Thermoplastic vulcanizates with lower carbon footprint

Abstract

Methods of forming thermoplastic vulcanizates and thermoplastic vulcanizates are disclosed. The method includes dynamically vulcanizing a formulation comprising a thermoplastic resin, an elastomer, an oil comprising rerefined oil, and a curing agent to provide the thermoplastic vulcanizate comprising the thermoplastic resin and an at least partially cured elastomer. The thermoplastic vulcanizate comprises a thermoplastic resin in an amount of 5 wt.% or greater based on the weight of the thermoplastic vulcanizate, an at least partially cured elastomer in an amount of 5 wt.% or greater based on the weight of the thermoplastic vulcanizate, and an oil comprising a rerefined oil.

Description

Cross-references to related applications

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 497,514, filed April 21, 2023, which is hereby incorporated by reference in its entirety. Background Technology

[0002] Typically, thermoplastic vulcanizates are formed by dynamically vulcanizing a formulation comprising a thermoplastic resin and an elastomer. During this process, additional additives may be provided for various benefits and / or to obtain certain desired properties in the resulting thermoplastic vulcanizate. For example, oils may be provided to aid in the processability of the materials in the formulation and in the formation of the thermoplastic vulcanizate. Furthermore, various additives such as colorants and / or fillers may be provided to obtain certain desired properties in the resulting thermoplastic vulcanizate. Typically, the additives used in the formation of thermoplastic vulcanizates are virgin materials. For example, oils typically used are derived from crude oil and may carry a high carbon footprint.

[0003] Therefore, there is a need to provide a thermoplastic vulcanizate with a relatively low carbon footprint and a relatively high recycling content while maintaining a balance of properties, along with an improved method for forming the thermoplastic vulcanizate. Summary of the Invention

[0004] According to one embodiment of this disclosure, a method for forming a thermoplastic vulcanizate is disclosed. The method includes dynamically vulcanizing a formulation comprising a thermoplastic resin, an elastomer, an oil comprising a refining oil, and a curing agent to provide a thermoplastic vulcanizate comprising a thermoplastic resin and at least partially cured elastomer.

[0005] According to another embodiment of this disclosure, a thermoplastic vulcanizate is disclosed. The thermoplastic vulcanizate comprises a thermoplastic resin in an amount of 5 wt.% or more by weight of the thermoplastic vulcanizate, an elastomer in an amount of at least partially cured in an amount of 5 wt.% or more by weight of the thermoplastic vulcanizate, and an oil comprising refining oil.

[0006] Other features and aspects of this disclosure are described in more detail below. Detailed Implementation

[0007] Those skilled in the art will understand that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of this disclosure.

[0008] Generally, this disclosure relates to a method for forming thermoplastic vulcanizates. This method particularly utilizes refining oils. For example, typically, the method may include the step of dynamically vulcanizing a formulation comprising a thermoplastic resin, an elastomer, an oil comprising the refining oil, and a curing agent to provide a thermoplastic vulcanizate comprising a thermoplastic resin and at least partially cured elastomer. In this respect, the inventors of this invention have discovered that by utilizing the refining oil as disclosed herein, the resulting thermoplastic vulcanizate can achieve desired properties, while also providing a more environmentally friendly method and the resulting thermoplastic vulcanizate. Therefore, this method allows for higher sustainability properties than some other general methods and also provides a reduction in the overall carbon footprint of the thermoplastic vulcanizate.

[0009] Various embodiments disclosed herein will now be described in more detail. I. thermoplastic vulcanized rubber A. thermoplastic resin

[0010] As noted above, thermoplastic vulcanizates contain thermoplastic resins. In this regard, thermoplastic vulcanizates may contain one or more thermoplastic resins. In one embodiment, a single thermoplastic resin may be used as the thermoplastic resin. In other embodiments, the thermoplastic resin may comprise a mixture of thermoplastic resins. For example, more than one thermoplastic resin, such as two or three thermoplastic resins, may be used in the thermoplastic vulcanizate. Furthermore, the thermoplastic resin may be a homopolymer or a copolymer. In one embodiment, the thermoplastic resin may be a homopolymer. In another embodiment, the thermoplastic resin may be a copolymer.

[0011] Generally, any thermoplastic resin suitable for use in the manufacture of thermoplastic vulcanizates can be used as a thermoplastic resin. For example, thermoplastic resins may include polyolefins, polyimides, polyesters, polyamides, poly(phenylene ether), polycarbonates, styrene-acrylonitrile copolymers, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polystyrene derivatives, polyphenylene ether, polyoxymethylene, fluorinated thermoplastic resins, or mixtures thereof.

[0012] In one embodiment, the thermoplastic resin may include at least one polyolefin. The polyolefin can be formed by polymerizing one or more α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propylene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. According to this disclosure, copolymers of ethylene and propylene, or ethylene or propylene with another α-olefin such as 1-butene, 1-hexene, 1-octene, 2-methyl-1-propylene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, or mixtures thereof, can also be used. In one embodiment, when the primary monomer is ethylene, the copolymer may be propylene or another C4-C8 α-olefin monomer. In one embodiment, the comonomer may be propylene. In another embodiment, the comonomer may be a C4-C8 α-olefin monomer, such as hexene. When the primary monomer is propylene, the copolymer may be ethylene or another C4-C8 α-olefin monomer. In one embodiment, the comonomer may be ethylene. In another embodiment, the comonomer may be a C4-C8 α-olefin monomer.

[0013] Other suitable polyolefin copolymers may include copolymers of olefins with styrene, such as styrene-ethylene copolymers, or polymers of olefins with α,β-unsaturated acids or α,β-unsaturated esters, such as polyethylene-acrylate copolymers. Non-olefin thermoplastic resins may include polymers and copolymers of styrene, α,β-unsaturated acids, α,β-unsaturated esters, and mixtures thereof. For example, polystyrene, polyacrylates, and polymethacrylates may be used.

[0014] When the thermoplastic resin comprises a polyolefin copolymer formed from ethylene or propylene as the main monomer, the corresponding comonomer may be present in an amount based on the weight of the copolymer, such as 0.1 wt.% or more, such as 0.5 wt.% or more, such as 1 wt.% or more, such as 2 wt.% or more, such as 5 wt.% or more, such as 10 wt.% or more, such as 15 wt.% or more, such as 20 wt.% or more. The comonomer may be present in an amount based on the weight of the copolymer, such as 40 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 15 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 5 wt.% or less. Similarly, the corresponding comonomer may be present in amounts based on the total molar percentage in the copolymer, such as 0.1 mol.% or greater, such as 0.5 mol.% or greater, such as 1 mol.% or greater, such as 2 mol.% or greater, such as 5 mol.% or greater, such as 10 mol.% or greater, such as 15 mol.% or greater, such as 20 mol.% or greater. The comonomer may also be present in amounts based on the total molar percentage in the copolymer, such as 40 mol.% or less, such as 30 mol.% or less, such as 25 mol.% or less, such as 20 mol.% or less, such as 15 mol.% or less, such as 10 mol.% or less, such as 8 mol.% or less, such as 6 mol.% or less, such as 5 mol.% or less.

[0015] In one embodiment, the polyolefin may be an ethylene polymer, a propylene polymer, or a mixture thereof. In this regard, in one embodiment, the polyolefin may be an ethylene polymer. In another embodiment, the polyolefin may be a propylene polymer. In yet another embodiment, the polyolefin may be a mixture of an ethylene polymer and a propylene polymer.

[0016] In one embodiment, the ethylene polymer may be a polyethylene homopolymer. In another embodiment, the ethylene polymer may be an ethylene copolymer.

[0017] In addition to the above, in one embodiment, the ethylene polymer may have a specific density. For example, the density may be about 0.80 g / cm³. 3 Approximately 1 g / cm 3 For example, approximately 0.84 g / cm³ 3 To approximately 0.99 g / cm 3 For example, approximately 0.84 g / cm³ 3 Approximately 0.94 g / cm³ 3 Such as approximately 0.85 g / cm 3Approximately 0.94 g / cm³ 3 For example, approximately 0.91 g / cm³ 3 Approximately 0.94 g / cm³ 3 In this regard, the ethylene polymer can be linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), or mixtures thereof. Such polyethylenes can have a specific density as determined according to ASTM D792. For example, linear low-density polyethylene (LLDPE) can have a density of approximately 0.91 g / cm³. 3 Approximately 0.94 g / cm³ 3 The density can be within a certain range. Meanwhile, low-density polyethylene (LDPE) can have a density of approximately 0.91 g / cm³. 3 To approximately 0.925 g / cm 3 The density range is specified. Medium-density polyethylene (MDPE) can have a density of approximately 0.926 g / cm³. 3 Approximately 0.94 g / cm³ 3 The density can be within a certain range. Furthermore, high-density polyethylene (HDPE) can have a density of approximately 0.941 g / cm³. 3 To approximately 0.965 g / cm 3 The density is within the range specified. In one embodiment, the ethylene polymer may be low-density polyethylene. In another embodiment, the ethylene polymer may be linear low-density polyethylene. In yet another embodiment, the ethylene polymer may be medium-density polyethylene.

[0018] In one embodiment, the propylene polymer may be a polypropylene homopolymer. In another embodiment, the propylene polymer may be a polypropylene copolymer. Furthermore, the polypropylene polymer may be isotactic or syndiotactic polypropylene. For example, in one embodiment, the polypropylene polymer may be isotactic polypropylene. In another embodiment, the polypropylene polymer may be syndiotactic polypropylene.

[0019] These homopolymers and copolymers can be synthesized using any polymerization technique known in the art, such as, but not limited to, Phillips-catalyzed reactions, conventional Ziegler-Natta polymerization, and metallocene catalysis, including but not limited to metallocene-aluminoxane and metallocene-ion activator catalysis. Therefore, suitable catalyst systems include chiral metallocene catalyst systems, see, for example, U.S. Patent No. 5,441,920, and transition metal-centered heteroaryl ligand catalyst systems, see, for example, U.S. Patent No. 6,960,635.

[0020] In one embodiment, the thermoplastic resin may include a recycled thermoplastic resin. For example, the recycled thermoplastic resin may be a pre-consumer, post-industrial, or post-consumer thermoplastic resin as defined in ISO 14021, excluding materials that can be recycled within the same process in which they are generated. The thermoplastic resin may include a mixture of one or more virgin thermoplastic resins and one or more recycled thermoplastic resins. In one embodiment, the recycled thermoplastic resin may constitute the majority of the thermoplastic resin by weight. In this respect, it may be present in an amount greater than 50 wt.% based on the total weight of the thermoplastic resin in the thermoplastic vulcanizate. In another embodiment, the recycled thermoplastic resin may constitute a minority of the thermoplastic resin by weight. In this respect, it may be present in an amount less than 50 wt.% based on the total weight of the thermoplastic resin in the thermoplastic vulcanizate. In yet another embodiment, the recycled thermoplastic resin may be provided in parts by weight equal to those of the virgin thermoplastic resin. The thermoplastic resin of the recycled thermoplastic resin may be any of the thermoplastic resins described above.

[0021] The recycled thermoplastic resin can be a recycled thermoplastic resin of any of the above-mentioned thermoplastic resins mentioned herein. In one embodiment, the recycled thermoplastic resin may include recycled polyolefins. For example, the recycled thermoplastic resin may include recycled polypropylene, recycled polyethylene, or mixtures thereof. In one specific embodiment, the recycled thermoplastic resin may include recycled polypropylene. In another specific embodiment, the recycled thermoplastic resin may include recycled polyethylene. In yet another specific embodiment, the recycled thermoplastic resin may include a mixture of recycled polyethylene and recycled polypropylene.

[0022] Typically, thermoplastic resins can comprise solid, usually high molecular weight polymer materials. Thermoplastic resins can have a molecular weight (Mw) of about 50,000 g / mol or greater, such as 75,000 g / mol or greater, such as 100,000 g / mol or greater, such as 200,000 g / mol or greater, such as 300,000 g / mol or greater, such as 400,000 g / mol or greater, such as 500,000 g / mol or greater, such as 750,000 g / mol or greater, such as 1,000,000 g / mol or greater, such as 2,000,000 g / mol or greater, such as 3,000,000 g / mol or greater. Mw can be about 6,000,000 g / mol or less, such as about 5,000,000 g / mol or less, such as 4,000,000 g / mol or less, such as 3,000,000 g / mol or less, such as 2,000,000 g / mol or less, such as 1,500,000 g / mol or less, such as 1,000,000 g / mol or less, such as 900,000 g / mol or less, such as 800,000 g / mol or less, such as 700,000 g / mol or less. In addition, the thermoplastic resin may have Mn of about 50,000 g / mol or greater, such as 75,000 g / mol or greater, such as 100,000 g / mol or greater, such as 200,000 g / mol or greater, such as 300,000 g / mol or greater, such as 400,000 g / mol or greater, such as 500,000 g / mol or greater, such as 750,000 g / mol or greater, such as 1,000,000 g / mol or greater, such as 2,000,000 g / mol or greater, such as 3,000,000 g / mol or greater. Mn can be about 6,000,000 g / mol or less, such as about 5,000,000 g / mol or less, such as 4,000,000 g / mol or less, such as 3,000,000 g / mol or less, such as 2,000,000 g / mol or less, such as 1,500,000 g / mol or less, such as 1,000,000 g / mol or less, such as 900,000 g / mol or less, such as 800,000 g / mol or less, such as 700,000 g / mol or less. Typically, molecular weight can be characterized using GPC (gel permeation chromatography) with polystyrene standards.

[0023] The thermoplastic resin may be a crystalline polymer in one embodiment or a semi-crystalline polymer in another embodiment. For example, the crystallinity may be at least 25% by weight, such as at least 35%, such as at least 45%, such as at least 55%, such as at least 65%, such as at least 70%. Crystallinity can be determined by differential scanning calorimetry. For example, crystallinity can be determined by dividing the heat of fusion of the sample by the heat of fusion of 100% crystalline polymer.

