (or about 1 hour to about 12 hours, or about 6 hours to about 18 hours, or about 8 hours to about 24 hours) at a temperature below which styrene polymerization occurs (preferably below about 50°C, or from room temperature to about 50°C).

[0109] The amount of styrene monomer in in-situ reactive extrusion should be determined based on the amount of styrene required in the final PBE-g-PS product. The amount of initiator is preferably greater than the amount of styrene required for polymerization, but excessive amounts should be avoided to prevent a large amount of initiator remaining in the PBE-g-PS product.

[0110] In-situ reactive extrusion can be performed at temperatures ranging from about 150°C to about 250°C (or from about 150°C to about 200°C, or from about 150°C to about 180°C).

[0111] The propylene-based polymer used to produce PBE-g-PS is preferably a propylene-based elastomer having 70 wt% to 95 wt% propylene-derived units and 5 wt% to 30 wt% C2-C6 α-olefin (not propylene)-derived units, and having a melting temperature of less than about 120°C and a heat of fusion of less than about 75 J / g. The C2-C6 α-olefin (not propylene) is preferably at least one selected from ethylene, isobutene, 1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 1-hexene. More preferably, the C2-C6 α-olefin is ethylene.

[0112] For example, the propylene-based polymer used to produce PBE-g-PS can be VISTAMAXX. TM 3588 polymer (8 g / 10 min MRF, 4 wt% C2) or VISTAMAXX TM 6102 polymer (3 g / 10 min MRF, 16 wt% C2) (two propylene-based copolymers, available from ExxonMobil Chemical Company).

[0113] At 180°C, the PBE-g-PS described in this application can have a range from greater than 100 Pa·s to less than 8 × 10⁻⁶ Pa·s. 4 Tensile viscosity in Pa·s. For example, when using Vistamax... TM When used in PBE, VISTAMAXX-g-PS can have a range from greater than 300 Pa·s to less than 5 × 10⁻⁶ Pa·s. 5Tensile viscosity in Pa·s.

[0114] The MFR (230°C, 2.16 kg) for the production of propylene-based polymers for PBE-g-PS can be from about 0.1 g / 10 min to about 100 g / 10 min (or from about 1 g / 10 min to about 50 g / 10 min, or from about 2 g / 10 min to about 30 g / 10 min, or from about 3 g / 10 min to about 20 g / 10 min).

[0115] The polystyrene content of PBE-g-PS can be from about 1 wt% to about 50 wt% (or from about 1 wt% to about 20 wt%, or from about 5 wt% to about 25 wt%, or from about 10 wt% to about 30 wt%, or from about 20 wt% to about 40 wt%), based on the total weight of the grafted polymer.

[0116] The Mw of PBE-g-PS can be from about 100,000 g / mol to about 500,000 g / mol (or from about 100,000 g / mol to about 250,000 g / mol, or from about 150,000 g / mol to about 350,000 g / mol, or from about 250,000 g / mol to about 500,000 g / mol).

[0117] The Mn of PBE-g-PS can be from about 5,000 g / mol to about 50,000 g / mol (or from about 5,000 g / mol to about 25,000 g / mol, or from about 15,000 g / mol to about 30,000 g / mol, or from about 25,000 g / mol to about 50,000 g / mol).

[0118] The MWD of PBE-g-PS can be from about 3 to about 20 (or from about 3 g / mol to about 10 g / mol, or from about 5 g / mol to about 18 g / mol, or from about 10 g / mol to about 30 g / mol).

[0119] The density of PBE-g-PS at room temperature is approximately 0.85 g / cm³. 3 To approximately 1.0 g / cm 3 (or approximately 0.86 g / cm³) 3 To approximately 0.95 g / cm 3 or approximately 0.88 g / cm³ 3 To approximately 0.90 g / cm 3 ).

[0120] In some embodiments, PBE is a reactor-grade or reactor-blended polymer as defined above. That is, in some embodiments, PBE is a reactor blend of a first polymer component and a second polymer component. Therefore, the comonomer content of PBE can be adjusted by adjusting the comonomer content of the first polymer component, adjusting the comonomer content of the second polymer component, and / or adjusting the ratio of the first polymer component to the second polymer component present in the PBE.

[0121] In embodiments where PBE is a blended polymer, the α-olefin content (“R1”) of the first polymer component can be greater than 5 wt%, greater than 7 wt%, greater than 10 wt%, greater than 12 wt%, greater than 15 wt%, or greater than 17 wt%, based on the total weight of the first polymer component. The α-olefin content of the first polymer component can be less than 30 wt%, less than 27 wt%, less than 25 wt%, less than 22 wt%, less than 20 wt%, or less than 19 wt%, based on the total weight of the first polymer component. In some embodiments, the α-olefin content of the first polymer component can be in the ranges of 5 wt% to 30 wt%, 7 wt% to 27 wt%, 10 wt% to 25 wt%, 12 wt% to 22 wt%, from 15 wt% to 20 wt%, or from 17 wt% to 19 wt%. For example, the first polymer component comprises, or is substantially composed of, propylene and ethylene-derived units.

[0122] In embodiments where PBE is a blended polymer, the α-olefin content (“R2”) of the second polymer component can be greater than 1.0 wt%, greater than 1.5 wt%, greater than 2.0 wt%, greater than 2.5 wt%, greater than 2.75 wt%, or greater than 3.0 wt% of α-olefin, based on the total weight of the second polymer component. The α-olefin content of the second polymer component can be less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, or less than 5 wt%, based on the total weight of the second polymer component. In some embodiments, the α-olefin content of the second polymer component can be from 1.0 wt% to 10 wt%, or from 1.5 wt% to 9 wt%, or from 2.0 wt% to 8 wt%, or from 2.5 wt% to 7 wt%, or from 2.75 wt% to 6 wt%, or from 3 wt% to 5 wt%. For example, the second polymer component can have propylene and ethylene-derived units, or consist essentially of propylene and ethylene-derived units.

[0123] In embodiments where PBE is a blended polymer, the PBE may comprise 1 to 25 wt% of a second polymer component, 3 to 20 wt% of a second polymer component, 5 to 18 wt% of a second polymer component, 7 to 15 wt% of a second polymer component, or 8 to 12 wt% of a second polymer component, based on the weight of the PBE, wherein the desired range may include any lower limit to any upper limit. The PBE may comprise 75 to 99 wt% of a first polymer component, 80 to 97 wt% of a first polymer component, 85 to 93 wt% of a first polymer component, or 82 to 92 wt% of a first polymer component, based on the weight of the PBE, wherein the desired range may include any lower limit to any upper limit.

[0124] PBE can be prepared under homogeneous conditions, such as continuous solution polymerization. Exemplary methods for preparing PBE can be found in U.S. Patent Application No. 2019 / 0177449, which is incorporated herein by reference.

[0125] For example, PBE is catalyzed by a quinolinyl diamino catalyst. Exemplary methods for preparing PBE using a quinolinyl diamino catalyst can be found in U.S. Patent Application No. 2018 / 0002352, which is incorporated herein by reference. In at least one embodiment, PBE is prepared using a quinolinyl diamino catalyst represented by formula (I) or formula (II):

[0126]

[0127] in:

[0128] M is a metal belonging to Groups 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;

[0129] J is a three-atom-length bridge between quinoline and amino nitrogen;

[0130] E is selected from carbon, silicon, or germanium;

[0131] X is an anion leaving group;

[0132] L is a neutral Lewis base;

[0133] R 1 and R 13 Independently selected from hydrocarbon groups, substituted hydrocarbon groups, and silyl groups;

[0134] R 2 To R 12 Independently selected from hydrogen, hydrocarbon, alkoxy, silyl, amino, aryloxy, substituted hydrocarbon, halogen, and phosphine;

[0135] n is 1 or 2;

[0136] m is 0, 1, or 2;

[0137] n+m is not greater than 4; and

[0138] Any two adjacent R groups (e.g., R 1 and R 2 R 2 and R 3 (e.g.) can be linked to form substituted or unsubstituted hydrocarbon groups or heterocyclic rings, wherein the ring has 5, 6, 7 or 8 ring atoms and wherein substituents on the ring can be linked to form additional rings; any two X groups can be linked together to form a dianionic group; any two L groups can be linked together to form a bidentate Lewis base; X groups can be linked with L groups to form a monoanionic bidentate group.

[0139] Non-limiting examples of quinolinyl diamide catalysts for chelating transition metal complexes include:

[0140] N-(2,6-diisopropylphenyl)-2-{2-[(o-tolylamino)methyl]naphth-1-yl}quinoline-8-amino(Hf(Me)2);

[0141] N-(2,6-diisopropylphenyl)-2-{2-[(2,6-dimethylphenylamino)methyl]naphth-1-yl}quinoline-8-amino(Hf(Me)2);

[0142] N-(2,6-diisopropylphenyl)-2-[3-(phenylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino (Hf(Me)2);

[0143] N-(2,6-diisopropylphenyl)-2-[3-(o-tolylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino(Hf(Me)2);

[0144] 2-(8-anilino-5,6,7,8-tetrahydronaphth-1-yl)-N-(2,6-diisopropylphenyl)quinoline-8-amino(Hf(Me)2);

[0145] N-(2,6-diisopropylphenyl)-2-{2-[(o-tolylamino)methyl]naphth-1-yl}quinoline-8-amino(Hf(Cl)2);

[0146] N-(2,6-diisopropylphenyl)-2-{2-[(2,6-dimethylphenylamino)methyl]naphth-1-yl}quinoline-8-amino(Hf(Cl)2);

[0147] N-(2,6-diisopropylphenyl)-2-[3-(phenylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino(Hf(Cl)2);

[0148] N-(2,6-diisopropylphenyl)-2-[3-(o-tolylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino(Hf(Cl)2);

[0149] 2-(8-anilino-5,6,7,8-tetrahydronaphth-1-yl)-N-(2,6-diisopropylphenyl)quinoline-8-amino(Hf(Cl)2);

[0150] N-(2,6-diisopropylphenyl)-2-{2-[(o-tolylamino)methyl]naphth-1-yl}quinoline-8-amino(Zr(Me)2);

[0151] N-(2,6-diisopropylphenyl)-2-{2-[(2,6-dimethylphenylamino)methyl]naphth-1-yl}quinoline-8-amino(Zr(Me)2);

[0152] N-(2,6-diisopropylphenyl)-2-[3-(phenylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino(Zr(Me)2);

[0153] N-(2,6-diisopropylphenyl)-2-[3-(o-tolylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino(Zr(Me)2);

[0154] 2-(8-anilino-5,6,7,8-tetrahydronaphth-1-yl)-N-(2,6-diisopropylphenyl)quinoline-8-amino(Zr(Me)2);

[0155] N-(2,6-diisopropylphenyl)-2-{2-[(o-tolylamino)methyl]naphth-1-yl}quinoline-8-amino(Zr(Cl)2);

[0156] N-(2,6-diisopropylphenyl)-2-{2-[(2,6-dimethylphenylamino)methyl]naphth-1-yl}quinoline-8-amino(Zr(Cl)2);

[0157] N-(2,6-diisopropylphenyl)-2-[3-(phenylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino (Zr(Cl)2);

[0158] N-(2,6-diisopropylphenyl)-2-[3-(o-tolylamino)-2,3-dihydro-1H-inden-4-yl]quinoline-8-amino(Zr(Cl)2);

[0159] 2-(8-anilino-5,6,7,8-tetrahydronaphth-1-yl)-N-(2,6-diisopropylphenyl)quinoline-8-amino(Zr(Cl)2); or

[0160] Its mixture.

