Thermoplastic vulcanized materials with a lower carbon footprint

Abstract

A method for forming a thermoplastic vulcanized product and a thermoplastic vulcanized product are disclosed. The method includes dynamically vulcanizing a compound comprising a thermoplastic resin, an elastomer, an oil containing refined oil, and a curing agent to provide a thermoplastic vulcanized product comprising a thermoplastic resin and at least a partially cured elastomer. The thermoplastic vulcanized product comprises a thermoplastic resin in an amount of 5% by weight or more based on the weight of the thermoplastic vulcanized product, an at least 5% by weight or more based on the weight of the thermoplastic vulcanized product, and an oil containing refined oil.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 497,514, filed on 21 April 2023, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Generally, thermoplastic vulcanized products can be formed by dynamically vulcanizing a formulation containing a thermoplastic resin and an elastomer. During the process, other additives may also be provided for various benefits and / or to obtain specific desired properties in the resulting thermoplastic vulcanized product. For example, oil may be provided to aid in the processability of the materials in the formulation and in the formation of the thermoplastic vulcanized product. In addition, various additives such as colorants and / or fillers may be provided to obtain specific desired properties in the resulting thermoplastic vulcanized product. Typically, additives used in the formation of thermoplastic vulcanized products are unused materials. For example, oil, which is typically used, is produced from crude oil and may have a higher carbon footprint. [Overview of the project] [Problems that the invention aims to solve]

[0003] Therefore, there is currently a need to provide improved methods for forming thermoplastic vulcanized materials, as well as thermoplastic vulcanized materials that have a relatively higher recycled content and a relatively lower carbon footprint while still maintaining a balanced performance. [Means for solving the problem]

[0004] A method for forming a thermoplastic vulcanized product is disclosed according to one embodiment of the present disclosure. The method includes dynamically vulcanizing a compound comprising a thermoplastic resin, an elastomer, an oil containing a refined oil, and a curing agent to provide a thermoplastic vulcanized product comprising a thermoplastic resin and at least a partially cured elastomer.

[0005] A thermoplastic vulcanized product is disclosed according to another embodiment of the present disclosure. The thermoplastic vulcanized product comprises a thermoplastic resin in an amount of 5% by weight or more based on the weight of the thermoplastic vulcanized product, at least a partially cured elastomer in an amount of 5% by weight or more based on the weight of the thermoplastic vulcanized product, and an oil containing a re-refined oil.

[0006] Other features and aspects of this disclosure are described in more detail below. [Modes for carrying out the invention]

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

[0008] Generally speaking, this disclosure relates to a method for forming thermoplastic vulcanized products. The method particularly utilizes refined oil. For example, the method may generally include the step of dynamically vulcanizing a formulation comprising a thermoplastic resin, an elastomer, an oil containing refined oil, and a curing agent to provide a thermoplastic vulcanized product comprising a thermoplastic resin and at least a partially cured elastomer. In this regard, the inventors have found that by utilizing refined oil as disclosed herein, the resulting thermoplastic vulcanized product can exhibit desired properties while also providing a more environmentally friendly method and the resulting thermoplastic vulcanized product. Thus, the method enables higher sustainability characteristics than certain other common methods and also provides a reduction in the overall carbon footprint of the thermoplastic vulcanized product.

[0009] Various embodiments of this disclosure will now be described in more detail.

[0010] I. Thermoplastic vulcanizate A. Thermoplastic resin As shown above, thermoplastic vulcanized products contain thermoplastic resins. In this regard, thermoplastic vulcanized products may contain one or more thermoplastic resins. In one embodiment, one thermoplastic resin may be used as the thermoplastic resin. In other embodiments, the thermoplastic resin may include a mixture of thermoplastic resins. For example, two or more thermoplastic resins, such as two or three thermoplastic resins, may be used in the thermoplastic vulcanized product. 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] In general, any thermoplastic resin suitable for use in the manufacture of thermoplastic vulcanized products can be used as the thermoplastic resin. For example, thermoplastic resins may include polyolefins, polyimides, polyesters, polyamides, poly(phenylene ethers), polycarbonates, styrene-acrylonitrile copolymers, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polystyrene derivatives, polyphenylene oxide, polyoxymethylene, fluorine-containing thermoplastic resins, or mixtures thereof.