[0024] Thermoplastic resins can also have specific glass transition temperatures (“Tg”). For example, the glass transition temperature can be relatively high. In this respect, Tg can be approximately -120°C or greater, such as -110°C or greater, such as -100°C or greater, such as -90°C or greater, such as -70°C or greater, such as -50°C or greater, such as -30°C or greater, such as -25°C or greater, such as -20°C or greater, such as -15°C or greater, such as -10°C or greater, such as -5°C or greater, such as 0°C or greater, such as 5°C or greater, such as 10°C or greater, such as 20°C or greater, such as 30°C or greater, such as 50°C or greater, such as 80°C or greater, such as 100°C or greater, such as 120°C or greater, such as 140°C or greater, such as 160°C or greater, such as 180°C or greater, such as 200°C or greater. Tg can be approximately 300°C or less, such as 260°C or less, such as 220°C or less, such as 180°C or less, such as 140°C or less, such as 100°C or less, such as 80°C or less, such as 60°C or less, such as 40°C or less, such as 30°C or less, such as 20°C or less, such as 10°C or less, such as 5°C or less, such as 0°C or less, such as -5°C or less.

[0025] Furthermore, thermoplastic resins can have a specific melting temperature (“Tm”). For example, the melting temperature of a thermoplastic resin can be relatively high. Additionally, the melting temperature of a thermoplastic resin can be lower than the decomposition temperature of the elastomer in the thermoplastic vulcanizate, which is typically characterized as the point at which molecular bonds begin to break or dissociate, causing the molecular weight of the elastomer to begin to decrease. In this respect, Tm can be about 100°C or greater, such as 120°C or greater, such as 140°C or greater, such as 150°C or greater, such as 160°C or greater, such as 170°C or greater, such as 180°C or greater, such as 190°C or greater, such as 200°C or greater, such as 240°C or greater, such as 280°C or greater. Tm can be approximately 400°C or less, such as 360°C or less, such as 320°C or less, such as 300°C or less, such as 280°C or less, such as 250°C or less, such as 220°C or less, such as 200°C or less, such as 180°C or less, such as 160°C or less.

[0026] Thermoplastic resins can also be characterized by having a specific heat of fusion. For example, the heat of fusion can be about 0.1 J / g or greater, such as about 1 J / g or greater, such as about 2 J / g or greater, such as about 5 J / g or greater, such as about 10 J / g or greater, such as about 30 J / g or greater, such as 40 J / g or greater, such as 50 J / g or greater, such as 60 J / g or greater, such as 70 J / g or greater, such as 100 J / g or greater, such as 120 J / g or greater, such as 140 J / g or greater, such as 160 J / g or greater, such as 180 J / g or greater, such as 200 J / g or greater. The heat of fusion can be about 300 J / g or less, such as about 260 J / g or less, such as about 240 J / g or less, such as about 200 J / g or less, such as about 180 J / g or less, such as about 150 J / g or less, such as about 120 J / g or less, such as about 100 J / g or less, such as about 80 J / g or less, such as about 60 J / g or less, such as about 50 J / g or less, such as about 40 J / g or less, such as about 30 J / g or less, such as about 20 J / g or less.

[0027] Thermoplastic resins can have melt flow rates up to 400 g / 10 min. Typically, thermoplastic resins can have even better properties, with melt flow rates less than about 30 g / 10 min, preferably less than 10 g / 10 min, such as less than about 2 g / 10 min, such as less than about 1 g / 10 min, such as less than about 0.8 g / 10 min. Typically, melt flow rates can be 0.1 g / 10 min or greater, such as 0.2 g / 10 min or greater, such as 0.3 g / 10 min or greater, such as 0.4 g / 10 min or greater, such as 0.5 g / 10 min or greater. Melt flow rate is a measure of how easily a polymer flows under standard pressure and is measured using ASTM D-1238 at 190°C and a 2.16 kg load.

[0028] Thermoplastic resins may be present in amounts of about 10 phr or greater, such as about 20 phr or greater, such as about 30 phr or greater, such as about 40 phr or greater, such as about 50 phr or greater, such as about 60 phr or greater, such as about 70 phr or greater, such as about 80 phr or greater, such as about 90 phr or greater, such as about 100 phr or greater, such as about 150 phr or greater, such as about 200 phr or greater, such as about 250 phr or greater, such as about 300 phr or greater. Thermoplastic resins may be present in amounts of about 750 phr or less, such as about 700 phr or less, such as about 600 phr or less, such as about 500 phr or less, such as about 400 phr or less, such as about 350 phr or less, such as about 300 phr or less, such as about 250 phr or less, such as about 200 phr or less, such as about 180 phr or less, such as about 160 phr or less, such as about 140 phr or less, such as about 120 phr or less, such as about 100 phr or less, such as about 90 phr or less, such as about 80 phr or less, such as about 70 phr or less, such as about 60 phr or less, such as about 50 phr or less.

[0029] Thermoplastic vulcanizates and / or formulations may typically contain about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more of thermoplastic resin. Thermoplastic vulcanizates and / or formulations may contain about 90 wt.% or less, such as about 80 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 35 wt.% or less of thermoplastic resin. In another embodiment, such weight percentages may be based on the combined weight of the thermoplastic resin and elastomer combined within the thermoplastic vulcanizate.

[0030] When a thermoplastic vulcanizate comprises a first thermoplastic resin and a second thermoplastic resin, they may be present in certain amounts. For example, the thermoplastic resin may typically contain about 5 wt.% or more, such as about 8 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more of the first thermoplastic resin. The thermoplastic resin may contain about 98 wt.% or less, such as about 95 wt.% or less, such as about 90 wt.% or less, such as about 80 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 30 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less of a first thermoplastic resin.

[0031] Thermoplastic resins may typically contain about 5 wt.% or more, such as about 8 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more of a second thermoplastic resin. The thermoplastic resin may contain about 98 wt.% or less, such as about 95 wt.% or less, such as about 90 wt.% or less, such as about 80 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 30 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less of a second thermoplastic resin.

[0032] The weight ratio of the first thermoplastic resin to the second thermoplastic resin may be about 0.01 or greater, such as about 0.05 or greater, such as about 0.1 or greater, such as about 0.2 or greater, such as about 0.3 or greater, such as about 0.4 or greater, such as about 0.5 or greater, such as about 0.6 or greater, such as about 0.7 or greater, such as about 0.8 or greater, such as about 0.9 or greater, such as about 1 or greater, such as about 1.2 or greater, such as about 1.4 or greater, such as about 1.6 or greater, such as about 1.8 or greater, such as about 2 or greater, such as about 2.5 or greater, such as about 3 or greater, such as about 3.5 or greater, such as about 4 or greater, such as about 4.5 or greater, such as about 5 or greater. The weight ratio can be about 40 or less, such as about 35 or less, such as about 30 or less, such as about 28 or less, such as about 26 or less, such as about 24 or less, such as about 22 or less, such as about 20 or less, such as about 18 or less, such as about 16 or less, such as about 14 or less, such as about 12 or less, such as about 10 or less, such as about 9 or less, such as about 8 or less, such as about 7 or less, such as about 6 or less, such as about 5 or less, such as about 4.5 or less, such as about 4 or less, such as about 3.5 or less, such as about 3 or less, such as about 2.5 or less, such as about 2 or less, such as about 1.8 or less, such as about 1.6 or less, such as about 1.4 or less, such as about 1.2 or less, such as about 1 or less, such as about 0.8 or less, such as about 0.6 or less, such as about 0.4 or less.

[0033] As indicated above, in one embodiment, the thermoplastic resin may include recycled thermoplastic resin. The thermoplastic resin may typically contain about 1 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more of recycled thermoplastic resin. The thermoplastic resin may contain about 100 wt.% or less, such as about 98 wt.% or less, such as about 95 wt.% or less, such as about 90 wt.% or less, such as about 80 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 30 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less, such as about 5 wt.% or less of recycled thermoplastic resin.

[0034] The weight ratio of virgin thermoplastic resin to recycled thermoplastic resin can be about 0.01 or greater, such as about 0.05 or greater, such as about 0.1 or greater, such as about 0.2 or greater, such as about 0.3 or greater, such as about 0.4 or greater, such as about 0.5 or greater, such as about 0.6 or greater, such as about 0.7 or greater, such as about 0.8 or greater, such as about 0.9 or greater, such as about 1 or greater, such as about 1.2 or greater, such as about 1.4 or greater, such as about 1.6 or greater, such as about 1.8 or greater, such as about 2 or greater, such as about 2.5 or greater, such as about 3 or greater, such as about 3.5 or greater, such as about 4 or greater, such as about 4.5 or greater, such as about 5 or greater. The weight ratio can be about 40 or less, such as about 35 or less, such as about 30 or less, such as about 28 or less, such as about 26 or less, such as about 24 or less, such as about 22 or less, such as about 20 or less, such as about 18 or less, such as about 16 or less, such as about 14 or less, such as about 12 or less, such as about 10 or less, such as about 9 or less, such as about 8 or less, such as about 7 or less, such as about 6 or less, such as about 5 or less, such as about 4.5 or less, such as about 4 or less, such as about 3.5 or less, such as about 3 or less, such as about 2.5 or less, such as about 2 or less, such as about 1.8 or less, such as about 1.6 or less, such as about 1.4 or less, such as about 1.2 or less, such as about 1 or less, such as about 0.8 or less, such as about 0.6 or less, such as about 0.4 or less. B. elastomer

[0035] As noted above, thermoplastic vulcanizates contain elastomers. For example, thermoplastic vulcanizates contain at least partially cured elastomers due to dynamic vulcanization. Generally, any elastomer suitable for use in the manufacture of TPVs can be used according to this disclosure. In one embodiment, one elastomer can be used as the elastomer. In other embodiments, the elastomer can include a mixture of elastomers. For example, more than one elastomer, such as two or three elastomers, can be used in the thermoplastic vulcanizate.

[0036] Any elastomer or mixture thereof that can be vulcanized (i.e., crosslinked or cured) can be used as an elastomer (sometimes referred to herein as rubber). References to rubber or elastomers may include mixtures of more than one. Available elastomers typically contain a degree of unsaturation in their polymer backbone. Some non-limiting examples of these rubbers include polyolefin copolymer elastomers, butyl rubber, natural rubber, styrene-butadiene copolymer rubbers (e.g., styrene / ethylene-butadiene / styrene), butadiene rubber, acrylonitrile rubber, halogenated rubbers such as brominated and chlorinated isobutylene-isoprene copolymer rubbers, butadiene-styrene-vinylpyridine rubbers, urethane rubbers, polyisoprene rubbers, epichlorohydrin terpolymer rubbers, and polychloroprene.

[0037] Vulcanizable elastomers include polyolefin copolymer elastomers. These copolymers are prepared from ethylene and one or more higher α-olefins, which may include, but are not limited to, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof, plus one or more copolymerizable polyunsaturated comonomers, such as dienes or diene monomers. The α-olefin may be propylene, 1-hexene, 1-octene, or combinations thereof. These rubbers may lack substantial crystallinity and may suitably be amorphous copolymers.

[0038] Diene monomers may include, but are not limited to, 5-ethylidene-2-norbornene; 1,4-hexadiene; 5-methylene-2-norbornene; 1,6-octadiene; 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene; dicyclopentadiene; 5-vinyl-2-norbornene; divinylbenzene, etc.; or combinations thereof. The diene monomer may be 5-ethylidene-2-norbornene and / or 5-vinyl-2-norbornene. If the copolymer is prepared from ethylene, α-olefins, and diene monomers, the copolymer may be referred to as a terpolymer (EPDM rubber) or a quaternary copolymer (EAODM rubber) when using multiple α-olefins or dienes or both.

[0039] The elastomer, as a polyolefin elastomer copolymer, may contain about 15 to about 90 molar percentages of ethylene units derived from ethylene monomers, about 40 to about 85 molar percentages, or about 50 to about 80 molar percentages of ethylene units. The copolymer may contain about 10 to about 85 molar percentages, or about 15 to about 50 molar percentages, or about 20 to about 40 molar percentages of α-olefin units derived from α-olefin monomers. The aforementioned molar percentages are based on the total number of moles of monomer units in the polymer. In the case where the copolymer contains diene units, the copolymer may contain about 0.1 to about 14 weight percentages, about 0.2 to about 13 weight percentages, or about 1 to about 12 weight percentages of units derived from diene monomers. The weight percentage of diene units derived from dienes can be determined according to ASTM D-6047. In some cases, the copolymer contains less than 5.5 weight percentages, such as less than 5.0 weight percentages, such as less than 4.5 weight percentages, such as less than 4.0 weight percentages of units derived from diene monomers. In other cases, the copolymer contains more than 6.0% by weight, such as more than 6.2% by weight, such as more than 6.5% by weight, such as more than 7.0% by weight, such as more than 8.0% by weight, units derived from diene monomers.

[0040] Polyolefin elastomer copolymers can be obtained using polymerization techniques known in the art, such as conventional solution or slurry polymerization processes. For example, catalysts used to polymerize ethylene, α-olefins, and diene monomers into elastomer copolymers can include conventional Ziegler-Natta catalyst systems, particularly those including titanium and vanadium compounds, and metallocene catalysts for Group 3-6 (titanium, zirconium, and hafnium) metallocene catalysts, particularly bridged monocyclopentadienyl or dicyclopentadienyl metallocene catalysts. Other catalyst systems, such as the Brookhart catalyst system, can also be used.

[0041] In one embodiment, the elastomer may include butyl rubber. For example, butyl rubber includes copolymers and terpolymers of isobutylene and at least one other comonomer. Available comonomers include isoprene, divinyl aromatic monomers, alkyl-substituted vinyl aromatic monomers, and mixtures thereof. Exemplary divinyl aromatic monomers include vinylstyrene. Exemplary alkyl-substituted vinyl aromatic monomers include α-methylstyrene and p-methylstyrene. These copolymers and terpolymers may also be halogenated, as in the case of chlorinated and brominated butyl rubber. In one or more embodiments, these halogenated polymers may be derived from monomers such as p-bromomethylstyrene.