[0161] In another example, PBE is prepared using a catalyst comprising a Group 4 bis(phenolate) complex. An exemplary method for preparing PBE using a catalyst comprising a Group 4 bis(phenolate) complex can be found in PCT patent application PCT / US2020 / 045819, which is incorporated herein by reference. In at least one embodiment, PBE is prepared using a catalyst comprising a Group 4 bis(phenolate) complex represented by formula (III).

[0162]

[0163] in:

[0164] M is a group 3-6 transition metal or a lanthanide element;

[0165] E and E′ are each independently O, S, or NR. 9 , where R 9 Independently hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituting hydrocarbon groups or groups containing heteroatoms;

[0166] Q is a group 14, 15, or 16 atom that forms a coordinate bond with metal M;

[0167] A 1 QA 1′ It is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which connects A through a 3-atom bridge. 2 Connect to A 2′ And Q is the central atom of the 3-atom bridge.

[0168] A 1 and A 1′ Independently C, N or C(R) 22 ), where R 22 Selected from hydrogen, C1-C 20 Hydrocarbon group, C1-C 20 Substitute hydrocarbon groups;

[0169] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms through a 2-atom bridge. 1 Aryl groups bonded to E;

[0170] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms through a 2-atom bridge. 1′ Aryl groups bonded to E;

[0171] A 1 The aryl group is linked to the E′ bond via a 2-atom bridge;

[0172] L is a neutral Lewis base;

[0173] X is an anionic ligand;

[0174] n is 1, 2, or 3;

[0175] m is 0, 1, or 2;

[0176] n+m is not greater than 4;

[0177] R 1 R 2 R 3 R 4 R 1′ R 2′ R 3′ and R 4′ Each independently is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituting hydrocarbon groups, heteroatoms, or heteroatom-containing groups, or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 1′ and R 2′ R 2′ and R 3′ R 3′ and R 4′ One or more of them can be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocyclic rings or unsubstituted heterocyclic rings, each having 5, 6, 7 or 8 ring atoms, and the substituents on the rings can be linked to form additional rings;

[0178] Any two L groups can be linked together to form a bidentate Lewis base;

[0179] The X group can be linked with the L group to form a monoanionic bidentate group;

[0180] Any two X groups can be linked together to form a bianion ligand group.

[0181] thermoplastic resin

[0182] The compositions described in this application may include one or more thermoplastic resins. "Thermoplastic resin" can be any material other than "propylene-based elastomer" as described herein. For example, a thermoplastic resin can be a polymer or polymer blend that is considered by those skilled in the art to be inherently thermoplastic, such as a polymer that softens when exposed to heat and returns to its original state when cooled to room temperature. The thermoplastic resin component may be an olefin thermoplastic resin (comprising one or more polyolefins), including polyolefin homopolymers and polyolefin copolymers. Unless otherwise stated, the term "copolymer" refers to a polymer (including terpolymers, tetrpolymers, etc.) derived from two or more monomers, and the term "polymer" refers to any carbon-containing compound having repeating units from one or more different monomers. The thermoplastic resin can be synthesized as disclosed in U.S. Patent Applications Publication Nos. US2019 / 0177449A1, US2018 / 0002352A1, and US2018 / 0134827, all of which are incorporated herein by reference.

[0183] Exemplary polyolefins can be prepared from monoolefin monomers, including but not limited to monomers having 2 to 7 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, mixtures thereof, and copolymers thereof. In at least one embodiment, the olefin thermoplastic resin is uncured or uncrosslinked.

[0184] Potentially useful ethylene-based polymers include those containing ethylene-derived units, one or more olefins selected from C3-C20 olefins (preferably 1-butene, 1-hexene, and / or 1-octene), and optionally one or more diene-derived units. The ethylene-based copolymer may have an ethylene content of greater than or equal to about 70 wt% (or about 70 wt% to about 100 wt%, or about 75 wt% to about 95 wt%, or about 80 wt% to about 90 wt%), based on the weight of the ethylene-based copolymer, with the remainder (if not 100% ethylene) being comonomer-derived units. The ethylene-based polymer may contain diene-derived units, which, when present, are present in about 0.05 wt% to about 6 wt% (or about 0.05 wt% to about 2 wt%, or about 1 wt% to about 5 wt%, or about 2 wt% to about 6 wt%).

[0185] Useful vinyl polymers may possess one or more of the following properties: (1) a density of about 0.85 g / cm³ 3 Approximately 0.91 g / cm³ 3 (or approximately 0.86 g / cm³) 3 Approximately 0.91 g / cm³ 3 or approximately 0.87 g / cm³ 3Approximately 0.91 g / cm³ 3 or approximately 0.88 g / cm³ 3 Approximately 0.905 g / cm³ 3 or approximately 0.88 g / cm³ 3 Approximately 0.902 g / cm³ 3 or approximately 0.885 g / cm³ 3 Approximately 0.902 g / cm³ 3 (2) Heat of fusion (Hf) of about 90 J / g or less (or about 10 J / g to about 70 J / g, or about 10 J / g to about 50 J / g, or about 10 J / g to about 30 J / g); (3) Crystallinity of about 5 wt% to about 40% (or about 5 wt% to about 30%, or about 5 wt% to about 20%); (4) Crystallinity of about 100 °C or less (or about 40 °C to about 100 °C, or about 40 °C to about 90 °C, or about 40 °C to about 30 °C, or about 40 °C to about 40 °C, or about 40 °C to about 3 ... (5) Melting point (Tm) of 0°C to about 80°C, or about 40°C to about 70°C, or about 40°C to about 60°C, or about 40°C to about 50°C; (6) Crystallization temperature (Tc) of 90°C or lower (or about 30°C to about 100°C, or about 30°C to about 90°C, or about 30°C to about 80°C, or about 30°C to about 70°C, or about 30°C to about 60°C, or about 30°C to about 50°C, or about 30°C to about 40°C); (7) Glass The glass transition temperature (Tg) is -20°C or lower (or about -50°C to about -30°C, or about -50°C to about -40°C); (7) Mw is about 30 kg / mol to about 2,000 kg / mol (or about 50 kg / mol to about 1,000 kg / mol, or about 90 kg / mol to about 500 kg / mol); (8) Mw / Mn is about 1 to about 5 (or about 1.4 to about 4.5, or about 1.6 to about 4, or about 1.8 to about 3.5, or about 1.8 to about 2.5); and / or (9) MFR (2.16 kg at 190°C) of about 0.1 g / 10 min to about 100 g / 10 min (or about 0.3 g / 10 min to about 60 g / 10 min, or about 0.5 g / 10 min to about 40 g / 10 min, or about 0.7 g / 10 min to about 20 g / 10 min).

[0186] In some embodiments, the olefin thermoplastic resin includes polypropylene. As used herein, the term "polypropylene" refers to any polymer that a person skilled in the art would consider to be "polypropylene" and includes propylene homopolymers, impact-resistant and random copolymers. In at least one embodiment, the polypropylene used in the compositions described herein has a melting point above 110°C and comprises at least 90 wt% propylene-derived units. Polypropylene may also comprise isotactic, atactic, or syndiotactic sequences, and may include isotactic sequences. Polypropylene is either derived solely from propylene monomers (i.e., having only propylene-derived units) or comprises at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 93 wt%, or at least 95 wt%, or at least 97 wt%, or at least 98 wt%, or at least 99 wt% propylene-derived units, the remainder being derived from olefins, such as ethylene, and / or C4-C10 α-olefins.

[0187] According to DSC measurements, thermoplastic resins may have a melt temperature of at least 110°C, or at least 120°C, or at least 130°C, and may be between 110°C and 170°C or higher.

[0188] Thermoplastic resins may have a melt flow rate (MFR) of about 0.1 to 100 g / 10 min, as measured by ASTM D1238 at 230°C and 2.16 kg weight. In some embodiments, the thermoplastic resin may have a fractional MFR, such as polypropylene having a fractional MFR of less than about 5 g / 10 min, or less than about 4 g / 10 min, or less than about 3.5 g / 10 min. In some embodiments, the thermoplastic resin may have an MFR ranging from a lower limit of about 0.1, 0.5, 1, 1.5, 2, 2.5, or 3 g / 10 min to an upper limit of about 2.5, 3, 3.5, 4.5, 6, 10, 15, or 45 g / 10 min, wherein the desired range may include a range from any lower limit to any upper limit.

[0189] Suitable thermoplastic resins can be polypropylene, such as commercially available polypropylene. Examples of suitable thermoplastic resins include, but are not limited to, "PP3155" (EXXONMOBIL). TM PP 3155 is a polypropylene homopolymer with a density of 0.9 g / cc and a melt flow rate (MFR) (230°C; 2.16 kg) of 36 g / 10 min (ASTM D1238), obtained from ExxonMobil Chemical Company; "PP8244" (EXXONMOBIL) TMPP 8244E1 is a polypropylene impact copolymer with 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), obtained from ExxonMobil Chemical Company; and “PP7143” (EXXONMOBIL). TM PP 7143KNE1 is a polypropylene impact copolymer with 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), obtained from ExxonMobil Chemical Company.

[0190] As another example of thermoplastic resins, ExxonMobil TM PP 7032E2 is a polypropylene available from ExxonMobil Chemical Company. PP 7032E2 is a polypropylene impact copolymer with the following properties:

[0191] (1) Density is 0.9 g / cm³ 3 ;

[0192] (2) Melt mass flow rate (MFR) (230℃; 2.16kg) is 4.0g / 10min (ASTM D1238);

[0193] (3) Yield tensile strength of 2.0 in / min (51 mm / min) is 3,480 psi (24.0 MPa) (ASTM D638);

[0194] (4) Yield tensile stress is 3390 psi (23.4 MPa) (ISO 527-2 / 50);

[0195] (5) Yield elongation (2.0 in / min (51 mm / min)) is 6.4% (ASTM D638);

[0196] (6) Yield tensile strain is 6.2% (ISO 527-2 / 50);

[0197] (7) Flexural modulus - 1% secant (0.51 in / min) is 188,000 psi (1300 MPa) (ASTM D790B);

[0198] (8) The impact strength of the notched cantilever beam at 23℃ is 45kJ / m. 2 (ISO 180 / 1A);

[0199] (9) The Charpy notched impact strength at 23℃ is 48 kJ / m. 2 (ISO 179 / leA); and

[0200] (10) The hot flexural temperature (1.80 MPa) is 48.7 °C (ISO 75-2 / Af).

