Thermoplastic vulcanizate compositions containing metallocene multimodal copolymer rubbers and methods of making the same

Abstract

To provide a thermoplastic vulcanizate (TPV) composition containing a metallocene-based multimodal copolymer rubber.SOLUTION: The TPV composition comprises (a) ethylene-derived unit, from greater than 50 wt.% to less than 100 wt.% of a major polymer fraction having Mooney viscosities from about 15ML (1 + 4 @ 125 °C) to about 120ML (1 + 4 @ 125 °C), from greater than 0 wt.% to less than 50 wt.% of a minor polymer fraction having Mooney viscosities from about 120ML (1 + 4 @ 125 °C) to about 1500ML (1 + 4 @ 125 °C), average molecular weight distributions (Mw / Mn) from about 2.0 to about 4.5, an average branching index from about 0.7 to about 1.0; And less than 10 parts by weight of oil per 100 parts by weight of the multimodal copolymer rubber; (b) at least one other oil; (c) at least one thermoplastic polymer; and (d) a cure system comprising at least one cure material and at least one curative.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Patent No. 63 / 047,640, filed July 2, 2020, which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION

[0002] Embodiments of the present invention relate generally to thermoplastic vulcanizate compositions. More particularly, such embodiments relate to thermoplastic vulcanizate compositions containing metallocene-based multimodal copolymer rubbers that are essentially free of extender oils, and methods for making the same. [Background technology]

[0003] Thermoplastic vulcanizates (TPVs) comprise dynamically cured blends of rubber and thermoplastic polymers. The rubber can be dispersed in a thermoplastic polymer phase as finely divided rubber particles. These compositions often advantageously demonstrate many of the properties of thermoset elastomers, but can also be processed using common thermoplastic molding techniques such as injection molding, extrusion, and blow molding. Thermoplastic vulcanizates can be prepared by dynamically vulcanizing, or curing, the rubber with a curative material while mixing the rubber with the thermoplastic polymer.

[0004] Ethylene-based elastomers or rubbers, such as ethylene-propylene-diene (EPDM) elastomers, are often suitable for use in TPV applications. However, such elastomers are typically very high molecular weight polymers and inherently have very high viscosities, e.g., Mooney viscosities greater than 200 ML (1+4 @ 125°C). This inherent property of EPDM can lead to problems related to the processability of the elastomer. For example, efficient blending of EPDM elastomers during the TPV manufacturing process can be difficult to achieve. Extender oils are often added to EPDM elastomers to "bulk" the rubber phase and reduce the apparent viscosity of the TPV.

[0005] The required level of extender oil depends on the molecular weight of the EPDM elastomer, but is usually sufficient to reduce the apparent viscosity of the oil-extended EPDM to a Mooney viscosity of about 100 ml (1 + 4 @ 125°C) or less. Very high molecular weight EPDM elastomers suitable for use in TPV manufacturing processes typically contain about 50 to 125 phr of extender oil. Incorporation of such large amounts of extender oil can be difficult because the oil often cannot be completely dissolved in the EPDM elastomer, resulting in phase separation between the EPDM elastomer and the extender oil.

[0006] An exemplary EPDM elastomer that contains extender oil to improve processability is Vistalon™ 3666, available from ExxonMobil, which is a unimodal, high molecular weight amorphous elastomer prepared using a Ziegler-Natta catalyst. Amorphous elastomers often exhibit high creep flow and agglomeration and are therefore available as bales larger than particulates.

[0007] Due to the problems associated with Ziegler-Natta based EPDM elastomers, metallocene-based EPDM elastomers suitable for use in TPV manufacturing processes have been developed. Such EPDM elastomers are prepared using metallocene catalysts and typically have relatively narrow molecular weight distributions, relatively linear molecules, and high crystallinity. As such, these metallocene-based EPDM elastomers have a viscosity of less than about 90 ML (1+4@125 These EPDM elastomers can have an overall Mooney viscosity of 100-150°C and exhibit good processability without the need for extender oils. Because these EPDM elastomers are highly crystalline in nature, they advantageously exhibit low creep flow and agglomeration and can therefore be sold as particulates. Unfortunately, TPV products containing current metallocene-based EPDM elastomers can have inferior physical properties compared to Ziegler-Natta-based EPDM elastomers. Furthermore, the physical properties of such TPV products are often a trade-off between the two extremes.

[0008]

[0008] The TPV process typically involves adding an EPDM elastomer, filler, thermoplastic polymer, and a cure system to a reactor, followed by melt-mixing the components and curing or dynamically vulcanizing the EPDM elastomer. The cure system can include a curative material and a curative. Many of these materials do not melt and can adversely affect physical properties if not added as a very fine powder or dust. However, fine dusts tend to become airborne and can have serious industrial hygiene implications. Additionally, organic dust clouds can pose a dust explosion hazard. Summary of the Invention [Problem to be solved by the invention]

[0009]

[0009] Therefore, there remains a need for TPV compositions that can be economically prepared on a mass scale using metallocene-based EPDM elastomers that have a good balance of properties while maintaining industrial hygiene and safe operating conditions. [Means for solving the problem]

[0010]

[0010] A thermoplastic vulcanizate composition containing a metallocene-based multimodal copolymer rubber essentially free of extender oil and a method for making the same are provided. In one or more embodiments, the thermoplastic vulcanizate composition comprises (a) ethylene-derived units; from greater than 50% to less than 100% by weight, based on the total weight of the multimodal copolymer rubber, of a major polymer fraction having a Mooney viscosity of from about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C); from greater than 0% to less than 50% by weight, based on the total weight of the multimodal copolymer rubber, of a minor polymer fraction having a Mooney viscosity of from about 120 ML (1+4@125°C) to about 1500 ML (1+4@125°C); an average molecular weight distribution (Mw / Mn) of from about 2.0 to about 4.5; ), an average branching index of about 0.7 to about 1.0, and less than 10 parts by weight of oil per 100 parts by weight of the multimodal copolymer rubber; (b) at least one other oil; (c) at least one thermoplastic polymer; and (d) a cure system comprising at least one curative material and at least one curative.

[0011] In one or more embodiments, a method for preparing a thermoplastic vulcanizate composition includes introducing a multimodal copolymer rubber into a reactor, the multimodal copolymer rubber comprising: (a) ethylene-derived units; from greater than 50 wt.% to less than 100 wt.%, based on the total weight of the multimodal copolymer rubber, of a major polymer fraction having a Mooney viscosity of from about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C); and from greater than 0 wt.% to less than 50 wt.%, based on the total weight of the multimodal copolymer rubber, of a major polymer fraction having a Mooney viscosity of from about 120 ML (1+4@125°C) to about 1500 ML (1+4@125°C). the multimodal copolymer rubber containing a minor polymer fraction of about 2.0 to about 4.5, an average molecular weight distribution (Mw / Mn) of about 2.0 to about 4.5, an average branching index of about 0.7 to about 1.0, and less than 10 parts by weight of oil per 100 parts by weight of the multimodal copolymer rubber; (b) introducing into a reactor simultaneously or sequentially with the multimodal copolymer rubber at least one thermoplastic polymer, at least one other oil, and a curing system; (c) melt-mixing the multimodal copolymer rubber, the at least one thermoplastic polymer, and the curing system; and (d) curing the multimodal copolymer rubber.

[0012]

[0012] In one or more alternative embodiments, a method for producing a thermoplastic vulcanizate includes producing a pre-vulcanized blend, the pre-vulcanized blend comprising: (a) ethylene-derived units; from greater than 50 wt% to less than 100 wt%, based on the total weight of the multimodal copolymer rubber, of a major polymer fraction having a first Mooney viscosity of about 15 ML (1+4 @ 125°C) to about 120 ML (1+4 @ 125°C); from greater than 0 wt% to less than 50 wt% of a minor polymer fraction having a second Mooney viscosity lower than the first Mooney viscosity; and 100 parts by weight of the multimodal copolymer rubber. The method may include the steps of (a) introducing a pre-vulcanization blend into a reactor, (b) a multimodal copolymer rubber containing less than 10 parts by weight of oil per 100 parts by weight of the pre-vulcanization blend, and (c) at least one powdery curative, (d) introducing at least one thermoplastic polymer, at least one other oil, and at least one curative material into the reactor simultaneously or sequentially with the pre-vulcanization blend, melt-mixing the pre-vulcanization blend, the at least one thermoplastic polymer, and the at least one curative material, and curing the multimodal copolymer rubber. The pre-vulcanization blend may optionally contain at least one powdery filler, the at least one thermoplastic polymer, the at least one other oil, the at least one curative material, or a combination thereof. DETAILED DESCRIPTION OF THE INVENTION

[0013] It should be understood that the following disclosure describes several exemplary embodiments for implementing various features, structures, and / or functions of the present invention. While exemplary embodiments of components, arrangements, and configurations are described below to simplify the disclosure, these exemplary embodiments are provided merely as examples and are not intended to limit the scope of the present invention. In addition, the present disclosure may repeat reference numerals and / or letters in the various exemplary embodiments and throughout the figures described herein. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various exemplary embodiments and / or configurations discussed in the figures. Moreover, the exemplary embodiments listed below may be combined in any combination, i.e., any element of one exemplary embodiment may be used in any other exemplary embodiment without departing from the scope of the present disclosure.

[0014] Additionally, certain terms are used throughout the following description and claims to refer to particular components. Those skilled in the art will understand that, unless otherwise specified herein, various entities may refer to the same component by different names, and as such, the nomenclature for the components described herein is not intended to limit the scope of the present invention. Furthermore, the nomenclature used herein is not intended to distinguish between components that differ in name but function.

[0015] In the following description and claims, the terms "including" and "comprising" are used open-endedly and should therefore be understood to mean "including, but not limited to." The phrase "consisting essentially of" means that the composition as described / claimed does not contain any other component that would substantially alter its properties by more than 5%, and in any case does not contain any other component to a level of more than 3% by weight.

[0016]

[0016] The term "or" includes both exclusive and inclusive cases, i.e., "A" or "B" is intended to be synonymous with "at least one of A and B," unless expressly specified otherwise in this specification.

[0017] The indefinite articles "a" and "an" refer to both singular (i.e., "one") and plural referents (i.e., one or more) unless the context clearly dictates otherwise. For example, in embodiments using "an olefin" includes embodiments in which one, two, or more olefins are used, unless there is a contradiction or the context clearly indicates that only one olefin is used.

[0018] The terms "wt%" mean weight percentage, "vol%" mean volume percentage, "mol%" mean mole percentage, "phr" means based on 100 parts rubber, "ppm" means parts per million, and "ppm wt" and "wppm" are used interchangeably and mean parts per million by weight. All concentrations herein are expressed based on the total amount of the composition in question unless otherwise specified.