[0042] In one embodiment, the elastomer may comprise a multimodal copolymer rubber. For example, such rubber may include: ethylene-derived units; a major polymer fraction, based on the total weight of the multimodal copolymer rubber, greater than about 50 wt.% and less than about 100 wt.% having a Mooney viscosity of about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C); a minor polymer fraction, based on the total weight of the multimodal copolymer rubber, greater than about 0 wt.% and less than about 50 wt.% having a Mooney viscosity of about 120 ML (1+4@125°C) to about 1,500 ML (1+4@125°C); an average molecular weight distribution (Mw / Mn) of about 1.5 to about 4.5; and an average branching factor (BI) of about 0.7 to about 1.0. The average polymer fraction may also be inverse (e.g., a majority of higher molecular weights and a minority of lower molecular weights). Therefore, multimodal copolymer rubbers can have relatively narrow molecular weight distributions and total Mooney viscosity of less than about 90 ML (1+4@125°C), indicating that they can be easily processed and require little or no extender oil. Multimodal copolymer rubbers can be almost linear in structure, as indicated by their average branching coefficient, and can be completely amorphous or semi-crystalline in nature.

[0043] Multimodal copolymer rubber may include ethylene-derived units, α-olefin-derived units, and diene-derived units, preferably non-conjugated diene-derived units.

[0044] The α-olefin derivative unit may be or may include C2 to C20 α-olefins, such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof. The α-olefin derivative unit is preferably propylene, 1-butene, 1-hexene, 1-octene, or combinations thereof, more preferably propylene. The non-conjugated diene derivative unit 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), norbornene, 5-vinyl-2-norbornene (VNB), or combinations thereof. Examples of suitable ethylene-propylene-diene (EPDM) rubbers include Vistalon™ 5601, Vistalon™ 5702, Vistalon™ 7001, Vistalon™ 9301, etc., commercially available from ExxonMobil, and Nordel™ grades such as 4760, 4770, 4785, etc., commercially available from Dow. (SABIC) ® EPDM756, and Keltan, which is commercially available from Arlanxeo. ®Grades, such as 8550C, 8570C, etc.

[0045] The amount of ethylene-derived units present in the multimodal copolymer rubber can range from about 45 wt.% to about 80 wt.%, preferably about 50 wt.% to about 75 wt.%, and more preferably 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 can range from about 1 wt.% to about 10 wt.%, preferably about 2 wt.% to about 8 wt.%, and more preferably about 3 wt.% to about 6 wt.%, based on the total weight of the rubber. α-olefin-derived units may constitute the remainder of the polymer units.

[0046] Ethylene content can be determined by FTIR, ASTM D3900, without correction for diene content. ENB diene content can be determined by FTIR, ASTM D6047. Other dienes can be measured by ¾ NMR.

[0047] Multimodal copolymer rubbers are characterized by a multimodal molecular weight distribution, which can be simply referred to as multimodal molecular weight. In one or more embodiments, the multimodal copolymer rubber may comprise at least two fractions. Multimodality itself can manifest as M... W GPC LALLS The signal contains two distinct peaks, or a main peak and a shoulder peak. This multimodality can be caused by blending a very high molecular weight component with a very low molecular weight component as a result of sequential polymerization or physical blending techniques. In this respect, multimodal copolymers can be bimodal, trimodal, tetramodal, etc.

[0048] The multimodal copolymer rubber may include a major polymer fraction of greater than about 50 wt.% and less than about 100 wt.%, preferably greater than about 55 wt.% and less than about 95 wt.%, and more preferably greater than about 60 wt.% and less than about 90 wt.%. Based on the total weight of the multimodal copolymer rubber, the major polymer fraction may have a Mooney viscosity of about 15 ML (1+4@125°C) to about 120 ML (1+4@125°C), preferably about 25 ML (1+4@125°C) to about 90 ML (1+4@125°C), and more preferably about 30 ML (1+4@125°C) to about 80 ML (1+4@125°C).

[0049] The multimodal copolymer rubber may include a secondary polymer fraction greater than about 0 wt.% and less than about 50 wt.%, preferably greater than about 5 wt.% and less than about 45 wt.%, and more preferably greater than about 10 wt.% and less than about 40 wt.%. Based on the total weight of the multimodal copolymer rubber, the secondary polymer fraction may have a Mooney viscosity of about 120 ML (1+4@125 °C) to about 1,500 ML (1+4@125 °C), preferably about 120 ML (1+4@125 °C) to about 1,100 ML (1+4@125 °C), and more preferably about 120 ML (1+4@125 °C) to about 700 ML (1+4@125 °C).

[0050] Multimodal copolymer rubbers can have a total Mooney viscosity of about 20 ML (1+4@125°C) to about 90 ML (1+4@125°C), preferably about 25 ML (1+4@125°C) to about 85 ML (1+4@125°C), and more preferably about 30 ML (1+4@125°C) to about 80 ML (1+4@125°C). As used herein, Mooney viscosity is reported in the following format: rotor ([preheating time, min.] + [shearing time, min.] @ measurement temperature, °C), such that ML (1+4@125°C) indicates the Mooney viscosity determined according to ASTM D1646-99 using ML or a large rotor for a preheating time of 1 minute and a shearing time of 4 minutes at 125°C. Unless otherwise stated, Mooney viscosity is reported herein in ML (1+4@125°C) in Mooney units according to ASTM D-1646. However, under these conditions, Mooney viscosity values ​​greater than approximately 100 are typically unmeasurable. In this case, higher temperatures (i.e., 150°C) can be used, resulting in longer shear times (i.e., 1+8@125°C or 150°C). More preferably, for the purposes of this document, Mooney measurements are performed using a non-standard small rotor. This non-standard rotor design, where the variation in the Mooney scale allows the same instrument on the Mooney instrument to be used with polymers having Mooney viscosities exceeding approximately 100 ML (1+4@125°C). For the purposes of this document, this modified Mooney determination is referred to as Mooney Small Thin (MST).

[0051] ASTM D 1646-99 specifies the dimensions of rotors used within the cavity of Mooney instruments. This method allows for both large and small rotors, differing only in diameter. These different rotors are referred to in ASTM D 1646-99 as ML (Mouney Large) and MS (Mouney Small). However, EPDM rubber can be produced at such high molecular weights that the torque limits of Mooney instruments can be exceeded using rotors specified in this standard. In these cases, the test is run using a smaller and thinner MST rotor. Typically, when using an MST rotor, the test is also run with different time constants and temperatures. The preheating time is changed from the standard 1 minute to 5 minutes, and the test is run at 200°C instead of the standard 125°C. The values ​​obtained under these modified conditions are referred to herein as MST(5+4@200°C). Note: At the end of the 4-minute run, the Mooney readings are obtained as under the same standard conditions. When the MST is measured at (5+4@200°C) and the ML is measured at (1+4@125°C), one MST point is approximately equivalent to five ML points. Therefore, for the purpose of approximate conversion between these two measurement scales, the Mooney value of the MST (5+4@200°C) is multiplied by 5 to obtain an approximate ML (1+4@125°C) equivalent. The MST rotor used in this paper has a diameter of 30.48+ / -0.03 mm, a thickness of 2.8+ / -0.03 mm (determined by the top of the teeth), and a shaft with a diameter of 11 mm or less. The rotor has serrated surfaces and edges with square grooves approximately 0.8 mm wide and approximately 0.25–0.38 mm deep, cut at a center of 1.6 mm. The teeth will consist of two sets of grooves perpendicular to each other, thus forming a square profile. The rotor is positioned at the center of the mold cavity such that the centerline of the rotor disk coincides with the centerline of the mold cavity within a tolerance of + / -0.25 mm. Spacers or shims can be used to raise the shaft to the midpoint, consistent with typical practice in the art for Mooney measurements. The wear point (a tapered protrusion located at the center of the rotor's top surface) is machined flat against the rotor surface.

[0052] The Mooney viscosity of multimodal copolymer rubbers can be determined from blends of the polymers described herein. The Mooney viscosity of a specific component of the blend is obtained in this paper using the relationship shown in equation (1): log ML = n A log ML A +n B logML B (1), where all logarithms are base 10; ML represents each individual Mooney viscosity ML. A and ML B Mooney viscosity of a blend of polymers A and B; n AThis represents the wt.% fraction of polymer A in the blend; and n B This represents the wt.% fraction of polymer B in the blend. Equation (1) can be used to determine the Mooney viscosity of blends containing a high Mooney viscosity polymer (A) and a low Mooney viscosity polymer (B), which have measurable Mooney viscosities under (1+4@125°C) conditions. ML, ML A and n A ML can be calculated B The value of ML. However, for high Mooney viscosity polymers (i.e., Mooney viscosity greater than 100 ML(1+4@125°C), ML can be measured using an MST rotor as described above. A Then the Mooney viscosity of the low molecular weight polymer in the blend can be determined using Equation 1 above, where ML A The following correlation (2) was used to determine: ML A (1 + 4 @ 125°C) = 5.13 MST A (5+4@200°C) (2). In these or other embodiments, the Mooney viscosity of the high molecular weight polymer can be determined by using a Mooney viscometer model VR / 1132 (Ueshima Seisakusho), which can measure Mooney viscosity up to 400 units.

[0053] Multimodal copolymer rubbers can be prepared by polymerization using a metallocene catalyst. The resulting rubber can 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 weight-average particle size. These particles can be dusted, for example, with a powdering rate greater than about 0.1 phr to prevent the rubber particles from sticking together. Such particles can include, for example, polyethylene dust particles, inorganic filler materials such as calcium carbonate, talc, clay, etc.

[0054] In one or more embodiments, butyl rubber comprises copolymers of isobutylene and isoprene, copolymers of isobutylene and p-methylstyrene, terpolymers of isobutylene, isoprene, and divinylstyrene, branched butyl rubber, and brominated copolymers of isobutylene and p-methylstyrene (producing copolymers having p-bromomethylstyrene monomer units). These copolymers and terpolymers may be halogenated. Furthermore, butyl rubber can be prepared by polymerization using techniques known in the art, such as at low temperatures in the presence of a Friedel-Crafts catalyst.

[0055] In one embodiment, where the butyl rubber comprises an isobutylene-isoprene copolymer, the copolymer may comprise isoprene in weight of about 0.5 to about 30, or about 0.8 to about 5 percent, based on the total weight of the copolymer, with the remainder being isobutylene.

[0056] In another embodiment, where the butyl rubber comprises an isobutylene-p-methylstyrene copolymer, the copolymer may comprise about 0.5 to about 25% by weight of p-methylstyrene and about 2 to about 20% by weight of the total weight of the copolymer, with the remainder being isobutylene. In one embodiment, the isobutylene-p-methylstyrene copolymer may be halogenated, such as with bromine, and these halogenated copolymers may contain about 0 to about 10% by weight, or about 0.3 to about 7% by weight of halogenation.

[0057] In other embodiments, where the butyl rubber comprises isobutylene-isoprene-divinylstyrene, the terpolymer may comprise isobutylene in weight percentages of about 95 to about 99, or about 96 to about 98.5, based on the total weight of the terpolymer, and isoprene in weight percentages of about 0.5 to about 5, or about 0.8 to about 2.5, with the balance being divinylstyrene.

[0058] In the case of halogenated butyl rubber, the butyl rubber may include halogens in a weight percentage of about 0.1 to about 10, or about 0.3 to about 7, or about 0.5 to about 3 percent based on the total weight of the copolymer or terpolymer.

[0059] In one or more embodiments, the glass transition temperature (Tg) of butyl rubber may be less than about -55°C, or less than about -58°C, or less than about -60°C, or less than about -63°C. Furthermore, the Mooney viscosity (ML) of butyl rubber... 1+8 (@125°C) can be about 25 to about 75, or about 30 to about 60, or about 40 to about 55.

[0060] Regarding the materials used to form these elastomers, it should be understood that in some embodiments, they may include biorenewable monomers and / or recycled monomers. For example, at least some of the monomers may include such biorenewable monomers and / or recycled monomers. In one embodiment, all monomers used to manufacture the elastomer may be biorenewable monomers and / or recycled monomers. As an example, bioethanol may be a renewable source for the production of ethylene and / or propylene, which can be used to form polyolefin elastomer copolymers as defined herein.

[0061] Typically, elastomers, particularly polyolefin elastomer copolymers, can have a Mw of about 50,000 g / mol or greater, such as 75,000 g / mol or greater, such as 100,000 g / mol or greater, such as 200,000 g / mol or greater, such as 300,000 g / mol or greater, such as 400,000 g / mol or greater, such as 500,000 g / mol or greater, such as 750,000 g / mol or greater, such as 1,000,000 g / mol or greater. Mw can be about 3,000,000 g / mol or less, such as 2,000,000 g / mol or less, such as 1,500,000 g / mol or less, such as 1,000,000 g / mol or less, such as 900,000 g / mol or less, such as 800,000 g / mol or less, such as 700,000 g / mol or less, such as 600,000 g / mol or less, such as 500,000 g / mol or less, such as 400,000 g / mol or less, such as 300,000 g / mol or less. Furthermore, the elastomer, particularly the polyolefin elastomer copolymer, may have Mn of about 50,000 g / mol or greater, such as 75,000 g / mol or greater, such as 100,000 g / mol or greater, such as 200,000 g / mol or greater, such as 300,000 g / mol or greater, such as 400,000 g / mol or greater, such as 500,000 g / mol or greater, such as 750,000 g / mol or greater, such as 1,000,000 g / mol or greater. Mn can be about 3,000,000 g / mol or less, such as 2,000,000 g / mol or less, such as 1,500,000 g / mol or less, such as 1,000,000 g / mol or less, such as 900,000 g / mol or less, such as 800,000 g / mol or less, such as 700,000 g / mol or less, such as 600,000 g / mol or less, such as 500,000 g / mol or less, such as 400,000 g / mol or less, such as 300,000 g / mol or less. Typically, the molecular weight can be characterized using GPC (gel permeation chromatography) with polystyrene standards.

[0062] Thermoplastic vulcanized rubber and / or formulations may typically contain about 2 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more of elastomer. The thermoplastic vulcanizate and / or formulations may contain about 90 wt.% or less, such as about 80 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 35 wt.% or less, such as about 30 wt.% or less, such as about 25 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less. In another embodiment, such as the above weight percentages may be based on the combined weight of the thermoplastic resin and elastomer combined in the thermoplastic vulcanizate.