[0201] ExxonMobil TM PP 7032E3 is a polypropylene available from ExxonMobil Chemical Company. PP7032E3 is a polypropylene impact copolymer with the following properties:

[0202] (1) Density is 0.9 g / cm³ 3 ;

[0203] (2) Melt mass flow rate (MFR) (230℃; 2.16kg) is 4.0g / 10min (ASTM D1238);

[0204] (3) Yield tensile strength of 2.0 in / min (51 mm / min) is 3,470 psi (23.9 MPa) (ASTM D638);

[0205] (4) Yield tensile stress is 3390 psi (23.4 MPa) (ISO 527-2 / 50);

[0206] (5) Yield elongation (2.0 in / min (51 mm / min)) is 7.3% (ASTM D638);

[0207] (6) Yield tensile strain is 6.3% (ISO 527-2 / 50);

[0208] (7) Flexural modulus - 1% secant (0.50 in / min) is 180,000 psi (1240 MPa) (ASTM D790B);

[0209] (8) The impact strength of the notched cantilever beam at 23℃ is 28 kJ / m. 2 (ISO 180 / 1A);

[0210] (9) The Charpy notched impact strength at 23℃ is 18 kJ / m. 2 (ISO 179 / leA); and

[0211] (10) The hot flexural temperature (1.80 MPa) is 51.4℃ (ISO 75-2 / A).

[0212] ExxonMobil TMPP 7032KN is a polypropylene available from ExxonMobil Chemical Company. PP7032KN is a polypropylene impact copolymer with the following properties:

[0213] (1) Density is 0.9 g / cm³ 3 ;

[0214] (2) Melt mass flow rate (MFR) (230℃; 2.16kg) is 4.0g / 10min (ASTM D1238);

[0215] (3) The yield tensile strength of 2.0 in / min (51 mm / min) is 26.1 MPa (ASTM D638);

[0216] (4) The yield tensile stress is 26.3 MPa (ISO 527-2 / 50);

[0217] (5) Yield elongation (2.0 in / min (51 mm / min)) is 5.5% (ASTM D638);

[0218] (6) Yield tensile strain is 4.2% (ISO 527-2 / 50);

[0219] (7) Flexural modulus -1% secant (1.3 mm / min) is 1,340 MPa (ASTM D790A);

[0220] (8) The impact strength of the notched cantilever beam at 23℃ is 42kJ / m. 2 (ISO 180 / 1A);

[0221] (9) The Charpy notched impact strength at 23℃ is 14 kJ / m. 2 (ISO 179 / leA); and

[0222] (10) The hot flexural temperature (1.80 MPa) is 52.5℃ (ISO 75-2 / A).

[0223] ExxonMobil TM PP 7033E2 is a polypropylene available from ExxonMobil Chemical Company. PP7033E2 is a polypropylene impact copolymer with the following properties:

[0224] (1) Density is 0.9 g / cm³ 3 ;

[0225] (2) Melt mass flow rate (MFR) (230℃; 2.16kg) is 8.0g / 10min (ASTM D1238);

[0226] (3) Yield tensile strength of 2.0 in / min (51 mm / min) is 3,420 psi (ASTM D638);

[0227] (4) Yield tensile stress is 3340 psi (ISO 527-2 / 50);

[0228] (5) Yield elongation (2.0 in / min (51 mm / min)) is 6.2% (ASTM D638);

[0229] (6) Yield tensile strain is 6.3% (ISO 527-2 / 50); and

[0230] (7) Flexural modulus - 1% secant (0.51 in / min) is 176,000 psi (ASTM D790B).

[0231] ExxonMobil TM PP 7033N is a polypropylene available from ExxonMobil Chemical Company. PP7033N is a polypropylene impact copolymer with the following properties:

[0232] (1) Density is 0.9 g / cm³ 3 ;

[0233] (2) Melt mass flow rate (MFR) (230℃; 2.16kg) is 8.0g / 10min (ASTM D1238);

[0234] (3) Yield tensile strength of 2.0 in / min (51 mm / min) is 3,760 psi (ASTM D638);

[0235] (4) Yield tensile stress is 3,740 psi (ISO 527-2 / 50);

[0236] (5) Yield elongation (2.0 in / min (51 mm / min)) is 5.2% (ASTM D638);

[0237] (6) Yield tensile strain is 4.0% (ISO 527-2 / 50); and

[0238] (7) Flexural modulus - 1% secant (0.51 in / min) is 224,000 psi (ASTM D790B).

[0239] additive

[0240] The compositions described herein may include one or more additives. Additives may include reinforcing and non-reinforcing fillers, antioxidants, stabilizers, processing oils, compatibilizers, lubricants (e.g., oleamide), antiblocking agents, antistatic agents, waxes, coupling agents for fillers and / or pigments, pigments, flame retardants, antioxidants, or other processing aids.

[0241] If additives are present in the composition, the improved melt strength and processability provided by the compositions of this specification can provide uniform dispersion of the additives (e.g., fillers), which provides a more uniform layer (film) for roofing applications, thereby providing improved physical properties of the layer (film). For example, additives (such as fillers) typically tend to agglomerate in the composition. However, the compositions of this specification promote the dispersion of additives such that the additives (e.g., the fillers of this specification (present in the composition)) have an average agglomerate size of less than 50 micrometers, for example less than 40 micrometers, for example less than 30 micrometers, for example less than 20 micrometers, for example less than 10 micrometers, for example less than 5 micrometers, for example less than 1 micrometer, for example less than 0.5 micrometers, for example less than 0.1 micrometers, based on a 1 cm × 1 cm cross-section of the composition observed using a scanning electron microscope.

[0242] In some embodiments, the composition may include fillers and colorants. Exemplary materials include inorganic fillers such as calcium carbonate, clay, silica, talc, titanium dioxide, or carbon black. Any type of carbon black can be used, such as channel black, furnace black, thermal cracking black, acetylene black, lampblack, etc.

[0243] In some embodiments, the roofing composition may include a flame retardant, such as calcium carbonate, an inorganic clay containing hydrated water, such as aluminum hydroxide (“ATH”), or magnesium hydroxide. For example, calcium carbonate or magnesium hydroxide may be premixed with a thermoplastic resin, such as polypropylene, or a polyethylene, such as linear low-density polyethylene, to form a masterbatch. For example, the flame retardant may be premixed with polypropylene, impact-resistant polypropylene-ethylene copolymer, or polyethylene, wherein the masterbatch contains 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 the flame retardant, based on the weight of the masterbatch. The flame retardant masterbatch may 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 5 wt% to 40 wt%, or 10 wt% to 35 wt%, or 15 wt% to 30 wt% of flame retardant masterbatch, wherein the desired range may include any lower limit to any upper limit.

[0244] In some embodiments, the composition may contain a UV stabilizer, such as titanium dioxide or XT-850. UV stabilizers can be introduced into the roofing composition as part of a masterbatch. For example, the UV stabilizer can be premixed with a thermoplastic resin, such as polypropylene or polyethylene, such as linear low-density polyethylene, to form a masterbatch. For example, the UV stabilizer can be premixed with polypropylene, impact-resistant polypropylene-ethylene copolymer, or polyethylene, wherein the masterbatch contains 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 the 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 contains 5 wt% to 30 wt%, or 7 wt% to 25 wt%, or 10 wt% to 20 wt% of a flame-retardant masterbatch, wherein the desired range can include a range from any lower limit to any upper limit.

[0245] Other additives may include antioxidants and / or heat stabilizers. In an exemplary embodiment, processing and / or on-site heat stabilizers may include those available from BASF. B-225 and / or 1010.

[0246] End use

[0247] The compositions described in this specification are particularly suitable for roofing applications, such as for thermoplastic polyolefin roofing films. Films produced from these compositions can exhibit a beneficial combination of properties, and in particular an improved balance of elastic modulus (flexibility) at temperatures from -40°C to 40°C, elastic modulus at high temperatures (e.g., 100°C) (reducing roll adhesion properties), and higher melt strength (providing improved dimensional stability during sheeting).

[0248] The roofing compositions described herein can be prepared by pre-mixing or in-situ compounding using polymer manufacturing processes such as Banbury mixing or twin-screw extrusion. The compositions can then be formed into roofing membranes. Roofing membranes may be particularly useful in commercial roofing applications, such as on flat, low-slope, or steep-slope substrates.

[0249] The roof membrane can be adhered to or secured to the base roof by any suitable fastening method, such as by adhesive materials, ballast materials, point bonding, or mechanical point fastening. For example, the membrane can be installed and fastened through the roof slab using mechanical fasteners and plates placed along the edge sheets. Adjacent sheets of the flexible membrane are overlapped to cover the fasteners and plates, and preferably joined together, for example, by hot air welding. The membrane can also be completely adhered to or self-adheded to the insulation or roof slab material using adhesives. The insulation is typically secured to the roof slab with mechanical fasteners, while the flexible membrane is adhered to the insulation.

[0250] The roof membrane can be reinforced with any type of sparse fabric, including but not limited to polyester, glass fiber, glass fiber reinforced polyester, polypropylene, woven or nonwoven fabrics (e.g., nylon), or combinations thereof. For example, the sparse fabric can be glass fiber and / or polyester.

[0251] In some implementations, the surface layers of the top and / or bottom of the membrane can have textures with various patterns. Textures increase the surface area of ​​the membrane, reduce glare, and make the membrane surface less slippery. Examples of texture designs include, but are not limited to, polyhedra with polygonal bases and triangular faces intersecting at common vertices, such as pyramid bases; conical structures with circular or elliptical configurations; and random pattern configurations.

[0252] In at least one embodiment, the thickness of the roof membrane is 0.1 to 5 mm, or 0.5 to 4 mm.

[0253] The compositions of the present invention may include blends of a propylene-based elastomer, a thermoplastic resin, at least one flame retardant, and at least one UV stabilizer. In some embodiments, the blend composition further comprises a polyalphaolefin.

[0254] In at least one embodiment, the film can be manufactured as a composite structure comprising a reflective film (40 to 60 mils thick) (1 to 1.5 mm thick), a reinforcing layer (1 to 2 mils thick) (0.03 to 0.05 mm thick), and a coloring layer (40 to 60 mils thick) (1 to 1.5 mm thick). The reflective film can be a thermoplastic compounded with a white filler (e.g., titanium dioxide). The reinforcing layer can be a loosely woven polyester fiber. The coloring layer can be a thermoplastic compounded with carbon black.