[0019] The term "α-olefin" refers to any straight or branched chain compound of carbon and hydrogen having at least one double bond between the α and β carbon atoms. For purposes of this specification and the claims appended hereto, when a polymer or copolymer is said to comprise an α-olefin, e.g., a polyα-olefin, the α-olefin present in the polymer or copolymer is the polymerized form of the α-olefin.

[0020] The term "polymer" refers to two or more repeating units / mers or units, either the same or different. The term "homopolymer" refers to a polymer having the same units. The term "copolymer" refers to a polymer having two or more units that are different from each other, including terpolymers and the like. The term "terpolymer" refers to a polymer having three units that are different from each other. The term "different" refers to units that differ from each other by at least one atom, or are isomeric. Similarly, the definition of polymer, as used herein, includes homopolymers and copolymers and the like. For example, when a copolymer is said to have a "propylene" content of 10 wt% to 30 wt%, it is understood that the repeating units / mers or simply units in the copolymer are derived from propylene during the polymerization reaction, and that the derived units are present at 10 wt% to 30 wt% based on the weight of the copolymer.

[0021] The terms "rubber" and "elastomer" are used interchangeably and refer to elastic polymeric materials produced using polymerization techniques. The term "vulcanizate" refers to rubber that has been at least partially cured or reinforced. The term "thermoplastic" refers to a polymeric material that becomes moldable at elevated temperatures and solidifies upon cooling. The term "thermoplastic vulcanizate" refers to a material that contains an at least partially vulcanized polymer dispersed in a thermoplastic.

[0022] The nomenclature of these elements and groups used herein follows the periodic table used by the International Union of Pure and Applied Chemistry since 1988. An example of a periodic table is shown on the inside cover page of Advanced Inorganic Chemistry, 6th Edition, by F. Albert Cotton et al. (John Wiley & Sons, Inc., 1999).

[0023]

[0023] A detailed description will now be provided. Each claim in the following set forth claims defines an independent invention, which, for infringement purposes, is recognized as including equivalents to the various elements or limitations specified in the claim. Depending on the context, all references to the "invention" may, in some cases, refer only to certain specific embodiments. In other cases, it will be recognized that references to the "invention" refer to the subject matter recited in one or more of the claims, but not necessarily all of them. Each invention (including specific embodiments, variations, and examples) will now be described in more detail below, but the invention is not limited to these embodiments, variations, or examples, which, when combined with the information in this disclosure and publicly available information and techniques, will enable one of ordinary skill in the art to make and use the invention.

[0024] Thermoplastic vulcanizate composition

[0024] Thermoplastic vulcanizate (TPV) compositions are disclosed that can include a multimodal copolymer rubber essentially free of extender oil, at least one other oil, at least one thermoplastic polymer, and a cure system containing at least one curing material and at least one curative. The TPV composition can also contain fillers, if desired. As used herein, the term "essentially free of extender oil" means that the multimodal copolymer rubber contains less than about 10 parts by weight of extender oil per 100 parts by weight of rubber (also referred to as "parts per hundred rubber" or phr), preferably less than about 5 phr, and more preferably less than about 1 phr. The TPV composition can contain particles of vulcanized rubber (i.e., cured rubber) dispersed in a continuous phase or matrix of thermoplastic polymer.

[0025] The multimodal copolymer rubber comprises ethylene-derived units; a major polymer fraction of from about 50% to about 100% by weight, based on the total weight of the multimodal copolymer rubber, having a Mooney viscosity of from about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C); a minor polymer fraction of from about 0% to about 50% by weight, based on the total weight of the multimodal copolymer rubber, having a Mooney viscosity of from about 120 ML (1+4@125°C) to about 1500 ML (1+4@125°C); an average molecular weight distribution (M) of from about 1.5 to about 4.5; w / M n and an average branching index (BI) of about 0.7 to about 1.0. Correspondingly, the multimodal copolymer rubbers may have a relatively narrow molecular weight distribution and an overall Mooney viscosity of less than about 90 ML (1+4 @ 125°C), indicating that they are easily processable and therefore require little or no extender oil. The multimodal copolymer rubbers may be of a generally linear structure, as indicated by the average branching index, or may be completely amorphous or semi-crystalline in nature.

[0026] Multimodal copolymer rubbers can be prepared by polymerization using metallocene catalysts. The resulting rubber may be in the form of particles having a particle size of about 0.5 mm to about 15.0 mm, preferably about 1.0 mm to about 10.0 mm, and more preferably about 1.5 mm to about 8.0 mm. As used herein, "particle size" refers to the weight average particle size. These particles may be dispersed, for example, at greater than about 0.1 phr, to prevent the rubber particles from sticking together. Such particulates may include, for example, polyethylene particulates, inorganic fillers such as calcium carbonate, talc, clay, and the like.

[0027] Surprisingly, the TPV compositions can have a well-balanced set of properties that are superior to conventional metallocene-based TPV compositions. Without being bound by theory, it is believed that the attributes of the multimodal copolymer rubber described above may contribute to these improved properties. For example, the TPV compositions can have a relatively uniform phase morphology, excellent surface aesthetics as indicated by a relatively low extrusion surface roughness (ESR), and relatively high bond strength to other TPV materials. In particular, the TPV compositions can have an ESR of about 20 to about 200, preferably about 25 to about 100, and most preferably about 28 to about 80. The TPV compositions can also have bond strengths of about 1.0 MPa to about 5.0 MPa, more preferably about 1.5 MPa to about 4.5 MPa, and most preferably about 1.8 MPa to about 4.0 MPa. Due to the relatively uniform phase morphology, the TPV compositions can exhibit good molding performance and can therefore be used in applications requiring extrusion, injection molding, blow molding, and compression molding.

[0028] The TPV compositions also unexpectedly exhibit excellent hardness, elongation at break, and tensile strength performance. In particular, the TPV compositions may have a hardness of from about 30 Shore A to about 55 Shore D, preferably from about 35 Shore A to about 50 Shore D, and more preferably from about 40 Shore A to about 45 Shore D. The TPV compositions may have a hardness of from about 250% to about 900%, preferably from about 275% to about 800%. %, more preferably about 300% to about 750% elongation at break. The TPV composition may also have an ultimate tensile strength of about 2.0 MPa to about 15.0 MPa, preferably about 2.5 MPa to about 14.0 MPa, more preferably about 3.0 MPa to about 13.0 MPa.

[0029] Additionally, the TPV composition may have a relatively low relative density, i.e., specific gravity, and a relatively low apparent viscosity, i.e., applied shear stress / shear rate. The specific gravity of the TPV composition may range from about 0.86 to about 1.40, preferably from about 0.87 to about 1.25, and more preferably from about 0.88 to about 1.2. The apparent viscosity of the TPV composition may be in the range of 1200 s -1When measured at a shear rate of about 30 Pa*s to about 150 Pa*s, preferably about 40 Pa*s to about 140 Pa*s, and more preferably about 50 Pa*s to about 130 Pa*s.

[0030] The test methods used to determine the aforementioned properties of the TPV compositions are described in the Examples below.

[0031] The well-balanced properties of TPV compositions allow them to be used in a wide variety of applications, for example, in the automotive, industrial, and consumer markets. For example, TPV compositions can be used in the manufacture of hoses, sealants, gap fillers, floor mats, window seals, and weather seals. TPV compositions can also be used in foam applications by subjecting the TPV compositions to commonly known foam-forming techniques, such as microcell, chemical, or water foaming.

[0031]

[0032] In one or more embodiments, a method for producing a TPV composition may include introducing a multimodal copolymer rubber disclosed herein into a reactor, such as a twin-screw extruder; introducing at least one thermoplastic polymer, at least one oil, and a curing system into the reactor simultaneously or sequentially with the multimodal copolymer rubber; melt-mixing the multimodal copolymer rubber, the at least one thermoplastic polymer, and the curing system; and curing the multimodal copolymer rubber. As used herein, "melt-mixing" refers to placing in a molten state while mixing, and "curing" refers to solidification of the melt due to an increase in molecular weight as a result of a reaction. In some embodiments, at least one oil may be introduced before curing the multimodal copolymer rubber, and additional oil may be introduced into the reactor after curative injection. In this case, the ratio of oil introduced before curing to oil introduced after curing may be less than about 1.00, less than about 0.85, or less than about 0.70.

[0032]

[0033] In one or more additional embodiments, a pre-vulcanization blend of the multimodal copolymer rubber and one or more other components, particularly components in powder form (such as curatives and powdered fillers), can be prepared separately in a first step. A second step can then include introducing the pre-vulcanization blend into a reactor and simultaneously or sequentially introducing at least one thermoplastic polymer, at least one oil, and at least one curing material or curative into the reactor. The pre-vulcanization blend, at least one thermoplastic polymer, and at least one curing material or curative can then be melt-mixed together, and the multimodal copolymer rubber can be cured. Alternatively, the at least one thermoplastic polymer, at least one oil, and / or at least one curing material or curative can be included in the pre-vulcanization blend instead of being added to the reactor separately from the blend.

[0033]

[0034] Pre-vulcanization blends containing ingredients in powder form can be prepared in a separate step or even at a location separate from the TPV process, eliminating the risk of dust explosions and the potential adverse industrial hygiene impacts of using fine powders during the vulcanization process.

[0034] Multimodal Copolymer Rubber

[0035] The content of the multimodal copolymer rubber in the TPV composition may range from about 10 wt% to about 60 wt%, preferably from about 15 wt% to about 50 wt%, and more preferably from about 20 wt% to about 40 wt%, based on the total weight of the TPV composition. The multimodal copolymer rubber may include ethylene-derived units, α-olefin-derived units, and diene-derived units, preferably non-conjugated diene-derived units.

[0035]

[0036] The α-olefin-derived units are C3 to C6 units such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof. 20The α-olefin-derived units h may be or may include α-olefins. The α-olefin-derived units h are preferably propylene, 1-butene, 1-hexene, 1-octene, or a combination thereof, more preferably propylene. The non-conjugated diene-derived units may be or may include 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, dicyclopentadiene (DCPD), norbornadiene, 5-vinyl-2-norbornene (VNB), or a combination thereof. Examples of suitable ethylene-propylene-diene (EPDM) rubbers include Vistalon™ 5601, Vistalon™ 5702, Vistalon™ 7001, Vistalon™ 9301, and the like, commercially available from ExxonMobil.

[0036]

[0037] The amount of ethylene-derived units present in the multimodal copolymer rubber may range from about 45 wt% to about 80 wt%, preferably from about 50 wt% to about 75 wt%, and more preferably from about 55 wt% to about 70 wt%, based on the total weight of the rubber. The amount of diene-derived units present in the TPV multimodal copolymer rubber may range from about 1 wt% to about 10 wt%, preferably from about 2 wt% to about 8 wt%, and more preferably from about 3 wt% to about 6 wt%, based on the total weight of the rubber. The α-olefin-derived units may account for the remainder of the polymer units.