[0012] In one embodiment, the thermoplastic resin may comprise at least a polyolefin. The polyolefin can be formed by polymerizing one or more alpha-olefins, such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. Copolymers of ethylene and propylene, or ethylene or propylene with another alpha-olefin, such as 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, or mixtures thereof, may also be utilized in accordance with this disclosure. In one embodiment, when the main monomer is ethylene, the copolymer may be propylene or another C4-C8 alpha-olefin monomer. In one embodiment, the comonomer may be propylene. In another embodiment, the comonomer may be a C4-C8 alpha-olefin monomer, such as hexene. When the main monomer is propylene, the copolymer may be ethylene or another C4-C8 alpha-olefin monomer. In one embodiment, the comonomer may be ethylene. In another embodiment, the comonomer may be a C4-C8 alpha-olefin monomer.

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

[0014] When a thermoplastic resin contains a polyolefin copolymer formed from ethylene or propylene as the main monomer, the corresponding comonomer may be present in an amount of 0.1% by weight or more, for example, 0.5% by weight or more, for example, 1% by weight or more, for example, 2% by weight or more, for example, 5% by weight or more, for example, 10% by weight or more, for example, 15% by weight or more, for example, 20% by weight or more, based on the weight of the copolymer. The comonomer may be present in an amount of 40% by weight or less, for example, 30% by weight or less, for example, 25% by weight or less, for example, 20% by weight or less, for example, 15% by weight or less, for example, 10% by weight or less, for example, 8% by weight or less, for example, 6% by weight or less, for example, 5% by weight or less, based on the weight of the copolymer. Similarly, the corresponding comonomer may be present in an amount of 0.1 mol% or more, for example, 0.5 mol% or more, for example, 1 mol% or more, for example, 2 mol% or more, for example, 5 mol% or more, for example, 10 mol% or more, for example, 15 mol% or more, for example, 20 mol% or more, based on the total number of moles in the copolymer. Comonomers may be present in amounts of 40 mol% or less, for example, 30 mol% or less, for example, 25 mol% or less, for example, 20 mol% or less, for example, 15 mol% or less, for example, 10 mol% or less, for example, 8 mol% or less, for example, 6 mol% or less, for example, 5 mol% or less, based on the total number of moles in the copolymer.

[0015] In one embodiment, the polyolefin may be an ethylene polymer, a propylene polymer, or a mixture thereof. In this context, in one embodiment, the polyolefin may be an ethylene polymer. In another embodiment, the polyolefin may be a propylene polymer. In a further 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 ~Approx. 1g / cm3 , for example, about 0.84 g / cm 3 ~ about 0.99 g / cm 3 , for example, about 0.84 g / cm 3 ~ about 0.94 g / cm 3 , for example, about 0.85 g / cm 3 ~ about 0.94 g / cm 3 , for example, about 0.91 g / cm 3 ~ about 0.94 g / cm 3 can be. In this context, the ethylene polymer can be linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or a mixture thereof. Such polyethylene can have a specific density as measured according to ASTM D792. For example, linear low density polyethylene (LLDPE) can have a density in the range of about 0.91 g / cm 3 ~ about 0.94 g / cm 3 . On the other hand, low density polyethylene (LDPE) can have a density in the range of about 0.91 g / cm 3 ~ about 0.925 g / cm 3 . Medium density polyethylene (MDPE) can have a density in the range of about 0.926 g / cm 3 ~ about 0.94 g / cm 3 . Also, high density polyethylene (HDPE) can have a density in the range of about 0.941 g / cm 3 ~ about 0.965 g / cm 3 . In one embodiment, the ethylene polymer can be low density polyethylene. In another embodiment, the ethylene polymer can be linear low density polyethylene. In a further embodiment, the ethylene polymer can 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, including, but not limited to, Phillips catalytic reactions, conventional Ziegler-Natta polymerization, and metallocene catalysis, including, but not limited to, metallocene catalysis with metallocene-almoxane and metallocene-ionic activators. 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 material, post-industrial material, or post-consumer material as defined in ISO 14021, except for materials that can be reused within the same process in which they were produced. The thermoplastic resin may include a mixture of one or more unused thermoplastic resins and one or more recycled thermoplastic resins. In one embodiment, the recycled thermoplastic resin may constitute the main part of the thermoplastic resin by weight. In this context, it may be present in an amount greater than 50% by weight based on the total weight of the thermoplastic resins in the thermoplastic vulcanized product. In another embodiment, the recycled thermoplastic resin may constitute the minor part of the thermoplastic resin by weight. In this context, it may be present in an amount less than 50% by weight based on the total weight of the thermoplastic resins in the thermoplastic vulcanized product. In a further embodiment, the recycled thermoplastic resin may be provided in an amount equal to the unused thermoplastic resin. The thermoplastic resin of the recycled thermoplastic resin may be any of the aforementioned thermoplastic resins.