[0255] List of Implementation Plans

[0256] This specification provides, in particular, the following embodiments, each of which may be considered as optionally including any alternative embodiments.

[0257] Clause 1. A roofing composition comprising:

[0258] Polymer blends comprising:

[0259] Propylene-based elastomers, wherein the melt flow rate of the propylene-based elastomer according to ASTM D-1238 (2.16 kg weight @ 230 °C) is less than approximately 3 g / 10 min; and

[0260] Thermoplastic resin;

[0261] UV stabilizers; and

[0262] Flame retardant.

[0263] Clause 2. The roofing composition of Clause 1, wherein the propylene-based elastomer has:

[0264] Mw of approximately 300,000 g / mol to approximately 600,000 g / mol.

[0265] Clause 3. The roofing composition of any one of Clauses 1-2, wherein the propylene-based elastomer has at least one of the following properties:

[0266] Mw is approximately 500,000 g / mol to approximately 600,000 g / mol.

[0267] According to ASTM 1238 (2.16 kg @ 230 °C), the melt flow rate is approximately 0.1 dg / min to approximately 2 dg / min.

[0268] Crystallinity percentage less than approximately 3%,

[0269] According to ASTM D-1505, the density is approximately 0.85 g / cm³. 3 Approximately 0.87 g / cm³ 3 ,

[0270] According to ASTM D-1238 (2.16 kg @ 230 °C), the melt index is approximately 0.5 g / 10 min to approximately 3.0 g / 10 min.

[0271] The number-average molecular weight (Mn) is approximately 150,000 g / mol to approximately 350,000 g / mol.

[0272] Clause 4. The roofing composition of any one of Clauses 1-3, wherein the propylene-based polymer is prepared using a catalyst system comprising:

[0273] Activator and

[0274] Quinolinyl diamino catalyst.

[0275] Clause 5. The roofing composition of any one of Clauses 1-3, wherein the propylene-based polymer is formed using a catalyst system comprising:

[0276] Activator, and

[0277] Catalysts containing group 4 bis(phenolic salt) complexes.

[0278] Clause 6. The roofing composition of any one of Clauses 1-5, wherein the polymer blend contains 8 to 15 wt% ethylene, based on the total weight of the polymer blend.

[0279] Clause 7. A roofing composition comprising:

[0280] Polymer blends comprising:

[0281] A propylene-based elastomer, wherein the branching index g′ of the propylene-based elastomer according to GPC-4D is less than 1; and

[0282] Thermoplastic resin;

[0283] UV stabilizers; and

[0284] Flame retardant.

[0285] Clause 8. The roofing composition of Clause 7, wherein the propylene-based polymer comprises:

[0286] At least 60 wt% propylene-derived units;

[0287] 0.3 to 10 wt% diene-derived units; and

[0288] At least 6 wt% ethylene-derived units,

[0289] Each wt% is based on the total weight of the propylene-based elastomer, and

[0290] The propylene-based elastomer has isotactic polypropylene crystallinity, a DSC melting point equal to or less than or higher than 110℃, and a heat of fusion of 5J / g to 50J / g.

[0291] Clause 9. The roofing composition of Clause 8, wherein the diene is 5-vinyl-2-norbornene (VNB).

[0292] Clause 10. A roofing composition of any one of Clauses 7-9, wherein the propylene-based elastomer is partially insoluble and the fractions soluble at 23°C and 31°C, as measured by the extraction method described herein, have an ethylene content that differs by 5 wt% or less.

[0293] Clause 11. Clause 7's roofing composition, wherein the propylene-based elastomer is a branched propylene-based elastomer formed by a method comprising:

[0294] In a mixer, a first propylene-based elastomer, a free radical initiator, and an additive are mixed to form a branched propylene-based elastomer.

[0295] Clause 12. The roofing composition of Clause 11, wherein the method further comprises:

[0296] Before adding the auxiliary agent or the free radical initiator, a free radical scavenger is added to the first propylene-based polymer.

[0297] Clause 13. The roofing composition of Clause 12, wherein the free radical scavenger comprises:

[0298] At least one nitro oxygen radical; and

[0299] At least one unsaturated bond capable of undergoing a free radical reaction.

[0300] Clause 14. The roofing composition of any one of Clauses 12-13, wherein the free radical scavenger is 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxy (AOTEMPO).

[0301] Clause 15. The roofing composition of any one of Clauses 11-14, wherein the free radical initiator is selected from organic peroxides, organic peresters, and azo compounds. Examples of such compounds include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyn-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl peroctanoate, tert-butyl perpentylate, cumyl perpentylate, and tert-butyl perethylacetate, azoisobutyronitrile, and dimethyl azoisobutyrate.

[0302] Clause 16. The roofing composition of any one of Clauses 11-15, wherein the free radical initiator is 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0303] Clause 17. A roofing composition of any one of Clauses 11-16, wherein the additive is selected from triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, sulfur, N-phenylbismaleimide, zinc diacrylate, zinc dimethacrylate, divinylbenzene, 1,2-polybutadiene, trimethylolpropane trimethacrylate, butanediol diacrylate, trifunctional acrylate, dipentaerythritol pentaacrylate, polyfunctional acrylate, passivated cyclohexanediol diacrylate, polyfunctional methacrylate, metal salts of acrylic acid and methacrylate, such as oximes of quinone dioximes.

[0304] Clause 18. The roofing composition of any one of Clauses 11-17, wherein the additive is triallyl isocyanurate.

[0305] Clause 19. The roofing composition of any one of Clauses 12-14, wherein the branched propylene-based elastomer is formed from 95 to 99 wt% of a first propylene-based elastomer, 0.5 to 1 wt% of a free radical scavenger, 0.3 to 0.6 wt% of an additive and 0.5 to 1.5 wt% of a free radical initiator, wherein the wt% is based on the total weight of the branched propylene-based elastomer.

[0306] Clause 20. A roofing composition comprising:

[0307] Propylene-based elastomer-grafted polystyrene (PBE-g-PS) comprising approximately 20 wt% to approximately 50 wt% of the TPO film weight;

[0308] Thermoplastic resin comprising about 5 wt% to about 50 wt% of the roofing composition by weight;

[0309] UV stabilizers; and

[0310] Flame retardant.

[0311] Clause 21. The roofing composition of Clause 20, wherein the propylene-based elastomer of PBE-g-PS has 70 wt% to 95 wt% propylene-derived units and 5 wt% to 30 wt% C2 or C4-C6 α-olefin-derived units.

[0312] Clause 22. The roofing composition of any one of Clauses 20-21, wherein PBE-g-PS has at least one of the following properties:

[0313] Styrene content of approximately 1 wt% to approximately 40 wt%,

[0314] According to ASTM D1238 (2.16 kg @ 230 °C), the melt flow rate is approximately 1 g / 10 min to approximately 20 g / 10 min.

[0315] The weight-average molecular weight is approximately 100,000 g / mol to approximately 500,000 g / mol.

[0316] The number-average molecular weight is from about 5,000 g / mol to about 50,000 g / mol, and

[0317] The molecular weight distribution is from about 3 to about 20.

[0318] Clause 23. A roofing composition of any one of Clauses 1-22, wherein the roofing composition comprises about 5 wt% to about 50 wt% of a thermoplastic resin based on the total weight of the roofing membrane.

[0319] Clause 24. A roofing composition of any one of Clauses 1-23, wherein the thermoplastic resin is polypropylene.

[0320] Clause 25. The roofing composition of Clause 24, wherein the polypropylene comprises a comonomer and at least 85 wt% propylene-derived units.

[0321] Clause 26. Roofing compositions of Clause 25, wherein the comonomer is ethylene.

[0322] Clause 27. A roofing composition of any one of Clauses 1-26, wherein the thermoplastic resin is an impact copolymer.

[0323] Clause 28. A roofing composition of any one of Clauses 1-27, wherein the thermoplastic resin has a melt temperature of about 110°C to about 170°C, as measured by DSC.

[0324] Clause 29. A roofing composition of any one of Clauses 1-28, wherein the thermoplastic resin has a melt flow rate of about 0.1 to about 4 according to ASTM D1238 (2.16 kg weight @ 230 °C).

[0325] Clause 30. The roofing composition of any one of Clauses 1-29, wherein the thermoplastic resin is polypropylene having the following properties:

[0326] (1) The density is approximately 0.9 g / cm³. 3 ;

[0327] (2) The melt flow rate (MFR) according to ASTM D1238 (2.16 kg weight @ 230 °C) is approximately 4 g / 10 min;

[0328] (3) The yield tensile strength according to ASTM D638 (2.0 in / min; 51 mm / min) is approximately 3,500 psi (approximately 24 MPa);

[0329] (4) According to ISO 527-2 / 50, the yield tensile stress is approximately 3390 psi (23.4 MPa);

[0330] (5) The yield elongation is approximately 6.4% according to ASTM D638 (2.0 in / min; 51 mm / min);

[0331] (6) The yield tensile strain according to ISO 527-2 / 50 is approximately 6.2%;

[0332] (7) The flexural modulus according to ASTM D790B (1% secant; 0.51 in / min) is approximately 188,000 psi (approximately 1300 MPa);

[0333] (8) According to ISO 180 / 1A (23℃), the impact strength of a notched cantilever beam is approximately 45 kJ / m. 2 ;

[0334] (9) According to ISO 179 / leA (23℃), the Charpy notched impact strength is approximately 48 kJ / m. 2 ;and

[0335] (10) The thermal flexural temperature according to ISO 75-2 / Af (1.80MPa) is approximately 48.7℃.

[0336] Clause 31. The roofing composition of any one of Clauses 1-29, wherein the thermoplastic resin is polypropylene having the following properties:

[0337] (1) The density is approximately 0.9 g / cm³. 3 ;

[0338] (2) According to ASTM D1238 (230℃; 2.16kg), the melt flow rate (MFR) is approximately 4g / 10min;

[0339] (3) The yield tensile strength according to ASTM D638 (2.0 in / min; 51 mm / min) is approximately 3,470 psi (approximately 23.9 MPa);

[0340] (4) According to ISO 527-2 / 50, the yield tensile stress is approximately 3390 psi (approximately 23.4 MPa);

[0341] (5) The yield elongation is approximately 7.3% according to ASTM D638 (2.0 in / min; 51 mm / min);

[0342] (6) The yield tensile strain according to ISO 527-2 / 50 is approximately 6.3%;

[0343] (7) The flexural modulus according to ASTM D790B (1% secant; 0.50 in / min) is approximately 180,000 psi (approximately 1240 MPa);

[0344] (8) According to ISO 180 / 1A (23℃), the impact strength of a notched cantilever beam is approximately 28 kJ / m. 2 ;

[0345] (9) According to ISO 179 / leA (23℃), the Charpy notched impact strength is approximately 18 kJ / m. 2 ;and

[0346] (10) The thermal flexural temperature according to ISO 75-2 / A (1.80 MPa) is approximately 51.4 °C.