[0037]

[0038] Ethylene content can be determined by FTIR, ASTM D3900, and is not corrected for diene content. ENB diene content can be determined by FTIR, ASTM D6047. Other dienes include: 1 It can be measured by 1 H NMR.

[0038]

[0039] Multimodal copolymer rubbers may be characterized by a multimodal molecular weight distribution, which may simply be referred to as multimodal molecular weight. In one or more embodiments, the multimodal copolymer rubber may comprise at least two fractions. Multimodality may be defined as the M w GPC LALLS It can manifest itself as two distinct peaks in the signal, or as a main peak and a shoulder peak. This multimodality can arise by blending a very high molecular weight component with a very low molecular weight component, either as a result of step-growth polymerization or by physical blending techniques.

[0039]

[0040] The multimodal copolymer rubber may comprise a major polymer fraction of greater than about 50 wt% to less than about 100 wt%, preferably greater than about 55 wt% to less than about 95 wt%, and more preferably greater than about 60 wt% to less than about 90 wt%. The major polymer fraction may have a Mooney viscosity of from about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C), preferably from about 25 ML (1+4@125°C) to about 90 ML (1+4@125°C), and more preferably from about 30 ML (1+4@125°C) to about 80 ML (1+4@125°C), based on the total weight of the multimodal copolymer rubber.

[0040]

[0041] The multimodal copolymer rubber contains a minor amount of poly(ethylene glycol) of greater than about 0 wt% to less than about 50 wt%, preferably greater than about 5 wt% to less than about 45 wt%, more preferably greater than about 10 wt% to less than about 40 wt%. The minor polymer fraction may have a Mooney viscosity of about 120ML (1+4@125°C) to about 1500ML (1+4@125°C), preferably about 120ML (1+4@125°C) to about 1100ML (1+4@125°C), and more preferably about 120ML (1+4@125°C) to about 700ML (1+4@125°C), based on the total weight of the multimodal copolymer rubber.

[0041]

[0042] The multimodal copolymer rubber may have an overall Mooney viscosity of from about 20ML (1+4@125°C) to about 90ML (1+4@125°C), preferably from 25ML (1+4@125°C) to about 85ML (1+4@125°C), more preferably from about 30ML (1+4@125°C) to about 80ML (1+4@125°C).

[0042]

[0043] As used herein, Mooney viscosity is reported using the format: Rotor([warm-up time (min)] + [shear time (min)] @ measurement temperature (°C)), where ML(1 + 4 @ 125°C) indicates Mooney viscosity determined using an ML or large rotor according to ASTM D1646-99 (at a temperature of 125°C with a warm-up time of 1 minute and a shear time of 4 minutes).

[0043]

[0044] Unless otherwise specified, Mooney viscosity is reported herein as ML (1+4 @ 125°C) in Mooney units according to ASTM D-1646. However, Mooney viscosity values ​​above about 100 generally cannot be measured under these conditions. In this event, higher temperatures (i.e., 150°C) may be used, resulting in longer shear times (i.e., 1+8 @ 125°C or 150°C). More preferably, Mooney measurements for purposes herein are performed using a non-standard small rotor. The non-standard rotor design is employed to vary the Mooney scale, allowing the use of the same Mooney instrumentation with polymers having Mooney viscosities ranging from about 100 ML (1+4 @ 125°C). For purposes herein, this modified Mooney determination method is referred to as Mooney Small Thin (MST).

[0044]

[0045] ASTM D1646-99 specifies the rotor dimensions to be used in the Mooney instrument cavity. This method allows for both large and small rotors, differing only in diameter. These different rotors are referred to in ASTM D1646-99 as ML (Mooney Large) and MS (Mooney Small). However, EPDM rubber can be produced with such high molecular weights that the torque limit of the Mooney instrument may be exceeded using these standard rotors. In these instances, tests are performed using the smaller, more narrow MST rotor. Typically, when using MST rotors, tests are also performed at different time constants and temperatures. The preheat time is changed from the standard 1 minute to 5 minutes, and the test is performed at 200°C instead of the standard 125°C. Values ​​obtained under these modified conditions are referred to herein as MST(5+4@200°C). Note: The 4-minute runtime at the end at which the Mooney reading is taken remains the same as the standard conditions. When MST is measured at (5+4@200°C) and ML is measured at (1+4@125°C), one MST point is approximately equivalent to 5 ML points. Accordingly, for approximate conversion between the two measurement scales, multiply the MST (5+4@200°C) Mooney value by 5 to obtain the equivalent of the approximate ML (1+4@125°C) value.

[0045]

[0046] The MST rotor used herein has a diameter of 30.48 + / - 0.03 mm, a thickness of 2.8 + / - 0.03 mm (determined from the top of the serrations), and a shaft diameter of 11 mm or less. The rotor has a serrated face and edge with square grooves approximately 0.8 mm wide and approximately 0.25 to 0.38 mm deep, with a 1.6 mm cut in the center. The serrated edge consists of two sets of grooves perpendicular to each other, thereby forming a square crosshatch. The rotor is designed so that the centerline of the rotor disk is + / - 0.25 It is centered in the die cavity to coincide with the centerline of the die cavity within a tolerance of 1 / 2 mm. A spacer or shim may be used to raise the shaft to the midpoint, consistent with typical practice in the art for Mooney determinations. The wear point (a conical protrusion located in the center of the rotor's top surface) is machined flat on the rotor face.

[0046]

[0047] The Mooney viscosity of the multimodal copolymer rubber can be determined herein from a blend of polymers. The Mooney viscosity of a particular component of the blend is herein determined by the following formula (1): log ML=n A logML A +n B logML B (1) where logarithms are to the nearest ten and ML is the individual Mooney viscosity ML of two polymers A and B (each A and M.L. B is the Mooney viscosity of the blend of A represents the wt% fraction of polymer A in the blend, and n B represents the wt% fraction of polymer B in the blend] It is obtained using the relationship shown below.

[0047]

[0048] Equation (1) can be used to determine the Mooney viscosity of a blend containing a high Mooney viscosity polymer A and a low Mooney viscosity polymer B, having a measurable Mooney viscosity under the (1+4@125°C) condition: ML, ML A and n A By knowing the ML B The value of can be calculated.

[0048]

[0049] However, for polymers with high Mooney viscosity (i.e., Mooney viscosity greater than 100 ML (1+4 @ 125°C)), ML A The Mooney viscosity of the low molecular weight polymer in the blend can then be determined using Equation 1 above, where ML Ais expressed by the following relation (2): ML A (1+4@125℃)=5.13*MST A (5+4@200℃) (2) is determined using

[0049]

[0050] In these or other embodiments, the Mooney viscosity of high molecular weight polymers can be determined by using a Mooney Viscometer Model VR / 1132 (Ueshima Seisakusho Co., Ltd.), which can measure Mooney viscosity up to 400 units.

[0050]

[0051] The multimodal copolymer rubbers disclosed herein have a weight average molecular weight (M) of from about 100,000 g / mole to about 450,000 g / mole, preferably from about 125,000 g / mole to about 400,000 g / mole, and more preferably from about 150,000 g / mole to about 350,000 g / mole. w The multimodal copolymer rubber may also have an average molecular weight distribution (MWD) of from about 2.0 to about 4.5, preferably from about 2.0 to about 4.0, and more preferably from about 2.0 to about 3.5. As used herein, MWD is also referred to as polydispersity and is the weight average molecular weight (M) divided by the number average molecular weight of the polymer. w / M n) represents the molecular weight distribution (MWD). MWD can be determined using gel permeation chromatography on a Waters 150 gel permeation chromatograph equipped with a Chromatix KMX-6 using a differential refractive index (DRI) detector and an online light scattering photometer. Determinations can be performed at 135°C using 1,2,4-trichlorobenzene as the mobile phase and one of the Shodex (Showa Denko America, Inc.) polystyrene gel columns numbered 802, 803, 804, or 805. This technique is described in detail in LIQUID CHROMATOGRAPHY OF POLYMERS AND RELATED MATERIALS III 207 (J. Cazes, ed., Marcel Dekker, 1981), which is incorporated herein by reference. For further information, see U.S. Pat. No. 4,540,753 (Cazewith et al.) and the references cited therein, as well as Verstrate et al., 21 Macromolecules 3360 (1998). The data disclosed herein include , no correction for the diffusing column is used.

[0051]

[0052] M w / M n is preferably calculated from the elution time. These numerical analyses are performed using the commercially available Beckman / CIS customized LALLS software in conjunction with a standard gel permeation package. The calculations follow the work of F.A. Bovey in "Polymer Conformation and Configuration", Academic Press, New York, 1969. 13 C NMR was used to characterize the polymer. w / M n The reference to M w is the value reported using the LALLS detector, and M n is the value reported using the DRI detector.

[0052]

[0053] The relative degree of branching of a polymer can be determined using the average branching index factor (BI), also called the average branching index. The multimodal copolymer rubbers disclosed herein can have a BI of from about 0.7 to about 1.0, preferably from about 0.8 to about 0.99, and more preferably from about 0.85 to about 0.98, indicating a near linearity in structure.

[0053]

[0054] BI can be calculated using a series of four experimental measurements of polymer properties in solution, as disclosed in VerStrate, Gary, "Ethylene-Propylene Elastomers," Encyclopedia of Polymer Science and Engineering, 6, 2nd ed. (1986), which is incorporated herein by reference. The four measurements include: (i) weight average molecular weight (M), measured using a low angle light scattering detector (LALLS) in combination with gel permeation chromatography (GPC); w ) (referred to herein as "M w (ii) weight average molecular weight (M) determined using a differential refractive index (DRI) detector in combination with GPC w ) (referred to herein as "M w (iii) viscosity average molecular weight (M) determined using a differential refractive index (DRI) detector in combination with GPC v ) (referred to herein as "M v (iv) the intrinsic viscosity (also called inherent viscosity, abbreviated as IV) measured in decalin at 135°C. The first three measurements (i, ii, and iii) are obtained by GPC using a filtered dilute solution of the polymer in trichlorobenzene.

[0054]

[0055] BI is calculated by the following formula (3):

[0055]

number

[0056] [In the formula, M v、br =(IV / k)1 / a where "k" is a constant measured from linear polymers as described by Paul J. Flory in PRINCIPLES OF POLYMER CHEMISTRY 310 (1953), the sum is over the slices in the distribution, and "a" is the Mark-Houwink constant (equal to 0.759 for ethylene-propylene-diene rubber in decalin at 135°C). can be determined using

[0057] From equation (3), it follows that the BI for a linear polymer is 1.0. For branched polymers, the degree of branching is specified relative to the linear polymer. For a given number average molecular weight M n , (M w ) 分岐 >(M w ) 直鎖 In this case, the BI of a branched polymer is less than 1.0, with smaller BI values ​​indicating higher branching levels. In instances where measurement of IV in decalin is not possible, the IV is measured in tandem with the DRI and LALLS detectors in a so-called DPC-3D instrument. A viscosity detector aligned with the viscometer may be used to measure the viscosity for comparison with the present disclosure, where the "k" and "a" values ​​are selected to be appropriate for the GPC solvent used in making the determination.