[0063] Furthermore, when a mixture of elastomers is present, the primary elastomer may be present in an amount of about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more, up to less than 100 wt.% of the elastomer's weight. The secondary elastomer may be present in an amount of 40 wt.% or less, such as 30 wt.% or less, such as 20 wt.% or less, such as 15 wt.% or less, such as 10 wt.% or less, such as 5 wt.% or more, up to greater than 0 wt.% of the elastomer's weight. C. Curing composition

[0064] As indicated herein, TPV formulations, particularly the elastomers within the formulations, can undergo dynamic curing, in which the elastomer is at least partially cured. Generally, any curing agent capable of curing or crosslinking the elastomer can be used. Some non-limiting examples of such curing agents include phenolic resins, peroxides, maleimides, and silicone-containing curing agents. For the purpose of improving the overall cured state of the elastomer, these curing agents can be used with one or more coagents that act as initiators, catalysts, etc. For example, the curing compositions of some embodiments include one or both of zinc oxide (ZnO) and stannous chloride (SnCl2).

[0065] Generally, phenolic resins are not necessarily limited. For example, these can include fusible phenolic resins prepared by the condensation of alkyl-substituted or unsubstituted phenols with an aldehyde (which may be formaldehyde) in an alkaline medium or by the condensation of a difunctional phenolic glycol. The alkyl substituents in alkyl-substituted phenols typically contain 1 to about 10 carbon atoms. Dihydroxymethylphenol or phenolic resins with alkyl substituents at the para position containing 1 to about 10 carbon atoms can be used. These phenolic curing agents can be thermosetting resins and can be referred to as phenolic resin curing agents or phenolic resins. These phenolic resins can ideally be used in conjunction with catalyst systems. For example, non-halogenated phenolic cured resins are used in conjunction with a halogen donor and, optionally, a hydrogen halide scavenger. In the case of halogenated phenolic cured resins, a halogen donor is not required, but a hydrogen halide scavenger, such as ZnO, can be used.

[0066] Peroxide curing agents are typically selected from organic peroxides. Examples of organic peroxides include, but are not limited to, di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, α,α-bis(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, and mixtures thereof. Additionally, diaryl peroxides, ketone peroxides, peroxydicarbonates, peroxy esters, dialkyl peroxides, hydroperoxides, peroxyketals, and mixtures thereof can be used.

[0067] Silicon-containing curing agents typically comprise hydride compounds having at least two SiH groups. These compounds react with the carbon-carbon double bonds of unsaturated polymers in the presence of a hydrosilylation catalyst. Hydroxysilane compounds include, but are not limited to, methylhydropolysiloxanes, methylhydrodimethyl-siloxane copolymers, alkylmethylpolysiloxanes, bis(dimethylsilyl)alkanes, bis(dimethylsilyl)benzenes, and mixtures thereof.

[0068] As noted above, hydrosilylation curing can be carried out in the presence of a catalyst. These catalysts may include, but are not limited to, peroxide catalysts and catalysts including Group VIII transition metals. These metals include, but are not limited to, palladium, rhodium, and platinum, as well as complexes of these metals.

[0069] In some embodiments, the curing composition further includes one or both of ZnO and SnCl2. In one embodiment, the curing composition may include zinc oxide. In another embodiment, the curing composition may include stannous chloride. In yet another embodiment, the curing composition may include both zinc oxide and stannous chloride.

[0070] Additives may also be used in conjunction with curing agents such as phenolic resins and / or peroxides. Additives may include polyfunctional acrylates, polyfunctional methacrylates, or combinations thereof. In other words, the additive includes two or more organic acrylate or methacrylate substituents. Examples of polyfunctional acrylates include diethylene glycol diacrylate, trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, bis(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol triacrylate, cyclohexanediol diacrylate, di(trimethylolpropane) tetraacrylate, or combinations thereof. Examples of polyfunctional methacrylates include trimethylolpropane trimethacrylate (TMPTMA), ethylene glycol dimethacrylate, butanediol dimethacrylate, butanediol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, allyl methacrylate, or combinations thereof. Additives may also include triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, sulfur, N-phenyl-bis-maleamide, zinc diacrylate, zinc dimethacrylate, divinylbenzene, 1,2-polybutadiene, trimethylolpropane trimethacrylate, tetramethylene glycol diacrylate, trifunctional acrylates, dipentaerythritol pentaacrylate, polyfunctional acrylates, cyclohexanediol diacrylate, polyfunctional methacrylates, metal salts of acrylates and methacrylates, oximes (e.g., quinone dioximes), etc.

[0071] In addition, oils can be used in the curing system. Oils may also be referred to as process oils, filler oils, or plasticizers. Available oils include mineral oils, synthetic processing oils, or combinations thereof, and can act as plasticizers. Plasticizers include, but are not limited to, aromatic oils, naphthenic oils, and filler oils. Exemplary synthetic processing oils include low molecular weight polylinear α-olefins and polybranched α-olefins. Suitable esters include monomeric materials and oligomers having an average molecular weight of less than about 2,000 g / mol or less than about 600 g / mol. Specific examples include aliphatic monoesters or diesters or alternatively, oligoaliphatic esters or alkyl ether esters.

[0072] The curing composition can be added at one or more locations, including the feed hopper of a melt-mixing extruder. In some embodiments, the curing agent and any additional additives can be added together to the TPV formulation; in other embodiments, one or more additives can be added to the TPV formulation at any or more different times than the time at which the curing agent is added, while the TPV formulation is being processed to form TPV.

[0073] Typically, the amount of curing agent present should be sufficient to at least partially vulcanize the elastomer, and in some embodiments, sufficient to completely vulcanize the elastomer. For example, the curing composition may be present in an amount of 1 phr or greater, such as 2 phr or greater, such as 3 phr or greater, such as 5 phr or greater, such as 8 phr or greater, such as 10 phr or greater, such as 12 phr or greater, such as 14 phr or greater, such as 16 phr or greater, such as 18 phr or greater, such as 20 phr or greater. The curing composition may be present in an amount of 40 phr or less, such as 35 phr or less, such as 30 phr or less, such as 28 phr or less, such as 25 phr or less, such as 23 phr or less, such as 21 phr or less, such as 20 phr or less, such as 18 phr or less, such as 16 phr or less, such as 14 phr or less, such as 12 phr or less, such as 10 phr or less. Similarly, the curing agent may be present in amounts of 1 phr or greater, such as 2 phr or greater, such as 3 phr or greater, such as 5 phr or greater, such as 8 phr or greater, such as 10 phr or greater, such as 12 phr or greater, such as 14 phr or greater, such as 16 phr or greater, such as 18 phr or greater, such as 20 phr or greater. The curing agent may be present in amounts of 40 phr or less, such as 35 phr or less, such as 30 phr or less, such as 28 phr or less, such as 25 phr or less, such as 23 phr or less, such as 21 phr or less, such as 20 phr or less, such as 18 phr or less, such as 16 phr or less, such as 14 phr or less, such as 12 phr or less, such as 10 phr or less. D. Oil

[0074] The thermoplastic vulcanizates and formulations disclosed herein also contain oils. For example, oils include, but are not limited to, plasticizer oils, process oils, filler oils, or mixtures thereof. In this respect, the resulting thermoplastic vulcanizates may also contain one or more of these oils.

[0075] Furthermore, as indicated herein, oil includes re-refined oil. As used herein, "re-refined oil" refers to used or waste oil that has undergone a process similar to the original process used to prepare the crude oil for use (e.g., filtration, distillation, and / or dehydration, etc.). As examples, "re-refined oil" can be obtained from waste oil in auto repair shops during automotive service and / or from oil used in the metal cutting industry during its processes. During such refining processes, contaminants are typically removed. Re-refined oil may also include those re-refined oils based on any other oils disclosed below.

[0076] In this regard, in one embodiment, at least 85 wt.%, such as at least 90 wt.%, such as at least 93 wt.%, such as at least 95 wt.%, such as at least 97 wt.%, such as at least 98 wt.%, such as at least 99 wt.%, of the refining oil may be oil. For example, the balance may be contaminants. In this regard, less than 10 wt.%, such as less than 8 wt.%, such as less than 6 wt.%, such as less than 5 wt.%, such as less than 4 wt.%, such as less than 3 wt.%, such as less than 2 wt.%, such as less than 1 wt.%, of the refining oil may be contaminants.

[0077] Specifically, the refining oil may have a sulfur content of 1000 ppm or less, such as 800 ppm or less, such as 600 ppm or less, such as 500 ppm or less, such as 400 ppm or less, such as 300 ppm or less, such as 200 ppm or less, such as 150 ppm or less, such as 100 ppm or less, such as 80 ppm or less, such as 50 ppm or less, such as 30 ppm or less, such as 20 ppm or less, such as 10 ppm or less. The sulfur content can be determined according to ASTM D5185.

[0078] Furthermore, the refining oil may have a polycyclic aromatic hydrocarbon (PAH) content of 5 wt.% or less, such as 4.5 wt.% or less, such as 4 wt.% or less, such as 3.5 wt.% or less, such as 3 wt.% or less, such as 2.5 wt.% or less, such as 2 wt.% or less, such as 1.5 wt.% or less, such as 1 wt.% or less. The PAH content can be determined according to IP 346.

[0079] In addition, the refining oil may include 80 wt.% or more, such as 85 wt.% or more, such as 90 wt.% or more, such as 92 wt.% or more, such as 94 wt.% or more, such as 95 wt.% or more, such as 96 wt.% or more, such as 97 wt.% or more, such as 98 wt.% or more, such as 99 wt.% or more saturates.

[0080] The purity of refining oil can also be indicated by color as defined according to ASTM D1500. For example, refining oil may have a color value of 2 or less, such as 1.5 or less, such as 1.0 or less, such as 0.5 or less.

[0081] In some embodiments, the oil may contain virgin oil in addition to refined oil. In this respect, virgin oil may be oil that is not considered refined oil. For example, such oil may not be considered waste or used oil that has already been refined. Therefore, in one embodiment, the oil may comprise a mixture of refined oil and virgin oil.

[0082] In some embodiments, any suitable oil may be included. In specific embodiments, the oil may be selected from: (i) extension oil, i.e., oil present in oil-extended rubber (such as oil present with the elastomer); (ii) free oil, i.e., oil added during the vulcanization process (separate from any other TPV formulation components such as the elastomer and thermoplastic vulcanized rubber); (iii) curing agent oil, i.e., oil used to dissolve / disperse the curing agent, for example, an oil-encapsulated curing agent dispersion such as an oil-encapsulated phenolic resin (and in such embodiments, the curing composition may therefore be present in the TPV formulation as an oil-encapsulated curing agent additive); and (iv) any combination of the aforementioned oils from (i)-(iii). Thus, oil (such as refining oil) may be present in the TPV formulation as part of another component (e.g., as part of the elastomer when the process oil is an extension oil, such that the elastomer comprises the elastomer and the extension oil; or as part of the curing composition when the process oil is a carrier of the oil-encapsulated curing agent, such that the curing composition comprises the curing agent oil and the curing agent). On the other hand, oil can be added to TPV separately from other components (i.e., as free oil).

[0083] In one embodiment, the refining oil may be provided separately from any other component in the formulation. In another embodiment, the refining oil may be a filler oil, such that it is provided together with an elastomer. In this regard, such an elastomer may be an oil-filled elastomer, particularly an elastomer filled with refining oil.

[0084] In various embodiments, the filler oil, free oil, and / or curing agent oil may be the same or different oils. Process oils may include one or more of (i) “refined” or “mineral” oils and (ii) synthetic oils. As used herein, mineral oil refers to a lubricating viscosity (i.e., 1 mm at 100°C) derived from petroleum crude oil and subjected to one or more refining and / or hydrotreating steps (such as fractionation, hydrocracking, dewaxing, isomerization, and hydrorefining) to purify and chemically modify the components to achieve the final property set. 2 Any hydrocarbon liquid with a kinematic viscosity of 600 liters per second or greater. Such "refined" oils are the opposite of "synthetic" oils, which are manufactured by combining monomer units into larger molecules using catalysts, initiators, and / or heat.

[0085] Typically, refining or synthetic process oils according to some embodiments may include, but are not limited to, any one or more of aromatic oils, naphthenic oils, and paraffinic oils. Exemplary synthetic process oils are polylinear α-olefins, polybranched α-olefins, and hydrogenated polyα-olefins. Compositions according to some embodiments of the present invention may include organic esters, alkyl ethers, or combinations thereof.

[0086] In some embodiments, at least a portion of the oil (e.g., all or a portion of any one or more of filler oil, free oil, and / or curing agent oil) is a low aromatic / sulfur content oil and has (i) an aromatic content of less than 5 wt.%, or less than 3.5 wt.%, or less than 1.5 wt.%, based on the weight of that portion of the oil; and (ii) a sulfur content of less than 0.3 wt.%, or less than 0.003 wt.%, based on the weight of that portion of the oil. The aromatic content can be determined in a manner consistent with method ASTM D2007. In some embodiments, the percentage of aromatic carbon in the process oil is preferably less than 2%, 1%, or 0.5%. In some embodiments, aromatic carbon is absent in the process oil. The percentage of aromatic carbon (%) as used herein is the ratio (percentage) of the number of aromatic carbon atoms to the total number of carbon atoms, as determined by method according to ASTM D2140.

[0087] Suitable oils in specific embodiments may include API Group I, II, III, IV, and V base oils. See API 1509, Engine Oil Licensing and Certification System, 17th Edition, September 2012, Appendix E, which is incorporated herein by reference. In this regard, in one embodiment, the oil may be a re-refined base oil, such as API Group I, II, III, IV, and / or V base oils.