[0347] Clause 32. The roofing composition of any one of Clauses 1-29, wherein the thermoplastic resin is polypropylene having the following properties:

[0348] (1) The density is approximately 0.9 g / cm³. 3 ;

[0349] (2) According to ASTM D1238 (230℃; 2.16kg), the melt flow rate (MFR) is approximately 4g / 10min;

[0350] (3) The yield tensile strength according to ASTM D638 (2.0 in / min; 51 mm / min) is approximately 26.1 MPa;

[0351] (4) The yield tensile stress according to ISO 527-2 / 50 is approximately 26.3 MPa;

[0352] (5) The yield elongation is approximately 5.5% according to ASTM D638 (2.0 in / min; 51 mm / min);

[0353] (6) The yield tensile strain according to ISO 527-2 / 50 is approximately 4.2%;

[0354] (7) The flexural modulus according to ASTM D790B (1% secant; 0.50 in / min) is approximately 1,340 MPa;

[0355] (8) According to ISO 180 / 1A (23℃), the impact strength of a notched cantilever beam is approximately 42 kJ / m. 2 ;

[0356] (9) According to ISO 179 / leA (23℃), the Charpy notched impact strength is approximately 14 kJ / m. 2 ;and

[0357] (10) The thermal flexural temperature according to ISO 75-2 / A (1.80 MPa) is approximately 52.5 °C.

[0358] Clause 33. The roofing composition of Clause 1, wherein the propylene-based elastomer has at least one of the following properties:

[0359] Heat of fusion less than 25 J / g

[0360] According to ASTM D1505, the density is 0.862 g / cm³. 3 ,

[0361] The melt index is 1.4 g / 10 min (190℃ / 2.16 kg).

[0362] According to ASTM D1238 (230℃; 2.16kg), the melt flow rate is 3g / 10min.

[0363] The ethylene content is 16 wt%.

[0364] According to ASTM D638, the tensile strength at break is greater than 1,100 psi.

[0365] According to ASTM D638, the elongation at break is greater than 800%.

[0366] According to ASTM D790, the flexural modulus of 1% secant is 2,090 psi.

[0367] Clause 34. A roofing composition comprising:

[0368] Polymer blends comprising:

[0369] Acrylic-based elastomers; and

[0370] Thermoplastic polyolefins;

[0371] UV stabilizers; and

[0372] Flame retardant.

[0373] Clause 35. Roofing composition of Clause 34, wherein the roofing composition has a phase angle of about 73 or less at a complex modulus G* of 1,000 Pa.

[0374] Clause 36. A roofing composition according to any one of Clauses 34-35, wherein the roofing composition has a phase angle of about 72 or less at a complex modulus G* of 500.

[0375] Clause 37. The roofing composition of any one of Clauses 34-36, wherein the roofing composition is at a Henchy rate of 1 s at 0.1 seconds. -1 The tensile viscosity at 0.1 seconds is at least 50% greater than that of the control sample at 0.1 seconds, and

[0376] The roofing composition, at a Henchy rate of 1s, is described as being in operation at 1.0 seconds. -1 The tensile viscosity at this point is at least 100% greater than the tensile viscosity of the control sample at 1 second, and

[0377] The control sample has the same composition as the roofing composition, except that the first polyolefin is a propylene-based polymer with the following properties:

[0378] Heat of fusion less than 25 J / g

[0379] According to ASTM D1505, the density is 0.862 g / cm³. 3 ,

[0380] The melt index is 1.4 g / 10 min (190℃ / 2.16 kg).

[0381] According to ASTM D1238 (230℃; 2.16kg), the melt flow rate is 3g / 10min.

[0382] The ethylene content is 16 wt%.

[0383] According to ASTM D638, the tensile strength at break is greater than 1,100 psi.

[0384] According to ASTM D638, the elongation at break is greater than 800%.

[0385] According to ASTM D790, a 1% secant flexural modulus is 2,090 psi.

[0386] Secondary polyolefins are thermoplastic resins with the following properties:

[0387] The density is 0.9 g / cm³. 3 ;

[0388] The melt mass flow rate (MFR) (230°C; 2.16 kg) is 4.0 g / 10 min (ASTM D1238);

[0389] The yield tensile strength at 2.0 in / min (51 mm / min) is 3,480 psi (24.0 MPa) (ASTM D638);

[0390] The yield tensile stress is 3390 psi (23.4 MPa) (ISO 527-2 / 50);

[0391] The yield elongation (2.0 in / min (51 mm / min)) is 6.4% (ASTM D638); the yield tensile strain is 6.2% (ISO 527-2 / 50);

[0392] Flexural modulus -1% secant (0.51 in / min) is 188,000 psi (1300 MPa) (ASTM D790B);

[0393] The impact strength of the notched cantilever beam at 23℃ is 45 kJ / m. 2 (ISO 180 / 1A);

[0394] The Charpy notched impact strength at 23℃ is 48 kJ / m.2 (ISO 179 / leA); and

[0395] The hot flexural temperature (1.80 MPa) is 48.7 °C (ISO 75-2 / Af).

[0396] Clause 38. A roofing composition of any one of Clauses 34-37, wherein, when measured by the US-EV method, the roofing composition at a Henchy rate of 1 s at 0.1 s is [value missing]. -1 It has a tensile viscosity greater than 15,000 Pa-sec.

[0397] Clause 39. A roofing composition of any one of Clauses 34-38, wherein, when measured by the US-EV method, the roofing composition at a Henchy rate of 1 s is [value missing]. -1 It has a tensile viscosity greater than 40,000 Pa-sec.

[0398] Clause 40. The roofing composition of any one of Clauses 34-39, wherein the roofing composition comprises 30 to 70 wt% of a polymer blend based on the total weight of the roofing composition.

[0399] Clause 41. A roofing composition of any one of Clauses 34-40, wherein the polymer blend comprises 30 to 70 wt% of a first polyolefin, based on the total weight of the polymer blend.

[0400] Clause 42. The roofing composition of any one of Clauses 34-41, wherein the polymer blend comprises 30 to 70 wt% of a second polyolefin, based on the total weight of the polymer blend.

[0401] Clause 43. The roofing composition of any one of Clauses 34-42, wherein the first polyolefin is a propylene-based elastomer.

[0402] Clause 44. The roofing composition of any one of Clauses 34-43, wherein the second polyolefin is an impact copolymer comprising a polypropylene matrix phase and an ethylene-propylene rubber dispersion phase.

[0403] Clause 45. A roofing material comprising:

[0404] A membrane comprising any of the roofing compositions of clauses 1 to 44; and

[0405] The substrate material that is adhered to or fixed onto the membrane.

[0406] Clause 46. Roofing materials of Clause 45, wherein the membrane further includes a sparse cloth selected from polyester, glass fiber, glass fiber reinforced polyester, polypropylene, woven or nonwoven fabrics, and combinations thereof.

[0407] Clause 47. The roofing material of any one of Clauses 44 to 46, wherein the membrane has a thickness from about 0.5 mm to about 4 mm.

[0408] Clause 48. A method comprising:

[0409] A blend composition comprising:

[0410] Propylene-based elastomers, wherein the propylene-based elastomers have a melt flow rate of less than about 3 g / 10 min according to ASTM D-1238 (2.16 kg weight @ 230 °C);

[0411] Thermoplastic resin;

[0412] UV stabilizers; and

[0413] Flame retardant. Example

[0414] To address the dimensional stability requirements of the tableting process, polypropylene homopolymer (HPP) was blended with a propylene-based elastomer ranging from 10 wt% to 20 wt% of C2%, providing high melt strength and softness for TPO roofing formulations. The tested propylene-based elastomer offered enhanced melt strength compared to the Visamaxx 6102 polymer. Such formulations offer similar elastic modulus to Visamaxx 6102 formulations, providing softness.

[0415] I. High molecular weight propylene-based elastomers

[0416] The test methods used in the embodiments are listed in Table 1 below.

[0417] Table 1

[0418] Test performance Test methods melt flow rate ASTM D1238 density ASTM D1505 Yield tensile stress ASTM D638 Fracture tensile stress ASTM D638 Fracture tensile strain ASTM D638 1% secant of tensile modulus ASTM D638 Flexural modulus 1% secant ASTM D790 DMTA:E′ (below)

[0419] The samples prepared in the examples were subjected to dynamic mechanical thermal analysis (“DMTA”) to provide information about the small-strain mechanical response of the samples as a function of temperature. The samples were tested using a commercially available DMA instrument equipped with a double cantilever test fixture (e.g., TAInstruments DMA 2980 or Rheometrics RSA). The samples were cooled to -70°C and then heated to 100°C at a rate of 2°C / min, while being subjected to oscillating deformation at a strain of 0.1% and a frequency of 6.3 radians / second. The outputs of the DMTA test are the storage modulus (E′) and the loss modulus (E”). The storage modulus represents the elastic response, or the material’s ability to store energy, while the loss modulus represents the viscous response, or the material’s ability to dissipate energy. The ratio of E” / E′, called Tan-δ, gives a measure of the material’s damping capacity; the peak in Tan-δ is related to the material’s relaxation mode.

[0420] MFR is determined as follows: g / 10min. 2.16 kg of polymer is loaded into a die with dimensions L / D (8.000 mm / 2.095 mm) at 230°C. The weight (in grams) passing through the die is measured over 10 minutes at a constant temperature.

[0421] Ethylene content was determined as follows: Fourier Transform Infrared Spectroscopy (FTIR): At 150℃, the sample was pressed between two sheets of Teflon paper to form a thin film with a thickness of 100-200 micrometers. FTIR spectral imaging was performed using a PerkinElmer Spectrum 100 series spectrometer. The spectral resolution was 4 cm⁻¹. -1 The cumulative number of scans for each measurement is 16. The spectral range of the infrared spectrum is 4000 cm⁻¹. -1 Up to 450cm -1 The scanning speed is 0.2 cm / s.

[0422] Tensile viscosity was determined as follows: Transient uniaxial tensile viscosity was measured using an Anton-Paar MCR 501 or a TA Instruments DHR-3 on a SER Universal testing platform (Xpansion Instruments, LLC) model SER2-P, SER3-G, or SER-2-A. The SER testing platform was used with a Rheometrics ARES-LS (RSA3) strain-controlled rotational rheometer, which is available from TA Instruments Inc., New Castle, Del., USA. The SER (Sentmanat tensile rheometer) testing platform is disclosed in U.S. Patents US 6,578,413 and US 6,691,569, which are incorporated herein by reference. For example, a general description of transient uniaxial elongational viscosity measurement is disclosed in “Strain hardening of various polyolefins in uniaxial elongational flow”, The Society of Rheology, Inc., J. Rheol 47(3, 619-630 (2003); and “Measuring the transient extensional rheology of polyethylene melts using the SER universaltes ting platform”, The Society of Rheology, Inc., J. Rheol. 49(3), 585-606 (2005), which are incorporated herein by reference.