[0058]

[0057] The multimodal copolymer rubbers can be produced using any suitable polymerization method known in the art. For example, the multimodal copolymer rubbers can be produced using a series of reactors described below, using parallel reactors, or by forming different proportions of rubber via mechanical blending.

[0059]

[0058] When the multimodal copolymer rubber is produced by direct polymerization, the catalyst used is preferably a single-site catalyst, which generally has sufficient activity and life to polymerize in a homogeneous environment at a temperature of at least 100°C, so that fractions of different molecular weights can be produced in continuous reactors arranged in series by temperature and / or hydrogen control.

[0060] In one or more embodiments, the catalyst may be a bulky ligand transition metal catalyst, also known as a "metallocene" catalyst. The bulky ligand may contain a large number of bonding atoms, preferably carbon atoms, forming a group (which may be a ring with one or more optional heteroatoms). The bulky ligand may be a cyclopentadienyl derivative, which may be mononuclear or polynuclear. One or more bulky ligands may be bonded to the transition metal atom. According to prevailing scientific theories, the bulky ligands are hypothesized to remain in place during the course of polymerization, resulting in a uniform polymerization effect. Other ligands, such as hydrocarbyl groups or halogen leaving groups, may be bonded or coordinated to the transition metal, preferably removable by the catalyst or activator. Removal of any such ligand is believed to create a coordination site at which olefin monomers can be inserted into the polymer chain. The transition metal atom may be a transition metal of Group IV, V, or VI of the periodic table of the elements. The transition metal atom is preferably a Group IVB atom. The transition metal in the active catalytic state is in the 4+ oxidation state, while the positively charged cation, generally a neutral precursor transition metal complex, may be in a lower oxidation state. For a more detailed description of suitable metallocene complexes, see U.S. Pat. No. 6,211,312.

[0061] The catalyst may be a compound represented by the following formula (4): [L] m M[X] n (4) where L is a bulky ligand, X is a leaving group, M is a transition metal, and m and n are such that the total ligand valence corresponds to the transition metal valence. The catalyst may be derived from a compound represented by the formula: Preferably, the catalyst is tetracoordinated such that the compound is ionizable to a 1+ valence state. The ligands L and X may be bridged together, or when two ligands L and / or X are present, they may be bridged. The metallocene may be a full sandwich compound having two ligands L that are cyclopentadienyl groups, or a half sandwich compound having only one ligand L that is a cyclopentadienyl group.

[0062] Metallocenes can include compounds containing one or more cyclopentadienyl moieties in combination with a transition metal of the periodic table of the elements. The metallocene catalyst component can be represented by the general formula (Cp)mMRnR'p, where Cp is a substituted or unsubstituted cyclopentadienyl ring, M is a transition metal of Group IV, V, or VI, R and R' are independently selected from halogens, hydrocarbyl groups, or hydrocarboxyl groups having from 1 to 20 carbon atoms, m=I-3, n=O-3, P=O-3, and the sum of m+n+p is equal to the oxidation state of M. In one or more embodiments, useful metallocenes include those containing Group IV transition metals. Examples include biscyclopentadienyl derivatives of the formula (II), preferably zirconium or hafnium. See WO 1999 / 41294. These derivatives may contain fluorenyl and cyclopentadienyl ligands (linked by single carbon and silicon atoms) (see WO 1999 / 45040 and WO 1999 / 45041). In certain embodiments, the Cp ring is unsubstituted and / or the bridge contains alkyl substituents, such as alkylsilyl substituents, to aid in the alkane solubility of the metallocene. See WO 2000 / 24792 and WO 2000 / 24793, which are incorporated herein by reference in their entirety. Other metallocene catalyst systems may exhibit polymerization capabilities suitable for producing the multimodal copolymer rubbers disclosed herein. For example, EP 418044 uses a monocyclopentadienyl compound equivalent to that of EP 416815. Similar compounds are described in EP 420436. WO 1997 / 03992 describes catalysts in which a single Cp species and phenol are linked by a C or Si bond, such as MeC(Cp)(3-tBu-5-Me-2-phenoxy)TiCl. WO 2001 / 05849 discloses Cp-phosphinimine catalysts such as (Cp)((tBu)P=N-)TiCl.

[0063] The catalyst may be used with a cocatalyst or activator which, according to accepted theory, is believed to aid in the formation of the metallocene cation. Aluminum alkyl-derived activators may be used, of which methylalumoxane is a commonly known example. This material can also function as a scavenger and is available commercially from Albemarle or Schering.

[0064] Non- or weakly coordinating anions (NCAs) are preferred, generating activators of the type described in EP 277004. These activators are often used and are described in conjunction with metallocenes in the above-mentioned patent references for metallocenes. NCAs can be generated from precursors that may be neutral salts containing stabilizing anions or nonionic Lewis bases capable of removing groups from transition metal complexes to form stabilizing anions. Depending on the method of generation, NCAs can have three or four ligands substituted on the metal atom, such as boron or aluminum. The ligands are preferably fluorinated, more preferably perfluorinated, aromatic moieties (such as phenyl, bisphenyl, or naphthyl). See also WO 2001 / 42249, which describes other suitable NCA structures and is incorporated herein by reference in its entirety.

[0065] The high catalyst activity and low catalyst concentrations typically used on an industrial scale can result in increased susceptibility to poisons. Poisons can enter the polymerization reactor as impurities in the solvent or monomer feed, or can be generated by secondary processes such as catalyst quenching operations, which are generally carried out with water after the proper polymerization is complete. These poisons can be deactivated by using alkylaluminum scavengers such as triethylaluminum (TEAL), titanium boron aluminum (TIBAL), or n-octylaluminum. The presence of poisons can also be addressed by installing molecular sieves or other purification equipment as part of the recycle in a continuous reactor layout.

[0066]

[0066] The conditions between the first and second reactors can be differentiated as described in WO 1999 / 45047. Generally, terpolymers (containing suitable dienes) are produced by polymerizing ethylene, higher α-olefins (e.g., propylene, 1-(2-methyl-2-propanediol), ... The polymer may be made using a mixture of the first and second polymer components (butene, 1-hexene, and 1-octene), as well as non-conjugated dienes. Optionally, additional catalyst may be fed to the second reactor. The final polymer product may contain a mixture of the first and second polymer components.

[0067] After polymerization and catalyst deactivation or extinction, the solvent can be removed by one or more flushing steps or liquid phase separation as described in EP 552945, thus reducing the solvent content to 0.1 wt % or less. The solvent can be recycled and the polymer can be baled or pelletized.

[0068] thermoplastic polymer The content of the thermoplastic polymer in the TPV composition may range from about 20 phr to about 600 phr, preferably from 25 to about 500 phr, and more preferably from about 30 to about 400 phr. Thermoplastic polymers can include those commonly used in the manufacture of thermoplastic vulcanizates. For example, these thermoplastic polymers can also be referred to as thermoplastic resins or non-functionalized thermoplastics and can include solid, generally high molecular weight polymer resins. Examples of suitable thermoplastic polymers can include, or include, crystalline, semi-crystalline, and crystallizable polyolefins, olefin copolymers, and non-olefin polymers.

[0069] The thermoplastic polymer may be or may include a polyolefin homopolymer, a polyolefin copolymer, or a combination thereof, having a melt flow rate (MFR) of about 0.10 to about 100.00, preferably about 0.25 to about 50.00, and more preferably about 0.50 to about 30.00. In one or more embodiments, the thermoplastic polymer may be formed by polymerizing ethylene or an α-olefin (such as propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, or a mixture thereof). Copolymers of ethylene and propylene, as well as copolymers of ethylene and / or propylene with another α-olefin, such as 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, or mixtures thereof, are also contemplated. Specifically included are copolymers of propylene with ethylene or the higher α-olefins disclosed above or C 10 ~C 20These include reactor, impact, and random copolymers with diolefins. The comonomer content of these propylene copolymers may be from 1 wt% to about 30 wt% of the polymer's weight (see, for example, U.S. Pat. No. 6,867,260 B2). Examples of suitable copolymers are commercially available from ExxonMobil under the tradename VISTAMAXX™. Other polyolefin copolymers include copolymers of olefins and styrene, such as styrene-ethylene copolymers, or polymers of olefins and α,β-unsaturated acids or α,β-unsaturated esters, such as polyethylene-acrylate copolymers. Non-olefin thermoplastic polymers include polymers and copolymers of styrene, α,β-unsaturated acids, α,β-unsaturated esters, and mixtures thereof. For example, polystyrene, polyacrylate, and polymethacrylate can be used. Blends or mixtures of two or more polyolefin thermoplastics, as described herein, or those with other polymerization modifiers, are also suitable. Useful thermoplastic polymers can also include impact and reactor copolymers.

[0070] In one or more embodiments, thermoplastic resins can include propylene-based polymers, including solid, generally high molecular weight polymer resins that comprise primarily units derived from the polymerization of propylene. In certain embodiments, at least 75%, in other embodiments at least 90%, in other embodiments at least 95%, and in other embodiments at least 100%. At least 97% of the units of the propylene-based polymers are derived from the polymerization of propylene. In certain embodiments, these polymers comprise homopolymers of propylene.

[0071]

[0071] In certain embodiments, the propylene-based polymer may also include units derived from the polymerization of ethylene and / or α-olefins (such as 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof).

[0072] In one or more embodiments, the propylene-based polymers can include semi-crystalline polymers. In one or more embodiments, these polymers can be characterized by a crystallinity of at least 25 wt%, in other embodiments at least 55 wt%, in other embodiments at least 65 wt%, and in other embodiments at least 70 wt%. Crystallinity can be determined by dividing the heat of fusion of a sample by the heat of fusion of a 100% crystalline polymer, which for polypropylene is assumed to be 209 J / g. In one or more embodiments, these polymers can be characterized by an Hf of at least 52.3 J / g, in other embodiments greater than 100 J / g, in other embodiments greater than 125 J / g, and in other embodiments greater than 140 J / g.

[0073] In one or more embodiments, useful propylene-based polymers have an M of from about 50 to about 2000 kg / mole, and in other embodiments from about 100 to about 600 kg / mole. w These may be characterized by an M of from about 25 to about 1000 kg / mole, and in other embodiments from about 50 to about 300 kg / mole, as measured by GPC using polystyrene standards. n It can be characterized by:

[0074] In one or more embodiments, useful propylene-based polymers may have a melt flow rate (MFR) (ASTM D-1238, 2.16 kg @ 230° C.) of less than 50 dg / min, in other embodiments less than 10 dg / min, and in other embodiments less than 5 dg / min. In these or other embodiments, the propylene-based polymers may have an MFR of at least 0.1 dg / min, in other embodiments 0.2 dg / min, and in other embodiments at least 0.5 dg / min.