[0088] Oils can have a specific viscosity index as defined according to ASTM D2270. For example, a viscosity index can be 80 or greater, such as 85 or greater, such as 90 or greater, such as 95 or greater, such as 100 or greater, such as 105 or greater, such as 110 or greater, such as 115 or greater. A viscosity index can be 180 or less, such as 170 or less, such as 160 or less, such as 150 or less, such as 140 or less, such as 130 or less, such as 125 or less, such as 120 or less, such as 115 or less, such as 110 or less.

[0089] In addition to the viscosity index, refining oils can have a specific kinematic viscosity as defined according to ASTM D7279. For example, at 40°C, the kinematic viscosity can be 15 cSt or greater, such as 18 cSt or greater, such as 21 cSt or greater, such as 24 cSt or greater, such as 27 cSt or greater, such as 30 cSt. The kinematic viscosity at 40°C can be 70 cSt or less, such as 60 cSt or less, such as 50 cSt or less, such as 45 cSt or less, such as 42 cSt or less, such as 39 cSt or less, such as 36 cSt or less, such as 33 cSt or less, such as 30 cSt or less, such as 27 cSt or less, such as 24 cSt or less. The kinematic viscosity at 100°C can be 0.5 cSt or greater, such as 1 cSt or greater, such as 1.5 cSt or greater, such as 2 cSt or greater, such as 2.3 cSt or greater, such as 2.6 cSt or greater, such as 2.9 cSt or greater, such as 3.3 cSt or greater, such as 3.6 cSt or greater, such as 3.9 cSt or greater, such as 4.2 cSt or greater, such as 4.6 cSt or greater, such as 5 cSt or greater. The kinematic viscosity at 100°C can be 12 cSt or less, such as 10 cSt or less, such as 8 cSt or less, such as 7.6 cSt or less, such as 7.2 cSt or less, such as 6.8 cSt or less, such as 6.4 cSt or less, such as 6 cSt or less, such as 5.6 cSt or less, such as 5.2 cSt or less, such as 4.8 cSt or less, such as 4.4 cSt or less, such as 4 cSt or less.

[0090] Furthermore, refining oils may have specific pour points as determined according to ASTM D5949. For example, a pour point may be 15°C or less, such as 10°C or less, such as 5°C or less, such as 0°C or less, such as -2°C or less, such as -5°C or less, such as -8°C or less, such as -10°C or less, such as -12°C or less, such as -15°C or less, such as -18°C or less, such as -20°C or less, such as -25°C or less. A pour point may be -60°C or greater, such as -50°C or greater, such as -40°C or greater, such as -30°C or greater, such as -26°C or greater, such as -22°C or greater, such as -20°C or greater, such as -16°C or greater, such as -12°C or greater, such as -9°C or greater, such as -6°C or greater.

[0091] Oil (such as refining oil) may be present in formulations and / or thermoplastic vulcanizates in amounts of 10 phr or greater, such as 20 phr or greater, such as 30 phr or greater, such as 40 phr or greater, such as 50 phr or greater, such as 60 phr or greater, such as 70 phr or greater, such as 80 phr or greater, such as 90 phr or greater, such as 100 phr or greater, such as 110 phr or greater, such as 120 phr or greater, such as 130 phr or greater. Oil (such as refining oil) may be present in formulations and / or thermoplastic vulcanizates in amounts of 250 phr or less, such as 220 phr or less, such as 200 phr or less, such as 180 phr or less, such as 160 phr or less, such as 150 phr or less, such as 140 phr or less, such as 130 phr or less, such as 120 phr or less, such as 110 phr or less, such as 100 phr or less.

[0092] Thermoplastic vulcanizates and / or formulations may typically contain about 2 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more of oil, such as refining oil. Thermoplastic vulcanizates and / or formulations may contain about 60 wt.% or less, about 50 wt.% or less, such as about 40 wt.% or less, such as about 35 wt.% or less, such as about 30 wt.% or less, such as about 25 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less of oil, such as refining oil.

[0093] In one embodiment, a majority of the total oil provided may be supplied as free oil. For example, 50 wt.% or more, such as 60 wt.% or more, such as 70 wt.% or more, such as 75 wt.% or more, such as 80 wt.% or more, such as 85 wt.% or more, such as 90 wt.% or more, such as 95 wt.% or more, may be free oil. The remaining oil may be filler oil and / or curing agent oil. For example, 50 wt.% or less, such as 40 wt.% or less, such as 30 wt.% or less, such as 20 wt.% or less, such as 15 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 5 wt.% or less, may be filler oil and / or curing agent oil.

[0094] Furthermore, in one embodiment, the refining oil may be provided primarily as free oil rather than filler oil and / or curing agent oil. For example, in the provided refining oil, 50 wt.% or more, such as 60 wt.% or more, 70 wt.% or more, such as 75 wt.% or more, such as 80 wt.% or more, such as 85 wt.% or more, such as 90 wt.% or more, such as 95 wt.% or more, such as 98 wt.% or more, such as about 100 wt.%, may be provided as free oil. The remaining oil may be filler oil and / or curing agent oil.

[0095] In another embodiment, the refining oil may be provided primarily as a filler oil rather than as free oil and / or curing agent oil. For example, in the provided refining oil, 50 wt.% or more, such as 60 wt.% or more, 70 wt.% or more, such as 75 wt.% or more, such as 80 wt.% or more, such as 85 wt.% or more, such as 90 wt.% or more, such as 95 wt.% or more, such as 98 wt.% or more, such as about 100 wt.%, may be provided as a filler oil. The remaining oil may be free oil and / or curing agent oil. E. Other additives

[0096] Some embodiments of the thermoplastic vulcanized rubber formulation may optionally further comprise one or more additives. Suitable additional TPV additives include, but are not limited to, fillers (e.g., organic fillers, inorganic fillers, minerals, etc.), processing aids, acid scavengers, antioxidants, stabilizers, lubricants, antiblocking agents, antistatic agents, waxes, foaming agents, colorants / pigments, flame retardants, and other processing aids. In this regard, the resulting thermoplastic vulcanized rubber may also contain one or more of such additives.

[0097] Some embodiments of the TPV formulation may include polymer processing additives. The processing additives used in such embodiments are polymeric resins with very high melt flow indices. These polymeric resins include straight-chain and branched molecules having melt flow rates greater than about 500 dg / min, more preferably greater than about 750 dg / min, even more preferably greater than about 1000 dg / min, even more preferably greater than about 1200 dg / min, and even more preferably greater than about 1500 dg / min. The thermoplastic elastomers disclosed herein may include mixtures of various branched or linear polymer processing additives, as well as mixtures of both linear and branched polymer processing additives. Unless otherwise stated, references to polymer processing additives will include both linear and branched additives. Preferred linear polymer processing additives are polypropylene homopolymers. Preferred branched polymer processing additives include diene-modified polypropylene polymers.

[0098] Furthermore, the formulation may also include reinforcing and / or unreinforcing fillers. Available fillers and extenders include conventional inorganic materials such as calcium carbonate, clay, silica, talc, and titanium dioxide, as well as organic materials such as carbon blocks, graphene, and organic and inorganic nanofillers. In one embodiment, such filler may be a glass filler, such as glass fiber, glass beads, mixtures thereof, etc. In one embodiment, the formulation and the resulting thermoplastic vulcanizate may not contain any glass beads, particularly any glass beads. In this respect, such glass beads may be present in an amount less than 1 wt.%, such as less than 0.5 wt.%, such as less than 0.3 wt.%, such as less than 0.1 wt.%, such as less than 0.05 wt.%, such as less than 0.01 wt.%, such as about 0 wt.%, based on the weight of the thermoplastic vulcanizate.

[0099] In some embodiments, the TPV formulation may include an acid scavenger. These acid scavengers can be added to the thermoplastic vulcanizate after the desired curing level has been reached. Preferably, the acid scavenger is added after dynamic vulcanization. Available acid scavengers include hydrotalcite. Both synthetic and natural hydrotalcite can be used. An exemplary natural hydrotalcite can be made from the formula Mg6Al2(OH). 16 The chemical structure is represented by CO3•4H2O. Synthetic hydrotalcite compounds can have the formula Mg. 4.3 Al2(OH) 12 • 6CO3 •mH2O or Mg 4.5 Al2(OH) 13 CO3 • 3.5H2O.

[0100] These additives can be used in amounts that provide the desired effect. In this respect, additives can be present in amounts up to about 50% by weight of the total TPV formulation or TPV. In this respect, the corresponding additives and / or combinations of additives can be present in amounts of 0.001 wt.% or greater, such as 0.01 wt.% or greater, such as 0.05 wt.% or greater, such as 0.1 wt.% or greater, such as 0.2 wt.% or greater, such as 0.3 wt.% or greater, such as 0.5 wt.% or greater, such as 1 wt.% or greater, such as 2 wt.% or greater, such as 3 wt.% or greater, such as 5 wt.% or greater, such as 8 wt.% or greater, such as 10 wt.% or greater, such as 12 wt.% or greater, such as 15 wt.% or greater, such as 20 wt.% or greater, such as 25 wt.% or greater, such as 30 wt.% or greater. They may be present in amounts of 50 wt.% or less, such as 40 wt.% or less, such as 30 wt.% or less, such as 25 wt.% or less, such as 20 wt.% or less, such as 18 wt.% or less, such as 15 wt.% or less, such as 13 wt.% or less, such as 10 wt.% or less, such as 8 wt.% or less, such as 6 wt.% or less, such as 4 wt.% or less, such as 3 wt.% or less, such as 2 wt.% or less, such as 1 wt.% or less, such as 0.5 wt.% or less. In another embodiment, such percentages may be based on the weight of the thermoplastic resin. In another embodiment, such percentages may be based on the weight of the elastomer. In even another embodiment, such percentages may be based on the combined weight of the thermoplastic resin and the elastomer. F. TPV ingredients

[0101] Generally, as used herein, "TPV formulation" refers to a mixture of ingredients that are blended or otherwise assembled to form a TPV before or during the processing of the TPV formulation. This is based on the recognition that the ingredients that are blended together and then processed may or may not be present in the final TPV in the same amount added to the formulation, depending on the reactions that occur between some or all of the ingredients during the processing of the blended ingredients.

[0102] Typically, TPV formulations according to various embodiments include an elastomer, a thermoplastic resin, a curing agent (or curing composition), and an oil comprising refining oil, along with any other optional additives. As will be discussed in more detail below, TPV formulations undergo processing (including dynamic vulcanization or dynamic curing) to form TPV. In some embodiments, any other additives may be added to the TPV formulation during processing, either before or after dynamic vulcanization.

[0103] The relative amounts of various components in a TPV formulation are conveniently characterized based on the amount of elastomer in the formulation, particularly in parts by weight of 100 parts by weight of rubber (phr). In embodiments where the elastomer comprises both the elastomer and extension oil, as is common for many commercially available elastomers such as EPDM, the phr amount is based solely on the amount of elastomer, excluding the extension oil present with the elastomer. Thus, as an example, an elastomer containing 100 parts EPDM (rubber) and 75 parts extension oil would actually be considered to exist in the TPV formulation at 175 phr (i.e., based on 100 parts EPDM rubber). If such a TPV formulation is further characterized as containing 50 phr of thermoplastic resin, then the formulation would comprise 50 parts by weight of thermoplastic resin in addition to the 100 parts by weight of elastomer and the 75 parts by weight of extension oil.

[0104] Some embodiments of TPV formulations may include a thermoplastic resin in an amount of about 10 to about 300 parts per 100 parts by weight of elastomer or rubber (phr). In various embodiments, the thermoplastic resin is included in the TPV formulation in an amount ranging from the lower of any one of about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 165, 170, and 175 phr to the higher of any one of about 100, 125, 150, 175, 200, 225, 250, 275, 300, 350, 400, 450, 500, 550, 600, 650, 700, and 750 phr. The thermoplastic resin may be included in an amount ranging from any of the lower values ​​to any of the higher values ​​mentioned above, provided that the higher value is greater than or equal to the lower value. In a specific embodiment, increasing the amount of thermoplastic resin corresponds to increasing the hardness of the dynamically vulcanized TPV.

[0105] When the elastomer consists only of elastomer, it is present in 100 phr by definition (because it is the basis of the phr notation). However, in embodiments in which the elastomer component includes components other than the elastomer (such as filler oil), the elastomer may be included in the TPV formulation in an amount ranging from the lower of about 100.05, 100.1, 100.15, 100.2, 105, 110, 115 and 120 phr to the higher of about 110, 120, 125, 150, 175, 200, 225 and 250 phr.

[0106] As previously noted, some embodiments of the TPV formulation may optionally include additional TPV additives. The amount of the additional additives is separate and in addition to those already included in another component of the TPV formulation. For example, any additives included with the elastomer, such as extension oil, are considered as part of the amount of elastomer added to the formulation; therefore, the enumerated amounts of additional additives do not include those included with the elastomer. The additional additives may be present in the TPV formulation in aggregates in amounts ranging from about 0 phr to about 300 phr. In some embodiments, the additional additives may be present in the TPV in aggregates in amounts ranging from the lower of about 0, 5, 10, 15, 25, 30, 40, 50, 60, 70, 80, 90, and 100 phr to the higher of about 25, 30, 40, 50, 60, 80, 100, 125, 150, 175, 200, 225, 250, 275, and 300 phr. Additional additives may be included in a total amount ranging from any of the lower values ​​to any of the higher values ​​mentioned above, provided that the higher value is greater than or equal to the lower value. In one embodiment, such a phr may refer to a single additional additive rather than an aggregate.

[0107] For convenience, the components of the TPV formulations in various embodiments can alternatively be characterized based on their weight percentage in the TPV formulation according to the following:

[0108] Thermoplastic resins can be available in quantities ranging from the lowest of any one of about 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, and 25 wt.% to about 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%. The higher value of any one of the following wt.%, 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 43 wt.%, 44 wt.%, 45 wt.%, 46 wt.%, 47 wt.%, 48 wt.%, 49 wt.%, 50 wt.%, 51 wt.%, 52 wt.%, 53 wt.%, 54 wt.%, 55 wt.%, and 60 wt.% is present in the TPV formulation, provided that the higher value is greater than or equal to the lower value.