[0423] HifaxTM CA 10A is a reactor-grade TPO (thermoplastic polyolefin) manufactured using LyondellBasell's proprietary Catalloy process technology. It is suitable for industrial applications requiring good processability and excellent flexibility. It is widely used as a building block resin for flexible waterproof membranes. Hifax CA 10A features low stiffness, low hardness, and good impact resistance. Hifax CA 10A has the following properties:

[0424] • Density is 0.880 g / cm³ 3 ISO 1183-1, Method A

[0425] • Melt flowability, ISO 1133-1: 0.60 g / 10 min

[0426] • Hardness, Shore D, ISO 868 30 @ 15 seconds

[0427] • Tensile strength at break is 11 MPa, ISO 527-1,-2

[0428] • Elongation at break is 500%, ISO 527-1,-2

[0429] • Flexural modulus is 0.09 GPa, ISO 178

[0430] Charpy impact strength 11 J / cm 2 Notch, ISO 179, Failure Mode - Partial Fracture, at -20°C

[0431] • Flexural temperature at 0.46 MPa (66 psi) is 40 °C, ISO 75B-1,-2, unannealed

[0432] • Vicat softening point is 60℃, ISO 306, A50

[0433] • The DSC sensing temperature is 142℃, ISO 11357-3

[0434] Ethylene content is 19 wt%.

[0435] Vis tamaxx TM 6100 is a propylene-based elastomer available from ExxonMobil Chemical Company. (Vis tamaxx) TM The density of 6100 is 0.855 g / cm³. 3(ASTM D1505), melt index (190℃ / 2.16kg) is 3g / 10min, melt flow rate is 3g / 10min (ASTM D1238), and ethylene content is 16wt%, tensile strength at break (ASTM D638) is greater than 2,130psi, elongation at break (ASTM D638) is greater than 860%, and 1% secant flexural modulus (ASTM D790) is 2,770psi.

[0436] Vis tamaxx TM 6102 is a propylene-based elastomer available from ExxonMobil Chemical Company. (Vis tamaxx) TM The density of 6102 is 0.862 g / cm³. 3 (ASTM D1505), melt index (190℃ / 2.16kg) is 1.4g / 10min, melt flow rate is 3g / 10min, ethylene content is 16wt%, tensile strength at break (ASTM D638) is greater than 1,100psi, elongation at break (ASTM D638) is greater than 800%, and 1% secant flexural modulus (ASTM D790) is 2,090psi.

[0437] "PP7032" is ExxonMobil TM PP 7032E2 is a polypropylene available from ExxonMobil Chemical Company. PP7032 is a polypropylene impact copolymer with a density of 0.9 g / cc, a melt flow rate (MFR) of 4.0 g / 10 min (ASTM D1238) (230°C; 2.16 kg), and an ethylene content of 9 wt%.

[0438] The magnesium hydroxide masterbatch used in the examples is Vertex from JM Huber. TM 60 HST. It contains 70 wt% magnesium hydroxide and 30 wt% Adflex polypropylene impact copolymer from Lyondell Basell. TM KS 311P.

[0439] The white concentrated masterbatch used in the examples contains more than 50 wt% titanium dioxide, with the remainder being polypropylene homopolymer.

[0440] The UV stabilizer masterbatch used in the examples is a masterbatch containing UV stabilizing additives, titanium dioxide as a white pigment, and carrier resin, with a density of 1.04 g / cc.

[0441] Table 2 shows the raw materials used in the roofing formulation, including both polymers and additives. In Table 2, Exp.1, Exp.2, and Exp.3 are high MW propylene-based elastomers prepared using a quinolinyl diamino hafnium catalyst (as shown in Formula II above and described in U.S. Patent Application Publication No. 2018 / 0002352), with an MFR of approximately 0.5 g / 10 min. Vistamaxx TM 6100 propylene-based elastomer is a single-reactor PBE, free of RCP components. (Using Vistamaxx) TM 6102 Propylene-based elastomers and Hifax TM CA 10A production comparison formula.

[0442] Table 2

[0443] Components C2 (wt%) MFR (g / 10min) Density (g / cc) %filler VM 6102 16 3 0.862 VM 6100 16 3 0.862 Exp.1 9 0.46 0.862 Exp.2 19.2 0.47 0.862 Exp.3 12.3 0.49 0.862 PP 7032 9 3 0.900 CA 10A 19 0.5 0.880 <![CDATA[MgOH2 masterbatch]]> 1.920 30.0 UV stabilizer masterbatch 1.000 3.0 White Concentrated Masterbatch 1.000 7.0

[0444] Table 3 shows the TPO formulations. Examples C1, C2, and C3 are control examples. Example C3 contains Hifax. TM CA 10A, while embodiments C1 and C2 include Vistamaxx TM 6102 and 6100PBE. The flexural modulus of the formulations in Examples 1 to 3 of this invention is less than that of Examples C1 and C2. In Table 3, the “Tanδ peak” is the temperature associated with the inflection point of the Tanδ curve. This temperature is usually negative and is also called the glass transition temperature of the composition, while the entire Tanδ curve value (i.e., the ratio of the positive viscous modulus E” to the positive elastic modulus E′) is positive.

[0445] The formulation was compounded using an Intelli-Torque Brabender at a melt temperature of 210°C. In this experiment, a CWB Prep-Mixer was used for approximately 250g of material, and the polymer and filler were then introduced directly into the extruder hopper. Homogenization was completed within 3 minutes once the torque stabilized. The batch weight of the formulation was 250g.

[0446] Table 3

[0447] Example C1 C2 Example 1 Vistamaxx 6102 30.0 Vistamaxx 6100 30.0 Exp.1 30.0 Exp.2 Exp.3 PP 7032 30.0 30.0 30.0 CA 10A <![CDATA[MgOH2 masterbatch]]> 30.0 30.0 30.0 UV stabilizer masterbatch 3.0 3.0 3.0

[0448] Table 3 (continued)

[0449] White Concentrated Masterbatch 7.0 7.0 7.0 total 100 100 100 MFR 5.88±0.82 5.62±0.83 1.04±0.02 Tanδ peak C -30.2 -27.9 -13.5 E-peak C -31.9 -30.2 -17.8 Flexural modulus MPa 479 410 431 Flexural modulus (std dev) 22.8 16.3 13.5 1% secant modulus MPa 489.92 415.90 490.79 Example Example 2 Example 3 C3 Vistamaxx 6102 Vistamaxx 6100 Exp.1 Exp.2 30.0 Exp.3 30.0 PP 7032 30.0 30.0 CA 10A 60.0 <![CDATA[MgOH2 masterbatch]]> 30.0 30.0 30.0 UV stabilizer masterbatch 3.0 3.0 3.0 White Concentrated Masterbatch 7.0 7.0 7.0 total 100 100 100 MFR 1.25±0.01 0.95±0.01 0.93±0.01 Tanδ peak C -32.1 -24.7 -28.3 E-peak C -32.1 -26.5 -32.0 Flexural modulus MPa 382 358 227 Flexural modulus (std dev) 16.4 15.4 11.1 1% secant modulus MPa 360.00 361.63 235.43

[0450] Figure 2This is a graph illustrating the relationship between the elastic modulus E of the composition and temperature. The compositions of the present invention in Examples 1 to 3 exhibit moduli equivalent to those of Examples C1 and C2 at temperatures below -40°C, and similar moduli in the temperature range of -40°C to 40°C. At higher temperatures, the modulus values ​​are close to those of Control Examples C1 and C2, and much higher than those of Control Example C3, indicating an increase in modulus at high temperatures relative to Control Example C3.

[0451] Figure 3 This is a graph illustrating the tensile viscosity of the five compositions. Tensile tests were performed at 190°C on an ARES instrument equipped with an tensile viscosity fixture (EVF), with the Hencky rate set to 0.1 / s. A nitrogen atmosphere was used to avoid oxidative degradation. The formulations of the present invention in Examples 1 to 3 exhibited significantly higher melt strengths compared to Control Example C1, which is equivalent to Control Example C3. This indicates that the formulations of the present invention in Examples 1 to 3 provide processability parameters for TPO roofing applications.

[0452] II. Graded MFR Propylene-Based Elastomers

[0453] Table 4 shows the raw materials used in the roofing formulation, including both polymers and additives. Exp.4 is a graded MFR propylene-based elastomer prepared using a catalyst containing a Group 4 bis(phenolate) complex (as shown in Formula III above and described in PCT patent application PCT / US2020 / 045819) and having an MFR of approximately 0.9 g / 10 min. Conc.80 is a flame retardant masterbatch containing 80 wt% flame retardant. Conc.27UHP is a UV stabilizer masterbatch containing 27 wt% UV stabilizer.

[0454] Table 4

[0455] Components C2 (wt%) MFR (g / 10min) Density (g / cc) %filler VM 6102 16 3 0.862 Exp.4 16 0.88 N / A PP 7032 9 3 0.900 <![CDATA[Hifax TM AC 10A]]> 19 0.5 0.880 Conc.80 (Flame Retardant Masterbatch) NA 20％ Conc.27UHP (UV stabilizer masterbatch) NA 73％

[0456] Table 5 shows the TPO formulations in grams. Examples C4, C5, and C6 are control examples. Example C4 contains Hifax. TM CA 10A, while embodiments C5 and C6 include Vistamaxx. TM 6100PBE. The formulation was mixed in an Intelli-Torque Brabender at a melt temperature of 200°C at low RPM to flux, then mixed at 50 RPM for 3 minutes. The batch weight of each formulation is approximately 270 grams.

[0457] Table 5

[0458] C4 C5 C6 Example 4 (E4) Hifax CA10A 153 Vistamaxx 6100 75 75 Exp.4 75 PP 7032 75 75 Braskem TI 4007G 75

[0459] Table 5 (continued)

[0460] Conc.80 76 75 75 75 Conc 27UHP 44 43 43 43 Total [g] 273 269 269 269 MFR 1.09 3.7 2.0 0.8 Tanδ peak -26.7 -27.3 -27.3 -27.3 Flexural modulus 166 315 328 304 Flexural modulus (std dev) 25.4 22 45 11.2

[0461] The flexural modulus of the formulation of the present invention in Example 4 is less than that of Examples C5 and C6.