[0075] In one or more embodiments, useful propylene-based polymers have a melting temperature (T m The propylene-based polymer may have a glass transition temperature (T) of from about -10°C to about 10°C, in other embodiments from about -3°C to about 5°C, and in other embodiments from about 0°C to about 2°C. g In one or more embodiments, the propylene-based polymer may have a crystallization temperature (T) of at least about 75°C, in other embodiments at least about 95°C, in other embodiments at least about 100°C, in other embodiments at least 105°C, and in other embodiments in the range of 105°C to 130°C. c ).

[0076]

[0076] Propylene-based polymers can be synthesized using any suitable polymerization technique known in the art. For example, propylene-based polymers can be polymerized using Ziegler-Natta catalysts or single-site organometallic catalysts (such as metallocene catalysts).

[0077] In certain embodiments, the propylene-based polymer comprises a homopolymer of highly crystalline isotactic or syndiotactic polypropylene. The polypropylene may have a density of about 0.89 to about 0.91 g / cc, with highly isotactic polypropylene having a density of about 0.90 to about 0.91 g / cc. High and ultra-high molecular weight polypropylenes with fractional melt flow rates can also be used. One or more In some embodiments, the polypropylene resin may be characterized by an MFR (ASTM D-1238; 2.16 kg @ 230°C) of 10 dg / min or less, in other embodiments 1.0 dg / min or less, and in other embodiments 0.5 dg / min or less.

[0078] Examples of suitable polypropylene polymers include PP5341 (0.8 MFR), PP1074NKE1 (20 MFR), and PP3854E1 (24 MFR) available from ExxonMobil, and PP F180A (17 MFR) available from Braskem America, Inc. Examples of suitable polyethylene polymers include LD051.LQ (0.25 MI), LL3001.32 (1 MFR), LL6407.67 (6.8 MI), and HD7845.30 (0.45 MI) available from ExxonMobil. Post-consumer recycled polyolefins can also be used. Examples of suitable post-consumer recycled polypropylene and polyethylene include KW308A (8MFR), KW622 (10MFR and 20MFR), KWR621FDA (10MFR and 20MFR), KWR102 (0.5MI), and KWR105 (4MI), available from KW Plastics.

[0079] oil The oil content in the TPV composition may range from about 10 phr to about 250 phr, preferably from about 50 phr to about 200 phr, and most preferably from about 75 phr to about 150 phr. The oil may be or may include mineral oil, synthetic oil, or a combination thereof.

[0080] Mineral oils suitable for use in the TPV compositions include aromatic, naphthenic, paraffinic, isoparaffinic oils, and combinations thereof. The mineral oils may be treated or untreated. Useful mineral oils are available under the trade names SUNPAR™ 150, available from HollyFrontier; Paramount™ 6001, available from Chevron Corporation; and PLASTOL™ 517, available from ExxonMobil.

[0081] In one or more embodiments, suitable synthetic oils can include polymers and oligomers of butene, such as isobutene, 1-butene, 2-butene, butadiene, and mixtures thereof. In one or more embodiments, these oligomers have an M of from about 300 g / mole to about 9000 g / mole, and in other embodiments, from about 700 g / mole to about 1300 g / mole. n In one or more embodiments, these oligomers may include isobutenyl mer units. Exemplary synthetic oils may include polyisobutylene, poly(isobutylene-co-butene), and mixtures thereof. In one or more embodiments, suitable synthetic oils may also include polylinear α-olefins, multi-branched α-olefins, hydrogenated poly-α-olefins, and mixtures thereof.

[0082] In one or more embodiments, suitable synthetic oils may include synthetic polymers or copolymers having a viscosity greater than about 20 cp, in other embodiments greater than about 100 cp, and in other embodiments greater than about 190 cp, as measured by a Brookfield viscometer according to ASTM D-4402 at 38° C. In these or other embodiments, the viscosity of these oils may be less than 4000 cp, and in other embodiments less than 1000 cp.

[0083] Useful synthetic oils are available under the tradename Polybutene™, commercially available from Soltex, and Indopol™, commercially available from Innouvene. White synthetic oils commercially available from ExxonMobil under the trade name SPECTRASYN™ (ExxonMobil) may also be used. Oils described in U.S. Pat. No. 5,936,028 may also be used. It is believed that synthetic oils can provide enhanced low-temperature performance. High-temperature performance may also be enhanced based on molecular structure.

[0084] Hardening system The TPV composition may contain a cure system including a curing material and a curing agent. The curing material may serve to cure or toughen the multimodal copolymer rubber during the thermoplastic vulcanization process. The curing agent may be used in conjunction with the curing material to accelerate the curing process. The amount of curing material present in the TPV composition may range from about 0.1 phr to about 20.0 phr, preferably from about 0.5 phr to about 10.0 phr, and more preferably from about 1.0 phr to about 5.0 phr. The amount of curing agent present in the TPV composition may range from about 0.10 phr to about 10.00 phr, preferably from about 0.25 phr to about 6.00 phr, and more preferably from about 0.50 phr to about 3.00 phr.

[0085]

[0085] Examples of suitable curable materials include phenolic polymers, silicon-containing materials, and peroxides (ie, free radical curable materials).

[0086] Useful phenolic polymer curing materials are disclosed in U.S. Patent Nos. 2,972,600, 3,287,440, 5,952,425, and 6,437,030. In one or more embodiments, the phenolic polymer may include a resole polymer, which can be prepared by condensation of an alkyl-substituted or unsubstituted phenol with an aldehyde, preferably formaldehyde, in an alkaline medium or by condensation of a difunctional phenol dialcohol. The alkyl substituent of the alkyl-substituted phenol can contain 1 to about 10 carbon atoms. Dimethylolphenols or phenolic polymers substituted in the para position with alkyl groups containing 1 to about 10 carbon atoms may also be used.

[0086]

[0087] An exemplary phenolic polymer used as the curing material is a blend of octylphenol-formaldehyde and nonylphenol-formaldehyde polymers. In one or more embodiments, the blend may contain about 25 to about 40 wt% octylphenol-formaldehyde and about 75 to about 60 wt% nonylphenol-formaldehyde, and in other embodiments, about 30 to about 35 wt% octylphenol-formaldehyde and about 70 to about 65 wt% nonylphenol-formaldehyde. In one embodiment, the blend may contain about 33 wt% octylphenol-formaldehyde and about 67 wt% nonylphenol-formaldehyde, each containing methylol groups. This blend can be solubilized in paraffin oil at about 30% solids without phase separation.

[0087]

[0088] Useful phenolic polymers are available from Schenectady International under the trade names SP-1044 and SP-1045 and may be referred to as alkylphenol-formaldehyde polymers. SP-1045 is believed to be a blend of octylphenol and a nonylphenol-formaldehyde polymer containing methylol groups. SP-1044 and SP-1045 polymers are believed to be essentially free of halogen substituents or residual halogen compounds. By essentially free of halogen substituents, it is meant that the synthesis of the polymer produces a non-halogenated polymer that may contain only trace amounts of halogen-containing compounds.

[0088]

[0089] Examples of suitable phenolic polymers include those represented by the following general formula (5):

[0089] [ka]

[0090] [wherein Q is a divalent group selected from the group consisting of -CH2- and -CH2-O-CH2-, m is zero or a positive integer of 1 to 20, and R' is an organic group] In one embodiment, Q is a divalent group -CH2-O-CH2-, m is zero or a positive integer from 1 to 10, and R' is an organic group having fewer than 20 carbon atoms. In another embodiment, m is zero or a positive integer from 1 to 10, and R' is an organic group having 4 to 12 carbon atoms.

[0091] In one or more embodiments, the phenolic polymer is used in conjunction with a curing agent such as stannous chloride and a metal oxide, such as zinc oxide, which is believed to function as a scorch retarder and acid scavenger and / or polymer stabilizer. A suitable type of zinc oxide is commercially available from Horsehead, Corp. under the trade name Kadox™ 911. The zinc oxide may have an average particle size of about 0.05 to about 0.15 μm. In other embodiments, a curing agent, such as hydrotalcite, that acts as an acid scavenger may be added downstream of the cure.

[0092]

[0091] The free radical curing material can include peroxides such as organic peroxides. Examples of organic peroxides include di-tert-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α,α-bis(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (DBPH), 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, lauroyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, and mixtures thereof. Diaryl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, and mixtures thereof can also be used. Other suitable peroxides include azo initiators, such as Luazo™ AP, available from Archema. Useful peroxides and their use in the dynamic vulcanization of thermoplastic vulcanizates are disclosed in U.S. Pat. No. 5,656,693, which is incorporated herein by reference. In certain embodiments, cure systems such as those described in U.S. Pat. No. 6,747,099, U.S. Patent Application Publication No. 2004 / 0195550, and International Patent Application Publication Nos. 2002 / 28946, 2002 / 077089, and 2005 / 092966 can also be used.

[0093] In one or more embodiments, the free radical curing material can be used in conjunction with one or more curing agents. Suitable curing agents include high vinyl polydienes or polydiene copolymers, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, sulfur, N,N'-m-phenylene dimaleimide, N,N'-p-phenylene dimaleimide, divinylbenzene, trimethylolpropane trimethacrylate, tetramethylene glycol diacrylate, trifunctional acrylic esters, dipentaerythritol pentacrylate, multifunctional acrylates, delayed cyclohexanedimethanol diacrylate esters, multifunctional methacrylates, acrylate and methacrylate metal salts. , multifunctional acrylates, multifunctional methacrylates, oximers (such as quinone dioximes), or mixtures thereof. A combination of a high-vinyl polydienes and an α,β-ethylenically unsaturated metal carbonate is useful, as disclosed in U.S. Patent Application Serial No. 11 / 180,235. The curing agent may also be used neat or with a carrier. For example, suitable multifunctional acrylates or multifunctional methacrylates for use with a carrier are disclosed in U.S. Patent Publication No. 11 / 246,773. Alternatively, the curing material and / or curing agent may be premixed with the plastic prior to compounding the thermoplastic vulcanizate, as described in U.S. Patent No. 4,087,485.

[0094]

[0093] The silicon-containing curing material can include a silicon hydride compound having at least two SiH groups. Examples of silicon hydrides include methylhydrogenpolysiloxane, methylhydrogendimethylsiloxane copolymers, alkylmethyl-co-methylhydrogenpolysiloxane, bis(dimethylsilyl)alkane, bis(dimethylsilyl)benzene, and mixtures thereof. Such hydrosilylation-curing materials are particularly useful with unimodal copolymer rubbers containing diene units derived from 5-vinyl-2-norbornene.

[0095]

[0094] Examples of curing agents that act as catalysts for hydrosilylation include Group VIII transition metals and complexes of these metals. For example, palladium, rhodium, and platinum can be used as curing agents. Useful silicon-containing curing materials and curing agents are disclosed in U.S. Patent No. 5,936,028.