[0021] The recycled thermoplastic resin may be any of the aforementioned thermoplastic resins referred to 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 a mixture thereof. In one particular embodiment, the recycled thermoplastic resin may include recycled polypropylene. In another particular embodiment, the recycled thermoplastic resin may include recycled polyethylene. In yet another particular embodiment, the recycled thermoplastic resin may include a mixture of recycled polyethylene and recycled polypropylene.

[0022] Generally, thermoplastic resins can include solid, generally high molecular weight polymer materials. Thermoplastic resins can have a molecular weight (Mw) of approximately 50,000 g / mol or more, for example 75,000 g / mol or more, for example 100,000 g / mol or more, for example 200,000 g / mol or more, for example 300,000 g / mol or more, for example 400,000 g / mol or more, for example 500,000 g / mol or more, for example 750,000 g / mol or more, for example 1,000,000 g / mol or more, for example 2,000,000 g / mol or more, for example 3,000,000 g / mol or more. Mw can be approximately 6,000,000 g / mol or less, for example approximately 5,000,000 g / mol or less, for example 4,000,000 g / mol or less, for example 3,000,000 g / mol or less, for example 2,000,000 g / mol or less, for example 1,500,000 g / mol or less, for example 1,000,000 g / mol or less, for example 900,000 g / mol or less, for example 800,000 g / mol or less, for example 700,000 g / mol or less, and so on. Furthermore, thermoplastic resins can have a manganese content of approximately 50,000 g / mol or more, for example 75,000 g / mol or more, for example 100,000 g / mol or more, for example 200,000 g / mol or more, for example 300,000 g / mol or more, for example 400,000 g / mol or more, for example 500,000 g / mol or more, for example 750,000 g / mol or more, for example 1,000,000 g / mol or more, for example 2,000,000 g / mol or more, for example 3,000,000 g / mol or more. Mn can be approximately 6,000,000 g / mol or less, for example approximately 5,000,000 g / mol or less, for example 4,000,000 g / mol or less, for example 3,000,000 g / mol or less, for example 2,000,000 g / mol or less, for example 1,500,000 g / mol or less, for example 1,000,000 g / mol or less, for example 900,000 g / mol or less, for example 800,000 g / mol or less, for example 700,000 g / mol or less, etc. In general, molecular weight can be characterized by GPC (gel permeation chromatography) using polystyrene standards.

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

[0024] Thermoplastic resins may also have a specific glass transition temperature ("Tg"). For example, the glass transition temperature may be relatively high. In this regard, Tg may be approximately -120°C or higher, e.g., -110°C or higher, e.g., -100°C or higher, e.g., -90°C or higher, e.g., -70°C or higher, e.g., -50°C or higher, e.g., -30°C or higher, e.g., -25°C or higher, e.g., -20°C or higher, e.g., -15°C or higher, e.g., -10°C or higher, e.g., -5°C or higher, e.g., 0°C or higher, e.g., 5°C or higher, e.g., 10°C or higher, e.g., 20°C or higher, e.g., 30°C or higher, e.g., 50°C or higher, e.g., 80°C or higher, e.g., 100°C or higher, e.g., 120°C or higher, e.g., 140°C or higher, e.g., 160°C or higher, e.g., 180°C or higher, e.g., 200°C or higher, etc. Tg can be approximately 300°C or lower, for example, 260°C or lower, 220°C or lower, 180°C or lower, 140°C or lower, 100°C or lower, 80°C or lower, 60°C or lower, 40°C or lower, 30°C or lower, 20°C or lower, 10°C or lower, 5°C or lower, 0°C or lower, -5°C or lower, etc.