[0462] Figure 4 This is a graph illustrating the tensile viscosity of the four compositions. The US-EV method described above was used. Compared to Comparative Examples C5 and C6, the inventive formulation of Example 4 exhibits a much higher melt strength, equivalent to Comparative Example C4. This indicates that the inventive formulation of Example 4 provides processability parameters for TPO roofing applications.

[0463] Table 6 provides tensile viscosity data for control examples C4, C5, and C6 and Example 4 of the present invention. At shorter calibration times, i.e., 0.001 seconds, the test method may exhibit high levels of noise. At longer calibration times, where tensile viscosity measurements are more consistent and accurate, it can be seen that the performance of Example 4 of the present invention is comparable to control sample C4 and significantly superior to PBE control compositions C5 and C6.

[0464] Table 6

[0465] Correction time [s] C4 C5 C6 E4 0.001 NA 284.2 3281.7 854.1 0.01 3086.0 3383.3 5506.8 6537.3 0.1 24228.2 10435.9 20276.9 21958.3 1 58866.7 19290.0 41582.9 54747.8

[0466] Table 7 illustrates the percentage increase in tensile viscosity of Example 4 of the present invention compared to control sample C5. Sample C5 comprises a PBE with an MFR of 3, compared to Example 4 of the present invention (which includes a PBE with a graded MFR of 0.88). Achieving a PBE with a lower MFR (e.g., less than 1) corresponds to an improvement in tensile viscosity of approximately 100% or more across the entire test range. This further supports the fact that the formulation of Example 4 provides processability parameters for TPO roofing applications.

[0467] Table 7

[0468]

[0469]

[0470] III. PBE-VBN terpolymer

[0471] Table 8 shows the raw materials used in the roofing formulation, including both polymers and additives. Exp.5, Exp.6, and Exp.7 are PBE-VBN terpolymers with the MFRs determined in Table 8. The polymers were prepared using different VNB contents using the methods described above and those described in U.S. Patent Application No. US2005 / 0107534. Higher VNB contents resulted in lower MFRs for the PBE polymers.

[0472] Table 8

[0473]

[0474] Table 9 shows the TPO formulations in grams. Examples C4, C5, and C6 are control examples. Example C4 contains Hifax. TM CA 10A, while embodiments C5 and C6 include Vistamaxx. TM 6100PBE. The formulation was mixed in an Intelli-Torque Brabender at a melt temperature of 200°C at low RPM to flux, then mixed at 50 RPM for 3 minutes. The batch weight of each formulation is approximately 270 grams.

[0475] Table 9

[0476]

[0477]

[0478] Table 9 (continued)

[0479] PP 7032 75 75 75 75 Braskem TI 4007G 75 Conc.80 76 75 75 75 75 75 Conc.27UHP 44 43 43 43 43 43 Total [g] 273 269 269 269 269 269 MFR 1.09 3.7 2.0 2.4 1.9 1.5 Tanδ peak -26.7 -27.3 -27.3 -28.7 -29.2 -29.2 Flexural modulus 166 315 328 330 356 325 Flexural modulus (std dev) 25.4 22 45 23 20 26

[0480] Figure 5 This is a graph illustrating the tensile viscosity of the six compositions. The US-EV method described above was used. Compared to Comparative Examples C5 and C6, the formulations of the present invention in Examples 6 and 7 exhibit significantly higher melt strength, very close to the performance of Comparative Example C4. This indicates that the formulations of the present invention in Examples 6 and 7 provide processability parameters for TPO roofing applications.

[0481] Table 10 provides tensile viscosity data for control examples C4, C5, and C6 and embodiments E5, E6, and E7 of the present invention. At shorter calibration times, i.e., 0.001 seconds, the test method may exhibit high levels of noise. At longer calibration times, where tensile viscosity measurements are more consistent and accurate, embodiments E6 and E7 of the present invention are comparable to control sample C4 and significantly greater than PBE control compositions C5 and C6.

[0482] Table 10

[0483] Correction time [s] C4 C5 C6 E5 E6 E7 0.001 NA 284.2 3281.7 10734.8 3189.4 282.2 0.01 3086.0 3383.3 5506.8 12149.6 7219.3 1212.8 0.1 24228.2 10435.9 20276.9 18945.1 18837.3 17703.3 1 58866.7 19290.0 41582.9 42656.2 50399.1 48322.3

[0484] Table 11 illustrates the percentage increase in tensile viscosity for Examples E5, E6, and E7 of the present invention compared to control sample C5. Sample C5 comprises a PBE with an MFR of 3, while each example comprises a PBE with an MFR less than 2. Achieving a PBE with a lower MFR corresponds to an improvement in tensile viscosity of approximately 80%–150% or more across the entire test range. This further supports the fact that the PBE formulations of Examples E5, E6, and E7 of the present invention provide processability parameters for TPO roofing applications.

[0485] Table 11

[0486] Correction time [s] E5 E6 E7 0.001 3677％ 1022％ -1％ 0.01 259％ 113％ -64％ 0.1 82％ 81％ 70％ 1 121％ 161％ 151％

[0487] IV. Branched propylene-based elastomers

[0488] Exp.8, Exp.9, Exp.10, and Exp.11 are propylene-based elastomers with different branching amounts and different Mw values, prepared according to the methods described below and with the parameters described below. AOTEMPO is a free radical scavenger (4-acryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxy) available from Sigma Aldrich. 101 is a peroxide polymer initiator available from Arkema. TAIC is triallyl isocyanurate, an auxiliary agent available from Evonik.

[0489] Branched PBE Exp.8, Exp.9, Exp.10, and Exp.11 were prepared via melt blending. The branched PBE formulations were prepared in a 70cc brabender batch mixer at 100 rpm and a metal solidification temperature of 150°C. At time zero, Vis tamaxx TM 6100 was loaded into the mixer. After mixing for approximately 2-3 minutes, the free radical scavenger (AOTEMPO), the auxiliary agent (TAIC), and the peroxide ( 101) Load into the mixer. Continue mixing for another 4 minutes. For Exp. 8, first add the peroxide to Vis tamaxx. TM In 6100, the additive is added first; no free radical scavenger is used. For Exp.9, the free radical scavenger is added first, then the peroxide, and then the additive. For Exp.10, the free radical scavenger is added first, then the peroxide and the additive are added simultaneously. For Exp.11, the peroxide and the additive are added simultaneously; no free radical scavenger is used.

[0490] Table 12

[0491] Table 13 shows the raw materials used in the roofing formulation, including both polymers and additives.

[0492] Table 13

[0493] Composition C2 (wt%) MFR (g / 10min) Density (g / cc) %filler VM 6102 16 3 0.862 Exp.8 NA NA NA Exp.9 NA NA NA Exp.10 NA 4.2 NA Exp.11 NA 67.2 NA PP 7032 9 3 0.900 Conc.80 (Flame Retardant Masterbatch) NA 20％ Conc.27UHP (UV stabilizer masterbatch) NA 73％

[0494] Table 14 shows the TPO formulations, by weight percentage. Examples C7 and C8 are control examples; Example C7 contains Vistamaxx. TM 6102PBE, while embodiment C8 includes Hifax. TM CA 10A. The formulation is mixed in two stages. First, the branching process is carried out as described above at 190°C, and then the remaining TPO component (i.e., PP 7032) is added to the mixer. Then, the additives are added in the second mixing stage.

[0495] Table 14

[0496]

[0497] Figure 6 This is a graph illustrating the tensile viscosity of Comparative Example C7 and Inventive Example E11. Compared to Comparative Example C7, the inventive formulation of Example E11 exhibits higher melt strength. This indicates that the inventive formulation of Example E11, which includes long-chain branching, provides improved processability parameters for TPO roofing applications.

[0498] Table 15 provides tensile viscosity data for Comparative Example C7 and Example E11 of the present invention. Example E11 of the present invention outperforms the PBE control composition C7, which does not have long-chain branching.

[0499] Table 15

[0500] Correction time (s) C7 E11 0.1 12373.8 14796.2 1 23469.8 32635

[0501] Table 16 illustrates the percentage increase in tensile viscosity of Example E11 of the present invention compared to control sample C7. Sample C7, compared to Example E11 of the present invention, comprises PBE without long-chain branches, while each of them comprises PBE with indeed long-chain branches. Long-chain branching corresponds to an improvement in tensile viscosity of approximately 20%-30% or more across the entire test range. This further supports the addition of long-chain branching to propylene-based polymers, providing processability parameters for TPO roofing applications.

[0502] Table 16

[0503] Correction time (s) E11 0.1 19.6％ 1 39.1％

[0504] As is known to those skilled in the art, rheological data can be presented by plotting the phase angle against the absolute value of the complex shear modulus (G*) to generate a Van Gurp-Palmen plot of the complex modulus (Pa) against the phase angle (degrees). Figure 7 This is a Van Gurp-Palmen diagram (VGP diagram), which includes control samples C7 and C8 and examples E8, E9, E10, and E11 of the present invention. The Van Gurp-Palmen diagram provides a visualization of polymer elasticity. Each inventive example with long branches shows improved elasticity compared to the PBE control sample C7; that is, the phase angle of each given modulus of the inventive examples is smaller than the phase angle of the PBE control sample C7. Table 17 includes the phase angle values ​​for each example at moduli of 500 Pa and 1000 Pa. Examples E8 and E11 have performance close to or better than the commercial control sample C8; examples E9 and E10 show improved elasticity compared to the PBE control sample C7. The improved elasticity shown by the inventive examples indicates that adding long-chain branching to propylene-based polymers provides processability parameters for TPO roofing applications.

[0505] Table 17

[0506] G*(Pa) C7 C8 E8 E9 E10 E11 500 72.5 63 65 69 72 59 1000 75 68.5 69.5 72 73 65

[0507] V.PBE-g-PS

[0508] Samples were prepared according to Table 18, wherein the required amount of DCP was dissolved in styrene monomer, and then VISTAMAXX was impregnated with the styrene solution under mechanical stirring. TM Granules. Place the mixture in a sealed container and keep at room temperature for 8 hours to allow the monomers to react with Vistamax. TM Particle diffusion. All melt blending, in-situ grafting, and in-situ polymerization processes of the samples were carried out in a twin-screw extruder with a screw speed of 100 rpm. The extruder barrel temperature was set to 200°C from the feed zone to the die exit.

[0509] Table 18

[0510] Sample number <![CDATA[VISTAMAXX TM Category]]> PP (wt%) Styrene (wt%) DCP (wt%) PS-1 6102 100 0 0 PS-2 6102 90 10 0.6 PS-3 6102 80 20 1.2 PS-4 6102 70 30 1.8 PS-5 3588 80 20 1.2

[0511] GPC is used to assess changes in molecular weight. Figure 8A This describes the GPC data of the obtained polymer. Figure 8B yes Figure 8A (Enlarged image). Compared to pure Vista Maxx. TM In contrast, Mw and viscosity increase with increasing styrene content. Table 19 provides detailed information on GPC data for some samples.