[0096] Those skilled in the art will appreciate that the amount of curative material used to form a TPV composition may vary depending on the chemical nature of the curative material and / or curative used in conjunction. In these or other embodiments, the amount of curative material used may vary depending on the type of unimodal copolymer rubber used and the crosslinkable units present in the rubber.

[0097] filling material

[0096] Fillers may be included in the TPV composition in an amount of from about 0 phr to about 300 phr, preferably from about 0 phr to about 200 phr, and more preferably from about 0 phr to about 100 phr. Examples of suitable fillers include carbon black, clay, talc, silica, titanium dioxide, calcium carbonate, and combinations thereof.

[0098] Such fillers, having relatively high specific gravity, are often used in conventional TPV compositions containing rubber available in bales as an inexpensive way to break up the bales fed to the TPV reactor. In one or more embodiments, the filler can be significantly reduced or even eliminated to obtain a lower density TPV composition. This filler reduction is possible because the multimodal copolymer rubbers disclosed herein can be fed in the form of smaller particles rather than bales, thereby eliminating the need for a splitting agent.

[0099] Other additives In one or more embodiments, the TPV composition can include a polymeric processing additive having a very high melt flow index. Suitable polymeric processing additives include linear and branched polymers having an MFR of greater than about 500 dg / min, greater than about 750 dg / min, greater than about 1000 dg / min, greater than about 1200 dg / min, or greater than about 1500 dg / min. Mixtures of various branched or linear polymeric processing additives, as well as mixtures of both linear and branched polymeric processing additives, may also be used. Useful linear polymeric processing additives include polypropylene homopolymers. Useful branched polymeric processing additives include diene-modified polypropylene polymers. Suitable processing additives are described in U.S. Pat. Also disclosed in US Pat. No. 451,915.

[0100] The TPV composition can optionally contain other additives such as compatibilizers, pigments, colorants, dyes, dispersants, flame retardants, antioxidants, conductive particles, UV inhibitors, UV stabilizers, adhesion promoters, fatty acids, esters, paraffin waxes, neutralizing agents, metal deactivators, tackifiers, calcium stearate, moisture absorbers, stabilizers, light stabilizers, light absorbers, coupling agents such as silanes and titanates, plasticizers, lubricants, screening agents, antiblocking agents, antistatic agents, waxes, blowing agents, nucleating agents, slip agents, acid scavengers, lubricants, adjuvants, surfactants, crystallization aids, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, wetting agents, cure inhibitors, reinforcing and non-reinforcing fillers, and combinations thereof, as well as other processing aids commonly known in the rubber compounding art. These additives may be present in an amount of up to about 50 wt% of the total TPV composition.

[0101] Vulcanization Process

[0100] TPV compositions can be prepared by dynamic vulcanization of a multimodal copolymer rubber in the presence of an unvulcanized thermoplastic polymer. Dynamic vulcanization can include a vulcanization or curing process in which the rubber can be crosslinked under conditions of high shear at a temperature above the melting point of the thermoplastic polymer. In one embodiment, the rubber can be simultaneously crosslinked and dispersed as particulates in a thermoplastic matrix, although other morphologies can also exist.

[0102] In one or more embodiments, dynamic vulcanization can be achieved using a continuous process, which can include processes in which dynamic vulcanization of the rubber is achieved continuously, thermoplastic vulcanization product is continuously removed or collected from the system, and / or one or more raw materials or ingredients are continuously fed to the system, during the time it is desired to produce or manufacture the product.

[0103]

[0102] In one or more embodiments, continuous dynamic vulcanization can be achieved in a continuous mixing reactor (also referred to as a continuous mixer). A continuous mixing reactor can include a reactor to which components can be continuously fed and product can be continuously removed. Examples of continuous mixing reactors include twin-screw or multi-screw extruders, such as ring extruders. Methods and apparatus for continuously preparing TPV compositions are described in U.S. Patent Nos. 4,311,628, 4,594,390, 5,656,693, 6,147,160, and 6,042,260, which are incorporated herein by reference, and WO 2004 / 009327 A1. It has been discovered that methods using low shear rates can also be used. As the blend passes through various barrel sections or locations in the continuous reactor, the temperature of the blend can be varied, as is commonly known in the art. In particular, temperatures within the cure range can be controlled or manipulated depending on the half-life of the curing materials used.

[0104] In one or more embodiments, preparation of the TPV composition can be accomplished by introducing each component of the TPV composition into a continuous mixing reactor for vulcanization. In other embodiments, certain components are combined to form a pre-vulcanization blend, and then this blend is introduced into a continuous mixing reactor along with other components not included in the pre-vulcanization blend. Preferably, the pre-vulcanization blend contains components including a powder and its binder, such as a multi-modal copolymer rubber that can be dusted with the powder, a filler, and a curative, although the pre-vulcanization blend can contain any of the components used to prepare the TPV composition. [Example]

[0105]

[0104] The foregoing discussion can be further illustrated with reference to the following non-limiting examples. Six TPV compositions (Examples 1-6) were prepared containing one of the metallocene-based EPDM rubbers (ie, M-EPDM I and M-EPDM II) shown in Table 1 below. M-EPDM I is Vistalon™ 5601, and M-EPDM II is Vistalon™ 5702, both commercially available from ExxonMobil. Specific properties of M-EPDM I and M-EPDM II are listed in Table 1. M-EPDM I and M-EPDM II are non-oil-extended multimodal EPDM copolymers prepared using advanced metallocene catalyst technology and are available in pellet form. These copolymers are often referred to as inverse bimodal copolymers, having a minor (less than 50 wt%) polymer fraction with a Mooney viscosity greater than 120 ML (1+4 @ 125°C) and a major (more than 50 wt%) polymer fraction with a Mooney viscosity less than 120 ML (1+4 @ 125°C). The overall Mooney viscosity of these copolymers is about 90 ML (1+4 @ 125°C) or less. They also have a diene content of about 5 wt.%, a diene-free ethylene content (C2) of about 64 wt.% or greater, an MWD of less than 3.5, and a BI of greater than 0.85.

[0106] Two comparative TPV compositions (Comparative Examples 1-2) containing Ziegler-Natta EPDM rubber (ZN-EPDM) were also produced, as shown in Table 1 below. The ZN-EPDM is Vistalon™ 3666, commercially available from ExxonMobil. The ZN-EPDM is a 75 phr oil-extended, unimodal, branched EPDM copolymer prepared using a conventional Ziegler-Natta catalyst. Specific properties of the ZN-EPDM are listed in Table 1. The ZN-EPDM has a Mooney viscosity (ML, 1+4 @ 125°C) of about 50 after the addition of oil, an intrinsic viscosity in decalin at 135°C of about 4 dl / g, an M of about 850 kg / mole, and a viscoelasticity of about 1000 kJ / mol. w , approximately 170 kg / mole M n , MWD greater than 5, and a BI of about 0.5. ZN-EPDM also has a diene-free ethylene (C2) content of about 64 wt.%, and a diene content of about 4.2 wt.%.

[0107]

[0107]

[0108] [Table 1]

[0109] Table 2 below lists the amounts of specific metallocene-based EPDM rubbers used in Examples (Ex.) 1-6 and ZN-EPDM rubbers used in Comparative Examples (C.Ex.) 1-2. The TPV compositions of Ex. 1-6 and C.Ex. 1-2 were prepared by dynamically vulcanizing the rubber in a twin-screw extruder. The solid components, i.e., rubber, thermoplastic polyolefin mixture, curative material, curative, and filler, were added to the feed throat of the extruder and blended via melt mixing, thereby achieving a molten thermoplastic polyolefin mixture and curing the rubber. The thermoplastic polyolefin used was a mixture of polypropylene and polyethylene. The specific amounts of thermoplastic polyolefin used in the TPV compositions of Ex. 1-6 of the present invention were varied as shown in Table 2 to achieve similar hardness levels and overall balance of physical properties and processing capabilities as the TPV compositions of C.Ex. 1-2. In Ex. 1-6 and C. Ex. 1-2, the curing material used was a resol-type phenolic resin containing a blend of octylphenol and nonylphenol formaldehyde (0.5-10 phr). The curing agents used were zinc oxide and stannous chloride (0.5-5 phr). In Ex. 1-6, carbon black (1-40 phr) was used as the primary filler. In C.Ex.1 and C.Ex.2, calcium carbonate (0-100 phr) was used as the second inorganic mineral filler. In C.Ex.1 and C.Ex.2, carbon black (1-40 phr) was used as the first filler and clay (0-100 phr) was used as the second inorganic mineral filler.

[0110] Paraffin oil was added to the extruder before and after curing in the amounts listed in Table 2. Because the TPV compositions of Exs. 1-2 were prepared with oil-extended rubber, more oil (2-10 times greater) was present in the rubber before curing than after curing. In contrast to conventional TPV compositions, the TPV compositions of Exs. 1-6 were made with less oil added before curing and more oil after curing, allowing for in-process oil extension of the non-oil-extended metallocene EPDM rubber. This in-process oil extension is believed to help achieve optimal TPV phase morphology and thus provide a good overall balance of physical and aesthetic properties for the TPV compositions of Exs. 1-6 of the present invention.

[0111]

[0110]

[0112] [Table 2]

[0113] Various properties of the TPV compositions of Ex. 1-6 and C.Ex. 1-2 were determined as follows and are listed in Table 3 below. Specific gravity was measured according to TPE0105 under ISO 1183. Hardness was determined according to TPE0189 under ISO 868 at a time interval of 15 seconds. LCR viscosity was determined according to SOP-211 under ISO 11443 at 204°C. Compression set was measured at room temperature (RT) and at 70°C for 22 hours at 25% compression. The modulus at 100% elongation (M100), ultimate tensile strength, and elongation at break (%) were determined according to ISO 37 using an Instron testing machine at 50 mm / min at 23°C.

[0114] Extrusion Surface Roughness (ESR) is reported as the arithmetic mean of the surface irregularities (Ra) in microinches. Surface irregularities were measured as follows: Approximately 1 kg (2 lbs.) of the TPV composition to be tested was fed into a 2.54 cm (1 inch) or 3.81 cm (1.5 inch) diameter extruder equipped with a 24:1 length / diameter shaft with a compression ratio of 3.0 to 3.5. The extruder was fitted with a 25.4 mm (1 inch) wide x 0.5 mm (0.019 inch) thick x 7 to 10 mm (0.25 to 0.40 inch) long strip die. A breaker plate was used with the die, but no screen pack was placed before the breaker plate. The approximate temperature profile of the extruder was as follows: Zone 1 = 180°C (feed zone); Zone 2 = 190°C; Zone 3 = 200°C; Zone 4 = 205°C (die zone). Once the zone temperature was reached, the shaft was turned on. The shaft speed was set to maintain an output of approximately 50 g / min. For the first 5 minutes of extrusion, the extruder was run and the extruded material was discarded. A strip approximately 30.5 cm (12 inches) in length was extruded onto a flat substrate located directly below and in contact with the underside of the die. Three representative samples were collected in this manner. ESR was measured on the samples using a model EMD-04000-W5 Surfanalyzer System 4000 containing a general-purpose probe with a 200 mg stylus force and a Surfanalyzer appropriate tip type EPT-01049 (0.025 mm (0.0001 inch) stylus force radius).