[0109] The elastomer may be present in TPV formulations in an amount ranging from the lower of any one of about 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, and 35 wt.% to the higher of any one of 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, and 80 wt.%, provided that the higher value is greater than or equal to the lower value, and the elastomer is present in TPV formulations in the range of about 20 to about 300 phr.

[0110] Optional additional TPV additives may be present in the TPV formulation in an amount ranging from the low of any one of about 0 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, and 40 wt.% to the high of any one of about 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, and 65 wt.%, provided that the high value is greater than or equal to the low value, and the additive is present in the TPV formulation in the range of about 0 to about 300 phr.

[0111] As indicated herein, thermoplastic vulcanizates, as disclosed herein, include relatively high levels of recycling content. For example, thermoplastic formulations and / or thermoplastic vulcanizates may include refining oils as mentioned herein. Furthermore, thermoplastic formulations and / or thermoplastic vulcanizates may also include recycled thermoplastic resins. Therefore, the recycling content can include refining oils and any recycled thermoplastic resins. Currently, the recycling content may also include any recycled elastomers. Therefore, based on the total weight of the thermoplastic formulation and / or thermoplastic vulcanizate, the recycling content can be about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more. Based on the total weight of the thermoplastic formulation and / or thermoplastic vulcanized rubber, the recycling content may be about 95 wt.% or less, such as about 90 wt.% or less, such as about 80 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 30 wt.% or less, such as about 20 wt.% or less. G. Processing TPV ingredients

[0112] The thermoplastic vulcanizates disclosed herein are prepared using dynamic vulcanization technology. The term "dynamic vulcanization" refers to a vulcanization or curing process for TPV formulations containing elastomers, wherein the elastomers are vulcanized under high-shear mixing conditions at temperatures above the melting point of the thermoplastic resin to produce thermoplastic vulcanizates. In dynamic vulcanization, the elastomers are simultaneously crosslinked and dispersed as fine particles within the thermoplastic resin or matrix, although other morphologies, such as bicontinuous morphologies, may exist depending on the degree of curing, the viscosity ratio of the elastomer to the resin, the mixing strength, the residence time, and the temperature.

[0113] In this regard, this disclosure relates to a method for dynamically vulcanizing or dynamically curing a formulation comprising a thermoplastic resin, an elastomer, an oil comprising a refining oil, and a curing agent. Thus, dynamic vulcanization occurs in the presence of the refining oil. This method, in turn, can provide a thermoplastic vulcanizate comprising a thermoplastic resin and at least partially cured elastomer. For example, the thermoplastic resin can be provided as a continuous phase or matrix, wherein the at least partially cured elastomer is provided as a dispersed phase within the continuous thermoplastic phase.

[0114] In some embodiments, processing may include melt-blending a TPV formulation comprising an elastomer, a thermoplastic resin, and a curing agent in a chamber. The chamber can be any container suitable for blending the selected composition under the temperature and shear force conditions necessary to form a thermoplastic vulcanizate. In this regard, the chamber can be a mixer, such as a Banbury™ mixer or a Brabender™ mixer, and certain mixing extruders, such as co-rotating, counter-rotating, and twin-screw extruders, and co-kneaders, such as a Buss® kneader. According to one embodiment, the chamber is an extruder, which may be a single-screw or multi-screw extruder. The term "multi-screw extruder" means an extruder having two or more screws; two-screw and three-screw extruders are exemplary, and in some embodiments, two-screw or twin-screw extruders are preferred. The screw of the extruder may have multiple lobes; two- and three-lobed screws are preferred. It will be readily understood that other screw designs may be selected according to the methods of the embodiments disclosed herein. In some embodiments, dynamic vulcanization may occur during extrusion and / or as a result of extrusion. After being discharged from the mixer, the blend containing vulcanized rubber and thermoplastic can be milled, chopped, extruded, granulated, injection molded, or processed by any other desired technique.

[0115] Dynamic vulcanization of the elastomer can be performed to achieve relatively high shear rates. In specific embodiments, blending can be carried out at temperatures not exceeding about 400°C, preferably not exceeding about 300°C, and more preferably not exceeding about 250°C. The minimum temperature for melt blending is typically above or equal to about 130°C, preferably above or equal to about 150°C, and more particularly above about 180°C. The blending time is selected by taking into account the properties of the compounds used in the TPV formulation and the blending temperature. The time typically varies from about 5 seconds to about 120 minutes, and in most cases from about 10 seconds to about 30 minutes.

[0116] In some embodiments, dynamic vulcanization may include a phase inversion. As those skilled in the art will understand, dynamic vulcanization can be initiated by including a rubber comprising a larger volume fraction than the thermoplastic resin. Thus, when the volume fraction of rubber is greater than the volume fraction of the thermoplastic resin, the thermoplastic resin can exist as a discontinuous phase. As dynamic vulcanization proceeds, the viscosity of the rubber increases and a phase inversion occurs under dynamic mixing. In other words, during the phase inversion, the thermoplastic resin phase transforms into a continuous phase.

[0117] During dynamic vulcanization, one or more additional additives are preferably present in the TPV formulation, although in some embodiments, one or more additional additives (if any) may be added to the composition after curing and / or phase inversion (e.g., after the processed dynamic vulcanization portion). After dynamic vulcanization, additional additives can be included using a variety of techniques. In one embodiment, they may be added while the thermoplastic vulcanizate remains in its molten state from the dynamic vulcanization process. For example, additional additives may be added downstream of the dynamic vulcanization location within a process employing continuous processing equipment such as a single-screw or twin-screw extruder. In other embodiments, the thermoplastic vulcanizate may be “post-treated” or granulated, subsequently melted, and additional additives may be added to the molten thermoplastic vulcanizate product. This latter process may be referred to as a “second pass” addition of the component.

[0118] Although elastomers can be partially or completely cured, thermoplastic vulcanized rubbers can be processed and reprocessed using conventional plastics processing techniques such as extrusion, injection molding, and compression molding. The elastomers within these thermoplastic elastomers are typically in the form of finely and well-dispersed particles of vulcanized or cured rubber within a continuous thermoplastic phase or matrix, although bicontinuous morphologies or phase inversions are also possible. In those embodiments where the cured rubber is in the form of finely and well-dispersed particles within a thermoplastic medium, the rubber particles may have an average diameter of less than 50 μm, such as less than 30 μm, such as less than 10 μm, such as less than 5 μm, such as less than 1 μm. In preferred embodiments, at least 50%, such as at least 60%, such as at least 75%, of the rubber particles may have an average diameter of less than 5 μm, such as less than 2 μm, such as less than 1 μm.

[0119] The degree of curing can be measured by determining the amount of rubber extractable from the thermoplastic vulcanizate using cyclohexane or boiling xylene as an extractant. Preferably, the rubber may have a certain degree of curing in which no more than 15% by weight, such as no more than 10% by weight, such as no more than 5% by weight, such as no more than 3% by weight, is extractable from cyclohexane at 23°C, as described in U.S. Patent Nos. 4,311,628, 5,100,947, and 5,157,081 (all of which are incorporated herein by reference). Alternatively, the rubber may have a certain degree of curing such that the crosslinking density is at least 4 × 10⁻⁶. -5 Such as at least 7 × 10 -5 Such as at least 10 × 10 -5 Moles per milliliter of rubber. See Ellul et al., Rubber Chemistry and Technology, Vol. 68, pp. 573-584 (1995), Crosslink Densities and Phase Morphologies in Dynamically Vulcanized TPEs.

[0120] The resulting thermoplastic vulcanizate can have a desired density that allows it to be used in molded parts as described herein. In this respect, the density can be 0.3 g / cm³. 3 Or even higher, such as 0.4 g / cm³ 3 Or even higher, such as 0.5 g / cm³ 3 Or even higher, such as 0.6 g / cm³ 3 Or even higher, such as 0.65 g / cm³ 3 Or even higher, such as 0.7 g / cm³3 Or even higher, such as 0.75 g / cm³ 3 Or even higher, such as 0.8 g / cm³ 3 Or even higher, such as 0.85 g / cm³ 3 Or even higher, such as 0.9 g / cm³ 3 Or even higher, such as 0.95 g / cm³ 3 Or even higher, such as 1 g / cm³ 3 Or even higher, such as 1.05 g / cm³ 3 Or even higher, such as 1.1 g / cm³ 3 Or even higher, such as 1.15 g / cm³ 3 Or even higher, such as 1.2 g / cm³ 3 Or even higher. The density could be 2 g / cm³. 3 Or even smaller, such as 1.8 g / cm³ 3 Or even smaller, such as 1.6 g / cm³ 3 Or even smaller, such as 1.4 g / cm³ 3 Or even smaller, such as 1.3 g / cm³ 3 Or even smaller, such as 1.2 g / cm³ 3 Or even smaller, such as 1.1 g / cm³ 3 Or even smaller, such as 1.0 g / cm³ 3 Or even smaller, such as 0.95 g / cm³ 3 Or even smaller, such as 0.90 g / cm³ 3 Or even smaller, such as 0.7 g / cm 3 Or even smaller, such as 0.6 g / cm 3 Or even smaller, such as 0.55 g / cm³ 3 . H. Formation of molded parts

[0121] Once formed, the thermoplastic vulcanizate can be molded into a molded part using any of a variety of techniques known in the art. For example, the thermoplastic vulcanizate can be advantageously manufactured using typical molding processes such as injection molding, extrusion molding, compression molding, blow molding, rotational molding, overmolding, etc. Typically, these processes involve heating the thermoplastic vulcanizate to a temperature equal to or above the melt temperature of the thermoplastic resin to form a preform with a mold cavity, then forming the molded part, cooling the molded part to a temperature equal to or below the crystallization temperature of the thermoplastic vulcanizate, and demolding the molded part from the mold. The mold cavity defines the shape of the molded part. The molded part is cooled within the mold at a temperature equal to or below the crystallization temperature of the thermoplastic vulcanizate, and subsequently demolded from the mold.

[0122] Thermoplastic vulcanizates can also be shaped using extrusion molding to form molded parts. In this regard, thermoplastic vulcanizates can be extruded as described herein. Upon exiting the extruder, the thermoplastic vulcanizate can be formed or shaped to create a molded part. Such molded parts can be formed by using a specific die to shape the thermoplastic vulcanizate as it exits the extruder. This shaping / forming process (such as extrusion) can be automated or robotic. In this respect, the method of forming molded parts is not necessarily limited. I. characteristic

[0123] By utilizing refining oils as disclosed herein, thermoplastic vulcanizates can exhibit certain desired properties. For example, utilizing materials such as refining oils and optional other recycled materials, such as thermoplastic resins and elastomers, as disclosed herein can lead to a reduction in carbon footprint. Specifically, using the cradle-to-gate method, the carbon footprint can be 3.0 kg CO2 equivalent / kg or lower, such as 2.8 kg CO2 equivalent / kg or lower, such as 2.6 kg CO2 equivalent / kg or lower, such as 2.4 kg CO2 equivalent / kg or lower, such as 2.2 kg CO2 equivalent / kg or lower, such as 2.0 kg CO2 equivalent / kg or lower, such as 1.8 kg CO2 equivalent / kg or lower, such as 1.6 kg CO2 equivalent / kg or lower, such as 1.5 kg CO2 equivalent / kg or lower, such as 1.4 kg CO2 equivalent / kg or lower, such as 1.3 kg CO2 equivalent / kg or lower, such as 1.2 kg CO2 equivalent / kg or lower, such as 1.1 kg CO2 equivalent / kg or lower, such as 1.0 kg CO2 equivalent / kg or lower. The carbon footprint can be estimated using the following equation: Among them W i It is the weight fraction, X i This is the CO2 footprint of component i in the preparation, where C is a constant that can be added to account for CO2 emissions from energy use, raw material logistics, and packaging involved. In this disclosure, C is estimated to be approximately 0.35 kg CO2 equivalent / kg. CO2 footprint values ​​for the base raw materials are derived from the EcoInvent 3.6 database or supplied by the raw material manufacturers.

[0124] Furthermore, the inventors of this invention have discovered that the properties of these materials utilizing recycled content can be comparable to those exhibited by the same thermoplastic vulcanizates made from one or more virgin oils rather than from any one or more refining oils. In particular, any single corresponding property, as confirmed below for thermoplastic vulcanizates comprising refining oils as defined herein, can be found in the corresponding thermoplastic vulcanizates made from virgin oils rather than from any refining oils within 35%, such as within 30%, such as within 25%, such as within 20%, such as within 18%, such as within 16%, such as within 14%, such as within 12%, such as within 10%, such as within 9%, such as within 8%, such as within 7%, such as within 6%, such as within 5%, such as within 4%, such as within 3%, such as within 2%, such as within 1%.

[0125] In this regard, thermoplastic vulcanizates can exhibit a specific Shore A hardness (ASTM 2240-15(2021); 15 seconds), which is used to measure the hardness of thermoplastic vulcanizates and provide an indication of indentation resistance. Thermoplastic vulcanizates can have a Shore A hardness of 25 to 100. For example, thermoplastic vulcanizates can have a Shore A hardness of 25 or greater, such as 35 or greater, such as 40 or greater, such as 45 or greater, such as 50 or greater, such as 55 or greater, such as 60 or greater, such as 65 or greater, such as 70 or greater, such as 75 or greater. Thermoplastic vulcanizates can have a Shore A hardness of 100 or less, such as 95 or less, such as 90 or less, such as 80 or less, such as 70 or less, such as 65 or less, such as 60 or less, such as 55 or less, such as 50 or less. This hardness allows the thermoplastic resin and / or the resulting molded parts to provide the compliance required to effectively perform the desired application function. In one embodiment, the above-described Shore A hardness can be used on an unaged sample. In another embodiment, the above-described Shore A hardness can be used on an aged sample. For example, the sample can be aged in an oven at 70°C for 168 hours, at 110°C for 168 hours, and / or at 100°C for 1000 hours. In this respect, this Shore A hardness can be achieved under at least one of the above-described aging conditions, such as at least two, or such as all three.