[0512] Table 19

[0513] Sample number Mw(g / mol) Mn(g / mol) MWD Bulk comonomer IV (dL / g) PS-1 110,000 44,000 2.5 16 1.7 PS-3 215,000 25,000 8.8 18 2.6 PS-4 290,000 19,000 15.6 18 3.0

[0514] The blend compositions were prepared according to Table 20, wherein the MgOH2 masterbatch was prepared in ADFLEX. TM KS 311P (polypropylene impact copolymer, available from LyondellBasell) contains 30 wt% MgOH2; the UV stabilizer masterbatch contains UV stabilizer, titanium dioxide as a white pigment, and carrier resin, with a density of approximately 1.0 g / cm³. 3 The white concentrated masterbatch consists of 50 wt% titanium dioxide in propylene homopolymer. VISTAMAXX TM The preparation method of 3588-g-PS is similar to that of previous samples.

[0515] Table 20 also includes the properties of the blend. Blend C11 is comparable to compositions used in roofing membranes on the market.

[0516] Table 20

[0517]

[0518]

[0519] Due to Vista Max TM Regarding the grade selection, the tanδ peak of E12 in this embodiment of the invention is smaller than that in the control embodiment. Not limited by theory, it is believed that VISTAMAXX... TM 3588 compared to VISTAMAXX TM The much lower C2 content in 6100 and 6102 reduced the tanδ peak.

[0520] Figure 9 The graph shows the relationship between elastic modulus (E′) and temperature. Example E12 of the present invention exhibits a modulus comparable to the control blends C8, C1O, and C11 at temperatures below -40°C and a similar modulus over a temperature range of -40°C to 40°C, which is typical for TPO roofing membrane applications. Overall, the results indicate that the performance of E12 is comparable to the control samples.

[0521] Figure 10 The melt strength of the selected pure polymer is displayed. Figure 11 The melt strength of the selected blends is displayed. Tensile viscosity tests were performed at 190°C on an ARES instrument with an tensile viscosity fixture (EVF) and a Hencky rate set to 0.1 / s. A nitrogen atmosphere was used to avoid oxidative degradation. VISTAMAXX TM The melt strength of 3588-g-PS is higher than that of the control polymer VISTAMAXX. TM6102 and CA10. Furthermore, in the blends, the melt strength of Example E12 is comparable to that of blend C11, and is close to that of commercial blends.

[0522] Compared to control blend C9, Example E12 exhibits a significantly higher melt strength, equivalent to blend C11. This indicates that Example E12 meets the processability requirements for TPO roofing applications.

[0523] Figure 12 It shows a relatively pure Vista Max. TM 3588 and Vista Maxx TM DSC results of the thermal behavior of 3588-g-PS. Higher crystallization temperature means improved cycle time (or production time, as the product cures faster).

[0524] The higher melt strength makes the PP-g-PS described herein suitable for roofing applications. Furthermore, the higher crystallization temperature of the PP-g-PS described herein reduces cooling time, thus reducing the production time of the roofing material. Without being theoretically limited, it is believed that polystyrene grafting onto the polypropylene backbone simulates long-chain branching in other polypropylenes, where long-chain branching in such polymers increases melt strength and increases the crystallization temperature of the polypropylene.

[0525] Overall, the compositions and films of this specification offer an improved balance of elastic modulus (flexibility) at temperatures from -40°C to 40°C, elastic modulus at high temperatures (e.g., 100°C) (reducing roll adhesion properties), and higher melt strength (providing improved dimensional stability during tableting). If fillers are present in the composition, the improved melt strength and processability provided by the compositions of this specification can provide uniform dispersion of the fillers, resulting in a more uniform layer (film) for roofing applications, thereby providing improved physical properties of the layer (film).

[0526] Certain embodiments and features have been described using a set of upper and lower limits. It should be understood that, unless otherwise stated, a range from any lower to any upper limit is permissible. All values ​​are indicated as “about” or “approximately” and take into account experimental errors and variations expected by those skilled in the art.

[0527] If a term used in the claims is not defined above, the broadest definition given by a person skilled in the art, which is reflected in at least one printed publication or a published patent, shall be given.

[0528] Although this specification has been described with reference to various embodiments and examples, those skilled in the art who benefit from this specification will understand that other embodiments can be devised without departing from the scope and spirit of this specification.

Claims

1. A roofing composition, the composition comprising: a polymer blend, the blend comprising: a propylene-based elastomer, wherein the propylene-based elastomer has a melt flow rate of less than 3 g / 10 min according to ASTM D-1238 (2.16 kg weight @ 230 °C) and a branching index g'vis of less than 1, wherein the propylene-based elastomer has a Mw of 300,000 g / mol to 600,000 g / mol; and a thermoplastic resin; an ultraviolet light stabilizer; and a flame retardant, and wherein the roofing composition has a Henchy rate 1 s -1 has a tensile viscosity greater than 15,000 Pa-sec.

2. The roofing composition of claim 1, wherein the propylene-based elastomer has at least one of the following properties: a Mw of 500,000 g / mol to 600,000 g / mol, a melt flow rate of 0.1 dg / min to 2 dg / min according to ASTM 1238 (2.16 kg @ 230 °C), a percent crystallinity of less than 3, Density of 0.85 g / cm to 0.87 g / cm according to ASTM D-1505 3 3 Density of 0.85 g / cm to 0.87 g / cm according to ASTM D-1505​ a melt index of 0.5 g / 10 min to 3.0 g / 10 min according to ASTM D-1238 (2.16 kg @ 230 °C), and a number average molecular weight (Mn) of 150,000 g / mol to 350,000 g / mol.

3. The roofing composition of claim 1, wherein the polymer blend comprises 8 to 15 wt% ethylene, based on the total weight of the polymer blend.

4. A roofing composition, the composition comprising: a polymer blend, the blend comprising: a propylene-based elastomer, wherein the propylene-based elastomer has a branching index g'vis of less than 1 according to GPC-4D, wherein the propylene-based elastomer has a Mw of 300,000 g / mol to 600,000 g / mol; and a thermoplastic resin; an ultraviolet light stabilizer; and a flame retardant, and wherein the roofing composition has a Henchy rate 1 s -1 has a tensile viscosity greater than 15,000 Pa-sec.

5. The roofing composition of claim 4, wherein the propylene-based elastomer comprises: at least 60 wt% propylene-derived units; 0.3 to 10 wt% diene-derived units; and at least 6 wt% ethylene-derived units, wherein each wt% is based on the total weight of the propylene-based elastomer, and wherein the propylene-based elastomer has isotactic polypropylene crystallinity, a melting point as determined by DSC of 110 °C or less, and a heat of fusion of 5 J / g to 50 J / g.

6. The roofing composition of claim 5, wherein the diene is 5-vinyl-2-norbornene (VNB).

7. The roofing composition of claim 4, wherein the propylene-based elastomer is partially insoluble, and the fractions soluble at 23 °C and 31 °C have ethylene content that differs by 5 wt% or less.

8. A roofing composition, comprising: 20 wt% to 50 wt% of a propylene-based elastomer-grafted polystyrene (PBE-g-PS) based on the weight of the TPO membrane, wherein the PBE-g-PS has a crystallization temperature of 90 °C or less; 5 wt% to 50 wt% of a thermoplastic resin based on the weight of the roofing composition; an ultraviolet light stabilizer; and a flame retardant, and 9. The roofing composition of claim 8, wherein the propylene-based elastomer-grafted polystyrene (PBE-g-PS) has a crystallization temperature of 90 °C or less. wherein the roofing composition has a Henchy rate 1 s -1 has a tensile viscosity greater than 15,000 Pa-sec.

9. The roof composition of claim 8, wherein the propylene-based elastomer of the PBE-g-PS has 70 wt% to 95 wt% propylene-derived units and 5 wt% to 30 wt% of C2 or C4-C6 a-olefin-derived units.

10. The roof composition of claim 8, wherein the PBE-g-PS has at least one of the following properties: 1 wt% to 40 wt% styrene content, 1 g / 10 min to 20 g / 10 min melt flow rate according to ASTM D1238 (2.16 kg @ 230°C), 100,000 g / mol to 500,000 g / mol weight average molecular weight, 5,000 g / mol to 50,000 g / mol number average molecular weight, and 3 to 20 molecular weight distribution.

11. The roof composition of any one of claims 1-10, wherein the roof composition comprises 5 wt% to 50 wt% of the thermoplastic resin, based on the total weight of the roof membrane.

12. The roof composition of any one of claims 1-10, wherein the thermoplastic resin is polypropylene.

13. The roof composition of claim 12, wherein the polypropylene comprises a comonomer and at least 85 wt% propylene-derived units.

14. The roof composition of claim 13, wherein the comonomer is ethylene.

15. The roof composition of any one of claims 1-10, wherein the thermoplastic resin is an impact copolymer.

16. A roof composition, the composition comprising: a polymer blend, the blend comprising: a propylene-based elastomer, wherein the propylene-based elastomer has a branching index g'vis of less than 1, wherein the propylene-based elastomer has a Mw of 300,000 g / mol to 600,000 g / mol; and a thermoplastic polyolefin; an ultraviolet light stabilizer; and a flame retardant, and wherein the roofing composition has a Henchy rate 1 s -1 has a tensile viscosity greater than 15,000 Pa-sec.

17. The roof composition of claim 16, wherein the roof composition has a phase angle of 73 or less at a complex modulus G* of 1,000 Pa.

18. The roof composition of claim 16, wherein the polymer blend comprises 30 to 70 wt% of the first polyolefin, based on the total weight of the polymer blend.

19. The roof composition of claim 16, wherein the polymer blend comprises 30 to 70 wt% of the second polyolefin, based on the total weight of the polymer blend.

20. The roof composition of claim 16, wherein the first polyolefin is a propylene-based elastomer.

21. The roof composition of claim 16, wherein the second polyolefin is an impact copolymer comprising a polypropylene matrix phase and an ethylene-propylene rubber dispersed phase.

22. A roofing material, comprising: a membrane comprising the roof composition of any one of claims 1 to 21; and a base material adhered or secured to the membrane.

23. A method, comprising: blending a composition, the composition comprising: a propylene-based elastomer, wherein the propylene-based elastomer has a melt flow rate of less than 3 g / 10 min according to ASTM D-1238 (2.16 kg weight @ 230 °C) and a branching index g'vis of less than 1, wherein the propylene-based elastomer has a Mw of 300,000 g / mol to 600,000 g / mol; a thermoplastic resin; a UV stabilizer; and a flame retardant, and wherein the composition has a Henchy rate 1 s -1 has a tensile viscosity greater than 15,000 Pa-sec at 0.1 seconds.

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