[0025] In addition, thermoplastic resins may have a specific melting temperature ("Tm"). For example, the melting temperature of a thermoplastic resin may be relatively high. Furthermore, the melting temperature of a thermoplastic resin may be lower than the decomposition temperature of the elastomer in the thermoplastic vulcanized product, which is generally characterized as the point at which molecular bonds begin to break or cleave, causing the molecular weight of the elastomer to begin to decrease. In this context, Tm may be about 100°C or higher, e.g., 120°C or higher, e.g., 140°C or higher, e.g., 150°C or higher, e.g., 160°C or higher, e.g., 170°C or higher, e.g., 180°C or higher, e.g., 190°C or higher, e.g., 200°C or higher, e.g., 240°C or higher, e.g., 280°C or higher, etc. Tm can be approximately 400°C or lower, for example, 360°C or lower, for example, 320°C or lower, for example, 300°C or lower, for example, 280°C or lower, for example, 250°C or lower, for example, 220°C or lower, for example, 200°C or lower, for example, 180°C or lower, for example, 160°C or lower, etc.

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

[0027] Thermoplastic resins may have a melt flow rate of 400 g / 10 min or less. Generally, thermoplastic resins may have better properties if the melt flow rate is less than about 30 g / 10 min, preferably less than 10 g / 10 min, for example less than about 2 g / 10 min, for example less than about 1 g / 10 min, for example less than about 0.8 g / 10 min. Generally, the melt flow rate may be 0.1 g / 10 min or more, for example 0.2 g / 10 min or more, for example 0.3 g / 10 min or more, for example 0.4 g / 10 min or more, for example 0.5 g / 10 min or more. The 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 load of 2.16 kg.

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

[0029] Thermoplastic vulcanized products and / or formulations may generally contain thermoplastic resin in amounts of about 5% by weight or more, for example, about 10% by weight or more, for example, about 15% by weight or more, for example, about 20% by weight or more, for example, about 25% by weight or more, for example, about 30% by weight or more, for example, about 35% by weight or more, for example, about 40% by weight or more, for example, about 50% by weight or more, for example, about 60% by weight or more. Thermoplastic vulcanized products and / or formulations may contain thermoplastic resin in amounts of about 90% by weight or less, for example, about 80% by weight or less, for example, about 70% by weight or less, for example, about 60% by weight or less, for example, about 50% by weight or less, for example, about 40% by weight or less, for example, about 35% by weight or less. In another embodiment, such aforementioned weight percentages may be based on the total weight of the thermoplastic resin and elastomer combined in the thermoplastic vulcanized product.

[0030] If the thermoplastic vulcanized product contains a first thermoplastic resin and a second thermoplastic resin, they may be present in specific amounts. For example, the thermoplastic resin generally includes a first thermoplastic resin in amounts of about 5% by weight or more, e.g., about 8% by weight or more, e.g., about 10% by weight or more, e.g., about 15% by weight or more, e.g., about 20% by weight or more, e.g., about 25% by weight or more, e.g., about 30% by weight or more, e.g., about 35% by weight or more, e.g., about 40% by weight or more, e.g., about 50% by weight or more, e.g., about 60% by weight or more, e.g., about 70% by weight or more, e.g., about 80% by weight or more, e.g., about 90% by weight or more. The thermoplastic resin may include a first thermoplastic resin in an amount of approximately 98% by weight or less, for example, approximately 95% by weight or less, for example, approximately 90% by weight or less, for example, approximately 80% by weight or less, for example, approximately 70% by weight or less, for example, approximately 60% by weight or less, for example, approximately 50% by weight or less, for example, approximately 40% by weight or less, for example, approximately 30% by weight or less, for example, approximately 20% by weight or less, for example, approximately 15% by weight or less, or approximately 10% by weight or less.

[0031] The thermoplastic resin may generally contain a second thermoplastic resin in an amount of about 5% by weight or more, for example, about 8% by weight or more, for example, about 10% by weight or more, for example, about 15% by weight or more, for example, about 20% by weight or more, for example, about 25% by weight or more, for example, about 30% by weight or more, for example, about 35% by weight or more, for example, about 40% by weight or more, for example, about 50% by weight or more, for example, about 60% by weight or more, for example, about 70% by weight or more, for example, about 80% by weight or more, for example, about 90% by weight or more. The thermoplastic resin may contain a second thermoplastic resin in an amount of about 98% by weight or less, for example, about 95% by weight or less, for example, about 90% by weight or less, for example, about 80% by weight or less, for example, about 70% by weight or less, for example, about 60% by weight or less, for example, about 50% by weight or less, for example, about 40% by weight or less, for example, about 30% by weight or less, for example, about 20% by weight or less, for example, about 15% by weight or less, or about 10% by weight or less.