[0115] The bond strength of C.Ex.1 to the TPV composition was measured by first preparing joint dog-bone specimens and then testing them in an Instron machine. The joint dog-bone specimens were prepared by directly injection molding one half of the specimen with the TPV composition being tested and the other half with the TPV composition of C.Ex.1. The substrate half of the TPV composition of C.Ex.1 was prepared by cutting an entire injection-molded dog-bone in half.

[0116]

[0114]

[0117] [Table 3]

[0118] Surprisingly, a good balance of properties was obtained with the TPV compositions of Exs. 1-6 of the present invention, which contain non-oil-extended metallocene EPDM rubber. The physical, processing, and aesthetic performance of the TPV compositions of Exs. 1-6 was unexpectedly better than or comparable to that of the TPV compositions of C.Exs. 1-2, which contain oil-extended Ziegler-Natta EPDM rubber, and generally had similar density levels. For example, the hardness values ​​of the TPV compositions of Exs. 1-6 were advantageously higher than those of the TPV compositions of C.Exs. 1-2, and the ESR values ​​of Exs. 1-5 were advantageously lower. Additionally, the bond strength of the TPV composition of Ex. 3 was surprisingly higher than that of the TPV compositions of C.Exs. 1-2. For the TPV compositions of Ex. 1-6, ultimate tensile strength values ​​were greater than 5.5, elongation at break values ​​were greater than 395%, compression set was less than 35% at RT and less than 60% at 70°C, and ESR values ​​were generally less than 55 μin (for Ex. 1-5). Processing and aesthetic performance were evaluated at a shear rate of 200 -1 The apparent viscosity, as measured by LCR at 1000 W / m², was desirably in the range of about 300-500 Pa*s. Additionally, the TPV compositions of Ex. 5-6 of the present invention demonstrated an excellent overall balance of properties, resulting in reduced density.

[0119] List of embodiments

[0116] The present disclosure can further include any one or more of the following non-limiting embodiments.

[0120] 1. (a) Ethylene-derived units; a major polymer fraction having a Mooney viscosity of about 15 ML (1+4 @ 125°C) to about 120 ML (1+4 @ 125°C) that is greater than 50 wt% and less than 100 wt%, based on the total weight of the multimodal copolymer rubber; A thermoplastic vulcanizate composition comprising: a multimodal copolymer rubber comprising: greater than 0 wt% and less than 50 wt% by weight of a minor polymer fraction having a Mooney viscosity of from about 120 ML (1+4@125°C) to about 1500 ML (1+4@125°C); an average molecular weight distribution (Mw / Mn) of from about 2.0 to about 4.5; an average branching index of from about 0.7 to about 1.0; and less than 10 parts by weight of oil per 100 parts by weight of the multimodal copolymer rubber; (b) at least one other oil; (c) at least one thermoplastic polymer; and (d) a cure system comprising at least one curative material and at least one curative.

[0121]

[0118] 2. A thermoplastic vulcanizate composition of embodiment 1, wherein the multimodal copolymer rubber is formed using a metallocene catalyst and comprises from about 45 wt% to about 80 wt% ethylene-derived units; from about 1 wt% to about 10 wt% non-conjugated diene-derived units; and the remainder α-olefin-derived polymer units, and has an overall Mooney viscosity of from about 20 ML (1+4 @ 125°C) to about 90 ML (1+4 @ 125°C), all weight percentages being based on the total weight of the multimodal copolymer rubber.

[0122] 3. The thermoplastic vulcanizate composition of embodiment 1 or 2, further comprising particles of vulcanized rubber dispersed in the continuous phase or matrix of at least one thermoplastic polymer. 4. The thermoplastic vulcanizate composition of embodiments 1 to 3, wherein the multimodal copolymer rubber is in the form of particles having a particle size of from about 0.5 mm to about 15.0 mm.

[0123]

[0121] 5. The vulcanizate composition of embodiments 1 to 4, wherein the at least one thermoplastic polymer comprises polypropylene, polyethylene, a polyethylene copolymer, a polypropylene copolymer, a copolymer of ethylene and propylene, or a combination thereof, and the amount of the at least one thermoplastic polymer in the thermoplastic vulcanizate composition is from about 20 phr to about 600 phr.

[0124] 6. The thermoplastic vulcanizate composition of embodiment 5, wherein the polypropylene comprises recycled polypropylene. 7. The thermoplastic vulcanizate composition of embodiment 5, wherein the polyethylene comprises recycled polyethylene.

[0125] 8. The thermoplastic vulcanizate composition of embodiments 1 to 7, wherein the amount of the at least one other oil in the thermoplastic vulcanizate composition is from about 10 phr to about 250 phr. 9. The thermoplastic vulcanizate composition of embodiments 1 to 8, wherein the at least one curing material comprises a phenolic polymer present in the thermoplastic vulcanizate composition in an amount from about 0.1 phr to about 20.0 phr.

[0126] 10. The thermoplastic vulcanizate composition of embodiments 1 to 9, further comprising a filler present in the thermoplastic vulcanizate composition in an amount from about 0 phr to about 300 phr.

[0127] 11. Hardness of about 30 Shore A to about 55 Shore D, elongation at break of about 250% to about 900%, ultimate tensile strength of about 2.0 MPa to about 15.0 MPa, 1200 s -1 11. The thermoplastic vulcanizate composition of embodiment 1 to 10, further comprising an apparent viscosity of about 30 Pa*s to about 150 Pa*s at RT, a specific gravity of about 0.86 to about 1.40, a bond strength of about 1.0 MPa to about 5.0 MPa, and an extrusion surface roughness of about 20 to about 200.

[0127]

[0128] 12. A method for producing a thermoplastic vulcanizate composition, comprising the steps of introducing a multimodal copolymer rubber into a reactor, the multimodal copolymer rubber comprising: ethylene-derived units; a major polymer fraction having a Mooney viscosity of about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C) of greater than 50 wt% to less than 100 wt%, based on the total weight of the multimodal copolymer rubber; and a Mooney viscosity of about 120 ML (1+4@125°C) to about 1500 ML (1+4@125°C) of greater than 0 wt% to less than 50 wt%, based on the total weight of the multimodal copolymer rubber. a minor polymer fraction having an average molecular weight distribution (Mw / Mn) of about 2.0 to about 4.5; an average branching index of about 0.7 to about 1.0; and less than 10 parts by weight of oil per 100 parts by weight of multimodal copolymer rubber; introducing, simultaneously with or sequentially to the multimodal copolymer rubber, at least one thermoplastic polymer, at least one other oil, and a curing system into a reactor; melt-mixing the multimodal copolymer rubber, the at least one thermoplastic polymer, and the curing system; and curing the multimodal copolymer rubber.

[0128]

[0129] 13. The method of embodiment 12, wherein the step of curing the multimodal copolymer rubber forms particles of rubber dispersed in a continuous phase or matrix of at least one thermoplastic polymer.

[0129]

[0130] 14. The method of embodiment 12 or 13, comprising introducing at least one other oil prior to the step of curing the multimodal copolymer rubber, and further comprising introducing an additional oil following curing of said multimodal copolymer rubber, wherein the ratio of the at least one other oil to the additional oil is less than about 1.

[0130]

[0131] 15. The process of embodiments 12 to 14, wherein the multimodal copolymer rubber is formed using a metallocene catalyst and comprises about 45 wt % to about 80 wt % units derived from ethylene, about 1 wt % to about 10 wt % units derived from non-conjugated dienes, the remainder polymeric units derived from α-olefins, and has an overall Mooney viscosity of about 20 ML (1+4 @ 125°C) to about 90 ML (1+4 @ 125°C), all weight percentages being based on the total weight of the multimodal copolymer rubber.

[0131]

[0132] 16. The method of embodiments 12 to 15, wherein the multimodal copolymer rubber is in the form of particles having a particle size of about 0.5 mm to about 15.0 mm.

[0133] 17. The method of embodiments 12 to 16, wherein the at least one thermoplastic polymer comprises polypropylene, polyethylene, a polyethylene copolymer, a polypropylene copolymer, a copolymer of ethylene and propylene, or a combination thereof, and the amount of the at least one thermoplastic polymer in the thermoplastic vulcanizate composition is from about 20 phr to about 600 phr.

[0132]

[0134] 18. The method of embodiment 17, wherein the polypropylene comprises recycled polypropylene and the polyethylene comprises recycled polyethylene.

[0135] 19. The method of embodiments 12 to 18, wherein the amount of the at least one other oil in the thermoplastic vulcanizate composition is from about 10 phr to about 250 phr, the cure system comprises at least one curing material and at least one curing agent, and the at least one curing material comprises a phenolic polymer present in the thermoplastic vulcanizate composition in an amount from about 0.1 phr to about 20.0 phr.

[0133]

[0136] 20. The process of embodiments 12 to 19, further comprising introducing a filler into the reactor in an amount of from about 0 phr to about 300 phr simultaneously or sequentially with respect to the multimodal copolymer rubber.

[0134]

[0137] 21. A method for producing a thermoplastic vulcanizate, comprising the steps of: preparing a pre-vulcanization blend, the pre-vulcanization blend comprising: (a) ethylene-derived units; a major polymer fraction having a first Mooney viscosity of about 15 ML (1+4 @ 125°C) to about 120 ML (1+4 @ 125°C), from greater than 50 wt% to less than 100 wt%, based on the total weight of the multimodal copolymer rubber; a minor polymer fraction having a second Mooney viscosity lower than the first Mooney viscosity, from greater than 0 wt% to less than 50 wt%; a multimodal copolymer rubber comprising less than 10 parts by weight of oil per 100 parts by weight of the multimodal copolymer rubber; and (b) at least one powdered curative; , introducing a pre-vulcanized blend into a reactor; simultaneously or sequentially with the pre-vulcanized blend, introducing at least one thermoplastic polymer, at least one other oil, and at least one curing material into the reactor; melt-mixing the pre-vulcanized blend, the at least one thermoplastic polymer, and the at least one curing material; and curing the multimodal copolymer rubber.

[0135]

[0138] 22. The method of embodiment 21, wherein the step of preparing the pre-vulcanization blend occurs at a location separate from the step of introducing the pre-vulcanization blend into a reactor.

[0139] 23. The method of embodiment 21 or 22, wherein the pre-vulcanized blend further comprises at least one powder filler, at least one thermoplastic polymer, at least one other oil, at least one curing material, or a combination thereof.