[0126] Relatedly, thermoplastic vulcanizates can also exhibit specific Shore D hardness (ASTM 2240-15(2021); 15 seconds). In this regard, thermoplastic vulcanizates can have a Shore D hardness greater than 0 to 50. For example, thermoplastic vulcanizates can have a Shore D hardness greater than 0, such as 5 or greater, such as 10 or greater, such as 15 or greater, such as 20 or greater, such as 25 or greater, such as 30 or greater, such as 35 or greater, such as 40 or greater. Thermoplastic vulcanizates can have a Shore D hardness of 50 or less, such as 45 or less, such as 40 or less, such as 35 or less, such as 30 or less, such as 25 or less, such as 20 or less, such as 15 or less, such as 10 or less, such as 5 or less. In one embodiment, the above-mentioned Shore D hardness can be used for unaged samples. In another embodiment, the above-mentioned Shore D hardness can be used for aged samples. For example, a sample can be aged in an oven at 70°C for 168 hours, at 110°C for 168 hours, and / or at 100°C for 1000 hours. In this respect, such Shore D hardness can be achieved under at least one of the above aging conditions, such as at least two, or such as all three.

[0127] In addition, thermoplastic vulcanizates can exhibit a certain strength as indicated by certain mechanical properties. For example, thermoplastic vulcanizates can exhibit a 100% modulus (ASTM D412-16, Mold C, Crossflow) of at least 0.3 MPa, such as 0.3 to 50 MPa, such as 0.5 to 10 MPa, such as 1 to 8 MPa, such as 2 to 7 MPa, also known as the modulus at 100% elongation or M100. For example, 100% modulus can be 0.3 MPa or greater, such as 0.4 MPa or greater, such as 0.5 MPa or greater, such as 0.8 MPa or greater, such as 1 MPa or greater, such as 1.1 MPa or greater, such as 1.2 MPa or greater, such as 1.3 MPa or greater, such as 1.4 MPa or greater, such as 1.5 MPa or greater, such as 2 MPa or greater, such as 2.5 MPa or greater, such as 3 MPa or greater, such as 4 MPa or greater, such as 5 MPa or greater, such as 6 MPa or greater, such as 10 MPa or greater, such as 20 MPa or greater, such as 30 MPa or greater. The 100% modulus can be 50 MPa or less, such as 40 MPa or less, such as 30 MPa or less, such as 25 MPa or less, such as 20 MPa or less, such as 15 MPa or less, such as 10 MPa or less, such as 8 MPa or less, such as 6 MPa or less, such as 5 MPa or less, such as 4.5 MPa or less, such as 4 MPa or less, such as 3.8 MPa or less, such as 3.5 MPa or less, such as 3.3 MPa or less, such as 3 MPa or less, such as 2.8 MPa or less, such as 2.5 MPa or less, such as 2.3 MPa or less, such as 2 MPa or less, such as 1.9 MPa or less, such as 1.8 MPa or less, such as 1.5 MPa or less, such as 1.3 MPa or less, such as 1.1 MPa or less, such as 0.8 MPa or less. In one embodiment, the above-mentioned modulus at 100% elongation can be used for unaged samples. In another embodiment, the modulus at 100% elongation described above can be used to age the sample. For example, the sample can be aged in an oven at 70°C for 168 hours, at 110°C for 168 hours, and / or at 100°C for 1000 hours. In this respect, such a modulus at 100% elongation can be achieved under at least one of the above aging conditions, such as at least two, or such as all three.

[0128] In addition, thermoplastic vulcanizates can exhibit a certain strength as indicated by certain mechanical properties. For example, thermoplastic vulcanizates can exhibit a 50% modulus (ASTM D412-16, Mold C, Crossflow) of at least 0.3 MPa, such as 0.3 to 50 MPa, such as 0.5 to 10 MPa, such as 1 to 8 MPa, such as 2 to 7 MPa, also known as the modulus at 50% elongation or M50. For example, 50% modulus can be 0.3 MPa or greater, such as 0.4 MPa or greater, such as 0.5 MPa or greater, such as 0.8 MPa or greater, such as 1 MPa or greater, such as 1.1 MPa or greater, such as 1.2 MPa or greater, such as 1.3 MPa or greater, such as 1.4 MPa or greater, such as 1.5 MPa or greater, such as 2 MPa or greater, such as 2.5 MPa or greater, such as 3 MPa or greater, such as 4 MPa or greater, such as 5 MPa or greater, such as 6 MPa or greater, such as 10 MPa or greater, such as 20 MPa or greater, such as 30 MPa or greater. The 50% modulus can be 50 MPa or less, such as 40 MPa or less, such as 30 MPa or less, such as 25 MPa or less, such as 20 MPa or less, such as 15 MPa or less, such as 10 MPa or less, such as 8 MPa or less, such as 6 MPa or less, such as 5 MPa or less, such as 4.5 MPa or less, such as 4 MPa or less, such as 3.8 MPa or less, such as 3.5 MPa or less, such as 3.3 MPa or less, such as 3 MPa or less, such as 2.8 MPa or less, such as 2.5 MPa or less, such as 2.3 MPa or less, such as 2 MPa or less, such as 1.9 MPa or less, such as 1.8 MPa or less, such as 1.5 MPa or less, such as 1.3 MPa or less, such as 1.1 MPa or less, such as 0.8 MPa or less. In one embodiment, the above-mentioned modulus at 50% elongation can be used for unaged samples. In another embodiment, the modulus at 50% elongation described above can be used for aging samples. For example, the sample can be aged in an oven at 70°C for 168 hours, at 110°C for 168 hours, and / or at 100°C for 1000 hours. In this respect, such a modulus at 50% elongation can be achieved under at least one of the above aging conditions, such as at least two, or such as all three.

[0129] In addition, thermoplastic vulcanizates can exhibit a certain strength as indicated by certain mechanical properties. For example, thermoplastic vulcanizates can exhibit a 25% modulus (ASTM D412-16, Mold C, Crossflow) of at least 0.3 MPa, such as 0.3 to 50 MPa, such as 0.5 to 10 MPa, such as 1 to 8 MPa, such as 1 to 4 MPa, also known as the modulus at 25% elongation or M25. For example, a 25% modulus can be 0.3 MPa or greater, such as 0.4 MPa or greater, such as 0.5 MPa or greater, such as 0.8 MPa or greater, such as 1 MPa or greater, such as 1.1 MPa or greater, such as 1.2 MPa or greater, such as 1.3 MPa or greater, such as 1.4 MPa or greater, such as 1.5 MPa or greater, such as 2 MPa or greater, such as 2.5 MPa or greater, such as 3 MPa or greater, such as 4 MPa or greater, such as 5 MPa or greater, such as 6 MPa or greater, such as 10 MPa or greater, such as 20 MPa or greater, such as 30 MPa or greater. The 25% modulus can be 50 MPa or less, such as 40 MPa or less, such as 30 MPa or less, such as 25 MPa or less, such as 20 MPa or less, such as 15 MPa or less, such as 10 MPa or less, such as 8 MPa or less, such as 6 MPa or less, such as 5 MPa or less, such as 4.5 MPa or less, such as 4 MPa or less, such as 3.8 MPa or less, such as 3.5 MPa or less, such as 3.3 MPa or less, such as 3 MPa or less, such as 2.8 MPa or less, such as 2.5 MPa or less, such as 2.3 MPa or less, such as 2 MPa or less, such as 1.9 MPa or less, such as 1.8 MPa or less, such as 1.5 MPa or less, such as 1.3 MPa or less, such as 1.1 MPa or less, such as 0.8 MPa or less. In one embodiment, the above-mentioned modulus at 25% elongation can be used for unaged samples. In another embodiment, the modulus at 25% elongation described above can be used for aging samples. For example, the sample can be aged in an oven at 70°C for 168 hours, at 110°C for 168 hours, and / or at 100°C for 1000 hours. In this respect, such a modulus at 25% elongation can be achieved under at least one of the above aging conditions, such as at least two, or such as all three.

[0130] Thermoplastic vulcanizates can also exhibit tensile stresses (i.e., tensile strengths) of 0.5 to 50 MPa, such as 1 to 20 MPa, such as 2 to 12 MPa, such as 3 to 9 MPa. For example, thermoplastic vulcanizates can exhibit tensile stresses of 0.5 MPa or greater, such as 1 MPa or greater, such as 1.5 MPa or greater, such as 2 MPa or greater, such as 2.5 MPa or greater, such as 3 MPa or greater, such as 3.5 MPa or greater, such as 4 MPa or greater, such as 4.5 or greater, such as 5 MPa or greater, such as 5.5 or greater, such as 6 MPa or greater, such as 7 MPa or greater, such as 8 MPa or greater, such as 9 MPa or greater, such as 10 MPa or greater, such as 15 MPa or greater, such as 20 MPa or greater, such as 30 MPa or greater, such as 40 MPa or greater, such as 50 MPa or greater, such as 60 MPa or greater, such as 70 MPa or greater. The tensile stress can be 100 MPa or less, such as 80 MPa or less, such as 60 MPa or less, such as 50 MPa or less, such as 40 MPa or less, such as 30 MPa or less, such as 25 MPa or less, such as 20 MPa or less, such as 18 MPa or less, such as 15 MPa or less, such as 13 MPa or less, such as 11 MPa or less, such as 10 MPa or less, such as 9 MPa or less, such as 8 MPa or less, such as 7 MPa or less, such as 6.5 MPa or less, such as 6 MPa or less, such as 5.5 MPa or less, such as 5 MPa or less, such as 4.5 MPa or less, such as 4 MPa or less, such as 3.5 MPa or less, such as 3 MPa or less, such as 2.5 MPa or less. The tensile stress can be determined according to ASTM D412-16 at a temperature of 23°C (mold C, crossflow). In one embodiment, the above-mentioned fracture tensile stress can be used for an unaged sample. In another embodiment, the aforementioned tensile stress at break can be used to age the sample. For example, the sample can be aged in an oven at 70°C for 168 hours, at 110°C for 168 hours, and / or at 100°C for 1000 hours. In this respect, such tensile stress at break can be achieved under at least one of the aforementioned aging conditions, such as at least two, or such as all three.

[0131] Thermoplastic vulcanizates can also exhibit desired elongation at break. For example, elongation at break can be 20% or greater, such as 40% or greater, such as 60% or greater, such as 80% or greater, such as 100% or greater, such as 150% or greater, such as 200% or greater, such as 250% or greater, such as 300% or greater, such as 350% or greater, such as 400% or greater, such as 500% or greater, such as 550% or greater, such as 600% or greater, such as 650% or greater, such as 700% or greater, such as 750% or greater, such as 900% or greater. The elongation at break can be 2000% or less, such as 1800% or less, such as 1500% or less, such as 1300% or less, such as 1000% or less, such as 900% or less, such as 800% or less, such as 700% or less, such as 600% or less, such as 500% or less, such as 450% or less, such as 400% or less, such as 350% or less, such as 300% or less. The elongation at break can be determined according to ASTM D412-16 at a temperature of 23°C (mold C, crossflow). In one embodiment, the above-described elongation at break can be used for unaged samples. In another embodiment, the above-described elongation at break can be used for aged samples. For example, samples can be aged in an oven at 70°C for 168 hours, aged at 110°C for 168 hours, and / or aged at 100°C for 1000 hours. In this respect, such elongation at break can be achieved under at least one of the above-mentioned aging conditions, such as at least two, such as all three.

[0132] Thermoplastic vulcanizates are also characterized by advantageously low compression set. For example, the compression set can be 85% or less, such as 80% or less, such as 70% or less, such as 65% or less, such as 60% or less, such as 55% or less, such as 50% or less, such as 45% or less, such as 40% or less, such as 35% or less, such as 30% or less, such as 25% or less, such as 20% or less, such as 15% or less. The compression set can also be 5% or greater, such as 8% or greater, such as 10% or greater, such as 13% or greater, such as 15% or greater, such as 18% or greater, such as 20% or greater, such as 25% or greater, such as 30% or greater, such as 35% or greater, such as 40% or greater, such as 50% or greater, such as 60% or greater, such as 70% or greater. Compression deformation can be determined according to ASTM D395B-18 (Type 1 sample, 25%, 22 hours). This aforementioned compression deformation is based on temperatures of room temperature, 70°C, and / or 110°C. In this regard, in one embodiment, such compression deformation can be achieved at least one, such as at least two, such as at all three temperature conditions.

[0133] Thermoplastic vulcanizates are also characterized by advantageously high tear strength. For example, the tear strength can be 50 N / cm or greater, such as 100 N / cm or greater, such as 150 N / cm or greater, such as 200 N / cm or greater, such as 250 N / cm or greater, such as 300 N / cm or greater, such as 350 N / cm or greater, such as 400 N / cm or greater, such as 450 N / cm or greater, such as 500 N / cm or greater, such as 550 N / cm or greater, such as 600 N / cm or greater, such as 650 N / cm or greater. Tear strength can be 1200 N / cm or less, such as 1100 N / cm or less, such as 1000 N / cm or less, such as 900 N / cm or less, such as 800 N / cm or less, such as 700 N / cm or less, such as 650 N / cm or less, such as 600 N / cm or less, such as 550 N / cm or less, such as 500 N / cm or less, such as 450 N / cm or less, such as 400 N / cm or less, such as 350 N / cm or less, such as 300 N / cm or less. Tear strength can be determined according to ASTM D624 (die C, crossflow).

[0134] Thermoplastic vulcanizates can also be characterized by a value of 0.900 g / cm³ as defined by ASTM D-792. 3 Or even higher, such as 0.91 g / cm³ 3 Or even higher, such as 0.915 g / cm³ 3 Or even higher, such as 0.92 g / cm³ 3 Or even higher, such as 0.925 g / cm³ 3 Or even higher, such as 0.93 g / cm³ 3 Or even higher, such as 0.935 g / cm³ 3 Or even higher, such as 0.94 g / cm³ 3 Or even higher, such as 0.945 g / cm³ 3 Or even higher, such as 0.95 g / cm³ 3 Or even higher, such as 0.965 g / cm³ 3 Or even higher, such as 0.97 g / cm³ 3 Or even higher, such as 0.975 g / cm³ 3 Or even higher, such as 0.98 g / cm³ 3 Or a higher specific gravity. Specific gravity could be 1.1 g / cm³. 3 Or even smaller, such as 1.05 g / cm³ 3 Or even smaller, such as 1 g / cm³ 3Or even smaller, such as 0.995 g / cm³ 3 Or even smaller, such as 0.99 g / cm³ 3 Or even smaller, such as 0.985 g / cm³ 3 Or even smaller, such as 0.98 g / cm³ 3 Or even smaller, such as 0.975 g / cm³ 3 Or even smaller, such as 0.97 g / cm³ 3 Or even smaller, such as 0.965 g / cm³ 3 Or even smaller, such as 0.96 g / cm³ 3 Or smaller.