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

[0033] As shown above, in one embodiment, the thermoplastic resin may include recycled thermoplastic resin. The thermoplastic resin may generally include recycled thermoplastic resin in amounts of about 1% by weight or more, for example about 5% by weight or more, for example about 10% by weight or more, for example about 15% by weight or more, for example about 20% by weight or more, for example about 25% by weight or more, for example about 30% by weight or more, for example about 35% by weight or more, for example about 40% by weight or more, for example about 50% by weight or more, for example about 60% by weight or more, for example about 70% by weight or more, for example about 80% by weight or more, for example about 90% by weight or more. The thermoplastic resin may include recycled thermoplastic resins in amounts such as approximately 100% by weight or less, for example, approximately 98% by weight or less, for example, approximately 95% by weight or less, for example, approximately 90% by weight or less, for example, approximately 80% by weight or less, for example, approximately 70% by weight or less, for example, approximately 60% by weight or less, for example, approximately 50% by weight or less, for example, approximately 40% by weight or less, for example, approximately 30% by weight or less, for example, approximately 20% by weight or less, for example, approximately 15% by weight or less, for example, approximately 10% by weight or less, for example, approximately 5% by weight or less.

[0034] The weight ratio of unused thermoplastic resin to recycled thermoplastic resin may be approximately 0.01 or higher, for example approximately 0.05 or higher, for example approximately 0.1 or higher, for example approximately 0.2 or higher, for example approximately 0.3 or higher, for example approximately 0.4 or higher, for example approximately 0.5 or higher, for example approximately 0.6 or higher, for example approximately 0.7 or higher, for example approximately 0.8 or higher, for example approximately 0.9 or higher, for example approximately 1 or higher, for example approximately 1.2 or higher, for example approximately 1.4 or higher, for example approximately 1.6 or higher, for example approximately 1.8 or higher, for example approximately 2 or higher, for example approximately 2.5 or higher, for example approximately 3 or higher, for example approximately 3.5 or higher, for example approximately 4 or higher, for example approximately 4.5 or higher, for example approximately 5 or higher, etc. The weight ratio could be approximately 40 or less, for example approximately 35 or less, for example approximately 30 or less, for example approximately 28 or less, for example approximately 26 or less, for example approximately 24 or less, for example approximately 22 or less, for example approximately 20 or less, for example approximately 18 or less, for example approximately 16 or less, for example approximately 14 or less, for example approximately 12 or less, for example approximately 10 or less, for example approximately 9 or less, for example approximately 8 or less, for example approximately 7 or less, for example approximately 6 or less, for example approximately 5 or less, for example approximately 4.5 or less, for example approximately 4 or less, for example approximately 3.5 or less, for example approximately 3 or less, for example approximately 2.5 or less, for example approximately 2 or less, for example approximately 1.8 or less, for example approximately 1.6 or less, for example approximately 1.4 or less, for example approximately 1.2 or less, for example approximately 1 or less, for example approximately 0.8 or less, for example approximately 0.6 or less, for example approximately 0.4 or less, etc.

[0035] B. Elastomer As shown above, thermoplastic vulcanized materials contain elastomers. For example, for dynamic vulcanization, thermoplastic vulcanized materials contain at least a partially cured elastomer. In general, any elastomer suitable for use in the manufacture of TPV can be used in accordance with this disclosure. In one embodiment, one elastomer may be used as the elastomer. In other embodiments, the elastomer may include a mixture of elastomers. For example, two or more elastomers, such as two or three elastomers, may be used in the thermoplastic vulcanized material.