[0136]

[0140] 24. The method of embodiment 23, wherein the at least one powdered filler comprises calcium carbonate, carbon black, talc, or a combination thereof, and the at least one powdered curing agent comprises a metal oxide, stannous chloride, or a combination thereof.

[0137]

[0141] Certain embodiments and features have been described using a set of upper and lower numerical limits. It should be understood that ranges including combinations of any two values, such as any lower limit with any upper limit, any two lower limits, and / or any two upper limits, are contemplated unless otherwise specified. Specific lower limits, upper limits, and ranges are set forth in one or more claims below. All numerical values ​​are referred to as "about" or "approximately" the specified value to account for experimental error and variation that would be expected by one of ordinary skill in the art.

[0138]

[0142] Various terms have been defined above. The scope of terms used in the claims is not specified above, but should be given their broadest definition, as reflected in at least one printed publication or issued patent that one skilled in the art would recognize. Furthermore, all patents, test procedures, and other literature cited in this application are incorporated by reference in their entirety to the extent that their disclosures are not inconsistent with this application, and are subject to all authority to which such incorporation is permitted.

[0139]

[0143] The foregoing is directed to embodiments of the present invention; however, other and further embodiments of the invention may be devised without departing from the basic scope thereof, the scope of which is determined by the claims. The claims as of the filing of the parent application are reproduced below. (Aspect 1) A thermoplastic vulcanizate composition comprising: (a) a multimodal copolymer rubber, Ethylene-derived units, a major polymer fraction having a Mooney viscosity of from about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C) of from more than 50 wt% to less than 100 wt%, based on the total weight of the multimodal copolymer rubber; a minor polymer fraction having a Mooney viscosity of from about 120 ML (1+4@125°C) to about 1500 ML (1+4@125°C), from greater than 0 wt% to less than 50 wt%, based on the total weight of the multimodal copolymer rubber; Average molecular weight distribution (M w / M n ), an average branching index of about 0.7 to about 1.0, and less than 10 parts by weight of oil per 100 parts by weight of said multimodal copolymer rubber; The multimodal copolymer rubber comprising: (b) at least one other oil; (c) at least one thermoplastic polymer, and (d) a curing system comprising at least one curing material and at least one curing agent; The thermoplastic vulcanizate composition comprising: (Aspect 2) The thermoplastic vulcanizate composition of aspect 1, wherein the multimodal copolymer rubber is formed using a metallocene catalyst and comprises about 45 wt % to about 80 wt % of the ethylene-derived units; about 1 wt % to about 10 wt % of non-conjugated diene-derived units; and the remainder α-olefin-derived polymeric units, and has an overall Mooney viscosity of about 20 ML (1+4 @ 125°C) to about 90 ML (1+4 @ 125°C), all weight percentages being based on the total weight of the multimodal copolymer rubber. (Embodiment 3) The thermoplastic vulcanizate composition of embodiment 1, further comprising particles of vulcanized rubber dispersed within the continuous phase or matrix of the at least one thermoplastic polymer. (Aspect 4) The thermoplastic vulcanizate composition of aspect 1, wherein the multimodal copolymer rubber is in the form of particles having a particle size of about 0.5 mm to about 15.0 mm. (Embodiment 5) The thermoplastic vulcanizate composition of embodiment 1, wherein the at least one thermoplastic polymer comprises propylene, polyethylene, a polyethylene copolymer, a polypropylene copolymer, a copolymer of ethylene and propylene, or a combination thereof, and the amount of the at least one thermoplastic polymer in the thermoplastic vulcanizate composition is from about 20 phr to about 600 phr. (Aspect 6) The thermoplastic vulcanizate composition of aspect 5, wherein the polypropylene comprises recycled polypropylene. (Aspect 7) The thermoplastic vulcanizate composition of aspect 5, wherein the polyethylene comprises recycled polyethylene. (Embodiment 8) The thermoplastic vulcanizate composition of embodiment 1, wherein the amount of the at least one other oil in the thermoplastic vulcanizate composition is from about 10 phr to about 250 phr. (Embodiment 9) The thermoplastic vulcanizate composition of embodiment 1, wherein the at least one curing material comprises a phenolic polymer present in the thermoplastic vulcanizate composition in an amount of from about 0.1 phr to about 20.0 phr. (Embodiment 10) The thermoplastic vulcanizate composition of embodiment 1, further comprising a filler present in the thermoplastic vulcanizate composition in an amount from about 0 phr to about 300 phr. (Embodiment 11) A hardness of about 30 Shore A to about 55 Shore D, an elongation at break of about 250% to about 900%, an ultimate tensile strength of about 2.0 MPa to about 15.0 MPa, and a 1200 s -1 2. The thermoplastic vulcanizate composition of embodiment 1, further comprising an apparent viscosity of about 30 Pa*s to about 150 Pa*s at RT, a specific gravity of about 0.86 to about 1.40, a bond strength of about 1.0 MPa to about 5.0 MPa, and an extrusion surface roughness of about 20 to about 200. (Aspect 12) A method for producing a thermoplastic vulcanizate composition, comprising: introducing a multimodal copolymer rubber into a reactor, said multimodal copolymer rubber comprising: Ethylene-derived units, a major polymer fraction having a Mooney viscosity of from about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C) of from more than 50 wt% to less than 100 wt%, based on the total weight of the multimodal copolymer rubber; a minor polymer fraction having a Mooney viscosity of from about 120 ML (1+4@125°C) to about 1500 ML (1+4@125°C), from greater than 0 wt% to less than 50 wt%, based on the total weight of the multimodal copolymer rubber; Average molecular weight distribution (M w / M n ), an average branching index of about 0.7 to about 1.0, and less than 10 parts by weight of oil per 100 parts by weight of said multimodal copolymer rubber and introducing into the reactor, simultaneously or sequentially with the multimodal copolymer rubber, at least one thermoplastic polymer, at least one other oil, and a cure system; melt mixing the multimodal copolymer rubber, the at least one thermoplastic polymer, and the cure system; curing the multimodal copolymer rubber; A method comprising: (Aspect 13) The method described in Aspect 12, wherein the step of curing the multimodal copolymer rubber forms particles of rubber dispersed in a continuous phase or matrix of the at least one thermoplastic polymer. (Aspect 14) The method described in Aspect 12, further comprising introducing the at least one other oil prior to the step of curing the multimodal copolymer rubber, and further comprising introducing an additional oil following the curing of the multimodal copolymer rubber, wherein the ratio of the at least one oil to the additional oil is less than about 1. (Aspect 15) The method of aspect 12, wherein the multimodal copolymer rubber is formed using a metallocene catalyst and comprises about 45 wt% to about 80 wt% of the ethylene-derived units, about 1 wt% to about 10 wt% of non-conjugated diene-derived units, the remainder being polymeric units derived from α-olefins, and has an overall Mooney viscosity of about 20 ML (1+4 @ 125°C) to about 90 ML (1+4 @ 125°C), all weight percentages being based on the total weight of the multimodal copolymer rubber. (Aspect 16) The method of aspect 12, wherein the multimodal copolymer rubber is in the form of particles having a particle size of about 0.5 mm to about 15.0 mm. (Aspect 17) The method described in Aspect 12, wherein the at least one thermoplastic polymer comprises polypropylene, polyethylene, a polyethylene copolymer, a polypropylene copolymer, a copolymer of ethylene and propylene, or a combination thereof, and the amount of the at least one thermoplastic polymer in the thermoplastic vulcanizate composition is from about 20 phr to about 600 phr. (Aspect 18) The method of aspect 17, wherein the polypropylene comprises recycled polypropylene and the polyethylene comprises recycled polyethylene. (Aspect 19) The method described in Aspect 12, wherein the amount of the at least one other oil in the thermoplastic vulcanizate composition is from about 10 phr to about 250 phr, the curing system includes at least one curing material and at least one curing agent, and the at least one curing material includes a phenolic polymer present in the thermoplastic vulcanizate composition in an amount of from about 0.1 phr to about 20.0 phr. (Embodiment 20) The method of embodiment 12, further comprising introducing a filler into the reactor in an amount of from about 0 phr to about 300 phr simultaneously or sequentially with respect to the multimodal copolymer rubber. (Aspect 21) A method for producing a thermoplastic vulcanizate, comprising: preparing a pre-vulcanization blend, said pre-vulcanization blend comprising: (a) a multimodal copolymer rubber, Ethylene-derived units, a major polymer fraction having a first Mooney viscosity of from about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C) from greater than 50 wt% to less than 100 wt%, based on the total weight of the multimodal copolymer rubber; a minor polymer fraction having a second Mooney viscosity lower than the first Mooney viscosity, the minor polymer fraction having a second Mooney viscosity lower than the first Mooney viscosity, the minor polymer fraction having a second Mooney viscosity lower than the first Mooney viscosity, and less than 10 parts by weight of oil per 100 parts by weight of said multimodal copolymer rubber; the multimodal copolymer rubber comprising: (b) at least one powdered hardener and introducing the pre-vulcanization blend into a reactor; introducing into the reactor, simultaneously or sequentially with the pre-vulcanized blend, at least one thermoplastic polymer, at least one other oil, and at least one curing material; melt-mixing the pre-vulcanized blend, the at least one thermoplastic polymer, and the at least one curing material; curing the multimodal copolymer rubber; A method comprising: (Aspect 22) The method described in Aspect 21, wherein the step of preparing the pre-vulcanizing blend is performed in a location separate from the step of introducing the pre-vulcanizing blend into a reactor. (Aspect 23) The method described in Aspect 21, wherein the pre-vulcanized blend further comprises at least one powder filler, the at least one thermoplastic polymer, the at least one other oil, the at least one curing material, or a combination thereof. (Aspect 24) The method described in Aspect 23, wherein the at least one powdered filler comprises calcium carbonate, carbon black, talc, or a combination thereof, and the at least one powdered curing agent comprises a metal oxide, stannous chloride, or a combination thereof.

Claims

[Claim 1] 1. A thermoplastic vulcanizate composition comprising: (a) a multimodal copolymer rubber, Ethylene-derived units, greater than 50 wt % to less than 100 wt %, based on the total weight of said multimodal copolymer rubber, of a major polymer fraction having a Mooney viscosity of from about 15 ML (1+4 @ 125°C) to about 120 ML (1+4 @ 125°C); a minor polymer fraction having a Mooney viscosity of from about 120 ML (1+4 @ 125°C) to about 1500 ML (1+4 @ 125°C) from greater than 0 wt% to less than 50 wt%, based on the total weight of said multimodal copolymer rubber; Average molecular weight distribution (M ｗ / M ｎ ), an average branching index of about 0.7 to about 1.0, and less than 10 parts by weight of oil per 100 parts by weight of said multimodal copolymer rubber; The multimodal copolymer rubber comprising: (b) at least one other oil; (c) at least one thermoplastic polymer, and (d) a curing system comprising at least one curing material and at least one curing agent. The thermoplastic vulcanizate composition comprising:

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