[0135] Thermoplastic vulcanizates can also be characterized by weight gain, as determined by using IRM903 oil at 121°C for 24 hours according to ASTM D471. This weight percentage provides a percentage of oil swelling by weight as a implicit measure of the degree of curing or crosslinking of the elastomer. Generally, low or partial crosslinking of the elastomer produces a higher oil swelling value, while highly crosslinked dispersions will have lower oil swelling. In this respect, the weight gain can be 10% or more, such as 20% or more, such as 30% or more, such as 40% or more, such as 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 100% or more. The weight gain can be 150% or less, such as 130% or less, such as 110% or less, such as 100% or less, such as 90% or less, such as 80% or less, such as 70% or less, such as 60% or less, such as 50% or less, such as 40% or less.

[0136] Thermoplastic vulcanizates can also be characterized by their LCR viscosity, as determined according to ASTM D-3835 at 204°C using a mold with a diameter of 1 mm, a length of 30 mm, and an entry angle of 180°. For example, the LCR viscosity at 1200 s⁻¹ can be 30 Pa·s or greater, such as 40 Pa·s or greater, such as 50 Pa·s or greater, such as 60 Pa·s or greater, such as 70 Pa·s or greater, such as 80 Pa·s or greater, such as 85 Pa·s or greater, such as 90 Pa·s or greater, such as 95 Pa·s or greater, such as 100 Pa·s or greater. The LCR viscosity at 1200 s⁻¹ can be 200 Pa·s or less, such as 180 Pa·s or less, such as 160 Pa·s or less, such as 140 Pa·s or less, such as 130 Pa·s or less, such as 120 Pa·s or less, such as 115 Pa·s or less, such as 110 Pa·s or less, such as 105 Pa·s or less, such as 100 Pa·s or less, such as 95 Pa·s or less.

[0137] The LCR viscosity at 200 s⁻¹ can be 200 Pa·s or greater, such as 250 Pa·s or greater, such as 300 Pa·s or greater, such as 320 Pa·s or greater, such as 340 Pa·s or greater, such as 360 Pa·s or greater, such as 370 Pa·s or greater, such as 380 Pa·s or greater, such as 390 Pa·s or greater, such as 400 Pa·s or greater. The LCR viscosity at 200 s⁻¹ can be 700 Pa·s or less, such as 650 Pa·s or less, such as 600 Pa·s or less, such as 550 Pa·s or less, such as 500 Pa·s or less, such as 480 Pa·s or less, such as 460 Pa·s or less, such as 440 Pa·s or less, such as 430 Pa·s or less, such as 420 Pa·s or less, such as 415 Pa·s or less, such as 410 Pa·s or less, such as 405 Pa·s or less, such as 400 Pa·s or less, such as 395 Pa·s or less, such as 390 Pa·s or less, such as 385 Pa·s or less, such as 380 Pa·s or less, such as 370 Pa·s or less, such as 360 Pa·s or less, such as 350 Pa·s or less.

[0138] Another characteristic of thermoplastic vulcanizates is their extrusion surface roughness (ESR). ESR can determine the suitability and aesthetics of the final extruded product. In this regard, ESR can be 300 µin or less, such as 280 µin or less, such as 260 µin or less, such as 240 µin or less, such as 220 µin or less, such as 200 µin or less, such as 180 µin or less, such as 160 µin or less, such as 140 µin or less, such as 130 µin or less, such as 120 µin or less, such as 110 µin or less, such as 100 µin or less, such as 90 µin or less, such as 80 µin or less, such as 70 µin or less, such as 60 µin or less, such as 50 µin or less, such as 40 µin or less. ESR can be 0.1 µin or greater, such as 0.5 µin or greater, such as 1 µin or greater, such as 5 µin or greater, such as 10 µin or greater, such as 20 µin or greater, such as 30 µin or greater, such as 40 µin or greater, such as 50 µin or greater, such as 60 µin or greater, such as 70 µin or greater, such as 80 µin or greater, such as 90 µin or greater, such as 100 µin or greater, such as 110 µin or greater, such as 120 µin or greater, such as 130 µin or greater, such as 140 µin or greater, such as 150 µin or greater, such as 170 µin or greater, such as 190 µin or greater, such as 210 µin or greater, such as 230 µin or greater.

[0139] The following testing methods can be used to determine the characteristics mentioned in this article. Test methods

[0140] Melting temperature, glass transition temperature, and heat of fusion: Melting temperature (“Tm”), glass transition temperature (“Tg”), and heat of fusion (“Hf”) can be determined using commercially available equipment such as the TA Instruments model Q100, as known in the art, by differential scanning calorimetry (“DSC”). Typically, a sample of 6 to 10 mg, which has been stored at room temperature (about 23°C) for at least 48 hours, is sealed in an aluminum dish and loaded into the instrument at room temperature (about 23°C). The sample is equilibrated at 25°C and then cooled to -80°C at a cooling rate of 10°C. The sample is held at -80°C for 5 min and then heated to 25°C at a heating rate of 10°C. The glass transition temperature is measured from this heating cycle (“first heating”). For samples exhibiting multiple peaks, the melting point (or melting temperature) is defined as the peak melting temperature associated with the thermal response of the maximum endothermic heat from the DSC melting trace within that temperature range. T was measured by reheating the sample from -80°C to 80°C at a rate of 20°C / min (“second heating”). g The reported glass transition temperature is the midpoint of the step change during heating in the second heating cycle. The heat of transition (heat of fusion Hf at melting, or heat of crystallization Hc at crystallization; if the Hf value from melting differs from the Hc value obtained from the heat of crystallization, the value from melting (Tm) should be used) is determined using the area under the DSC curve. This heat can be used to calculate crystallinity (also known as crystallinity percentage). Crystallinity percentage (X %) is calculated using the following formula: [Area under curve (in J / g) / H° (in J / g)] 100, where H° is the heat of fusion of the homopolymer of the major monomer component. These values ​​of H° are obtained from John Wiley and Sons, Polymer Handbook, 4th Edition, New York, 1999, except that 290 J / g is used as the equilibrium heat of fusion (H°) for 100% crystalline polyethylene, 140 J / g as the equilibrium heat of fusion (H°) for 100% crystalline polybutene, and 207 J / g (H°) as the heat of fusion for 100% crystalline polypropylene.

[0141] Extrusion surface roughness: Feed approximately 1 kg (2 lbs.) of the TPV to be tested into a 1″ or 1½″ diameter extruder equipped with a 24:1 L / D screw with a compression ratio of 3.0 to 3.5. The extruder was equipped with a strip die with a width of 25.4 mm (1″), a thickness of 0.5 mm (0.019″), and a cutting edge length of 7 to 10 mm (0.25 to 0.40″). A breaker plate was used with the die, but the screen pack was not placed in front of the breaker plate. The temperature distribution of the extruder was as follows: Zone 1 = 180°C (feed zone); Zone 2 = 190°C (feed zone); Zone 3 = 200°C (feed zone); Zone 4 = 205°C (die zone). When the zone temperatures were reached, the screw was activated. The screw speed was set to maintain an output of approximately 50 g / min. After rinsing the extruder for 5 minutes, the extruded material was discarded and a strip approximately 30.5 cm (12″) in length was extruded onto a flat substrate placed directly below and in contact with the lower side of the die. Three representative samples were collected in this manner. The ESR on the sample was measured using the EMD-04000-W5 Surfanalyzer System 4000, which includes a universal probe with a 200 mg stylus force and a Surfanalyzer probe tip type EPT-01049 (0.025 mm [0.0001″] stylus radius). Example Example 1

[0142] The components identified in the table provided below are melt-blended and dynamically cured to provide a thermoplastic vulcanizate comprising at least partially cured EPDM. Examples 1-5 include refining oil as indicated below. Melt blending and dynamic vulcanization are performed using a twin-screw extruder set at a temperature between 90°C and 210°C. The speed is set to approximately 300 rpm. The sample is then injection-molded into a sheet and the sample is punched from the sheet and tested.

[0143] To evaluate short-term aging performance, the samples were thermally aged for 168 hours at 70°C and 110°C in an air-circulating oven. To evaluate long-term aging performance, the samples were thermally aged for 1000 hours at 100°C in an air-circulating oven.

[0144] These and other modifications and variations of this disclosure can be practiced by those skilled in the art without departing from the spirit and scope thereof. Furthermore, it should be understood that aspects of the various embodiments may be interchanged in whole or in part. Moreover, those skilled in the art will understand that the foregoing description is merely illustrative and not intended to limit the invention further described in such appended claims.

Claims

1. A method for forming thermoplastic vulcanizate, the method comprising: Dynamically vulcanize a formulation comprising a thermoplastic resin, an elastomer, an oil comprising a refining oil, and a curing agent to provide a thermoplastic vulcanized rubber comprising the thermoplastic resin and at least partially cured elastomer.

2. The method as described in claim 1, wherein, The oil comprises a mixture of the refined oil and the crude oil.

3. The method according to any one of claims 1-2, wherein, This thermoplastic resin contains polyolefins.

4. The method of claim 3, wherein, This polyolefin contains polypropylene.

5. The method according to any one of claims 1-2, wherein, The thermoplastic resin contains recycled thermoplastic resin.

6. The method of claim 5, wherein, The recycled thermoplastic resin comprises recycled polypropylene, recycled polyethylene, or a mixture thereof.

7. The method according to any one of claims 1-2, wherein, The thermoplastic resin comprises a mixture of virgin thermoplastic resin and recycled thermoplastic resin.

8. The method as described in any of the preceding claims, wherein, The elastomer contains ethylene / propylene / non-conjugated diene copolymer rubber (EPDM).

9. The method as claimed in any of the preceding claims, wherein, The refined oil, together with the elastomer, is provided as an elastomer for the refined oil.

10. The method as claimed in any of the preceding claims, wherein, The thermoplastic vulcanizate comprises about 5 wt.% to about 90 wt.% of the elastomer, about 5 wt.% to about 90 wt.% of the thermoplastic resin, and about 10 wt.% or more to about 60 wt.% or less of the refining oil, wherein the wt.% is based on the weight of the thermoplastic vulcanizate and wherein the thermoplastic vulcanizate has a recycling content of 5 wt.% to 95 wt.% based on the weight of the thermoplastic vulcanizate.

11. The method as claimed in any of the preceding claims, wherein, This thermoplastic vulcanizate exhibits one or more of the following: Shore A hardness of 25 to 100 according to ASTM 2240-15 (2021) (15 seconds; unaged); Shore D hardness of greater than 0 to 50 according to ASTM 2240-15 (2021) (15 seconds; unaged); 100% modulus of 0.3 MPa to 50 MPa as determined according to ASTM D412-16 (unaged); tensile stress at break of 0.5 MPa to 100 MPa as determined according to ASTM D412-16 (unaged); elongation at break of 20% to 2000% as determined according to ASTM D412-16 (unaged); or compression set of 70% or less as determined according to ASTM D395B-18 after 22 hours at room temperature.

12. A thermoplastic vulcanizate comprising a thermoplastic resin in an amount of 5 wt.% or more by weight of the thermoplastic vulcanizate, an elastomer in an amount of at least partially cured in an amount of 5 wt.% or more by weight of the thermoplastic vulcanizate, and an oil comprising refining oil.

13. The thermoplastic vulcanized rubber of claim 12, wherein, The oil comprises a mixture of the refined oil and the crude oil.

14. The thermoplastic vulcanizate rubber according to any one of claims 12-13, wherein, This thermoplastic resin contains polyolefins.

15. The thermoplastic vulcanizate rubber according to any one of claims 12-13, wherein, The thermoplastic resin contains recycled thermoplastic resin.

16. The thermoplastic vulcanized rubber of claim 15, wherein, The recycled thermoplastic resin comprises recycled polypropylene, recycled polyethylene, or a mixture thereof.

17. The thermoplastic vulcanizate rubber according to any one of claims 12-13, wherein, The thermoplastic resin comprises a mixture of virgin thermoplastic resin and recycled thermoplastic resin.

18. The thermoplastic vulcanized rubber of claim 12, wherein, The elastomer contains ethylene / propylene / non-conjugated diene copolymer rubber (EPDM).

19. The thermoplastic vulcanizate rubber according to any one of claims 12-18, wherein, The thermoplastic vulcanizate comprises about 5 wt.% to about 90 wt.% of the elastomer, about 5 wt.% to about 90 wt.% of the thermoplastic resin, and about 10 wt.% or more to about 60 wt.% or less of the refining oil, wherein the wt.% is based on the weight of the thermoplastic vulcanizate and wherein the thermoplastic vulcanizate has a recycling content of 5 wt.% to 95 wt.% based on the weight of the thermoplastic vulcanizate.

20. The thermoplastic vulcanizate rubber according to any one of claims 12-19, wherein, This thermoplastic vulcanizate exhibits one or more of the following: Shore A hardness of 25 to 100 according to ASTM 2240-15(2021) (15 seconds; unaged); Shore D hardness of greater than 0 to 50 according to ASTM 2240-15(2021) (15 seconds; unaged); 100% modulus of 0.3 MPa to 50 MPa as determined by ASTM D412-16 (unaged); tensile stress at break of 0.5 MPa to 100 MPa as determined by ASTM D412-16 (unaged); elongation at break of 20% to 2000% as determined by ASTM D412-16 (unaged); or compression set of 70% or less as determined by ASTM D395B-18 after 22 hours at room temperature.

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