[0036] Any elastomer or mixture thereof that can be vulcanized (i.e., crosslinked or cured) can be used as an elastomer (sometimes also referred to herein as rubber). References to rubber or elastomer may include mixtures of two or more. Useful elastomers typically contain some 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 rubber (e.g., styrene / ethylene-butadiene / styrene), butadiene rubber, acrylonitrile rubber, halogenated rubbers such as brominated and chlorinated isobutylene-isoprene copolymer rubber, butadiene-styrene-vinylpyridine rubber, urethane rubber, polyisoprene rubber, epichlorohydrin terpolymer rubber, and polychloroprene.

[0037] Examples of vulcanizable elastomers include polyolefin copolymer elastomers. These copolymers are produced from ethylene and one or more copolymerizable, polyunsaturated comonomers or diene monomers, including but not limited to propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof, plus diolefins. The alpha-olefins can be propylene, 1-hexene, 1-octene, or combinations thereof. These rubbers may lack substantial crystallinity and are preferably amorphous copolymers.

[0038] Examples of diene monomers 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. When the copolymer is prepared from ethylene, an alpha-olefin, and a diene monomer, the copolymer may be called a terpolymer (EPDM rubber), or a tetrapolymer (EAODM rubber) if multiple alpha-olefins or dienes, or both, are used.

[0039] The elastomer, being a polyolefin elastomer copolymer, may contain about 15 to about 90 mole percent of ethylene units, about 40 to about 85 mole percent, or about 50 to about 80 mole percent of ethylene units derived from ethylene monomer. The copolymer may contain about 10 to about 85 mole percent, or about 15 to about 50 mole percent, or about 20 to about 40 mole percent of alpha-olefin units derived from alpha-olefin monomer. The aforementioned mole percentages are based on the total moles of mer units of the polymer. If the copolymer contains diene units, the copolymer may contain 0.1 to about 14 weight percent, about 0.2 to about 13 weight percent, or about 1 to about 12 weight percent of units derived from diene monomer. The weight percentage of diene units derived from diene may be determined according to ASTM D-6047. In some cases, the copolymer contains units derived from diene monomer such as less than 5.5 weight percent, e.g., less than 5.0 weight percent, e.g., less than 4.5 weight percent, e.g., less than 4.0 weight percent. Furthermore, in other cases, the copolymer contains units derived from the diene monomer in amounts exceeding 6.0% by weight, for example, exceeding 6.2% by weight, for example, exceeding 6.5% by weight, for example, exceeding 7.0% by weight, for example, exceeding 8.0% by weight.

[0040] Polyolefin elastomer copolymers can be obtained using polymerization techniques known in the art, such as traditional solution or slurry polymerization processes. For example, catalysts used to polymerize ethylene, alpha-olefins, and diene monomers into elastomer copolymers include traditional Ziegler-Natta type catalyst systems, particularly those containing titanium and vanadium compounds, as well as Group 3-6 (titanium, zirconium, and hafnium) metallocene catalysts, especially metallocene catalysts for crosslinked mono- or biscyclopentadienyl metallocene catalysts. Other catalyst systems, such as Brookhart catalyst systems, may also be used.

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

[0042] In one embodiment, the elastomer may include a multimodal copolymer rubber. For example, such a rubber may include: ethylene-derived units; a major polymer fraction having a Mooney viscosity of about 15 ml (1+4 @ 125°C) to about 120 ml (1+4 @ 125°C), based on the total weight of the multimodal copolymer rubber, with a Mooney viscosity of about 120 ml (1+4 @ 125°C) to about 1,500 ml (1+4 @ 125°C), based on the total weight of the multimodal copolymer rubber, with a Mooney viscosity of about 0% to about 50% (1+4 @ 125°C); an average molecular weight distribution (Mw / Mn) of about 1.5 to about 4.5; and an average branching index (BI) of about 0.7 to about 1.0. The average polymer fraction may also be inverse (e.g., higher molecular weight in the major part and lower molecular weight in the minor part). Therefore, multimodal copolymer rubbers can have a relatively narrow molecular weight distribution and an overall Mooney viscosity of less than approximately 90 ml (1+4 @ 125°C), and it is possible that they can be easily processed and require little to no filler oil. Multimodal copolymer rubbers can have a nearly linear structure, as indicated by their average branching index, and it can be essentially completely amorphous or semicrystalline.

[0043] The multimodal copolymer rubber may contain ethylene-derived units, α-olefin-derived units, and diene-derived units, preferably non-conjugated diene-derived units.

[0044] The α-olefin-derived units may be or may include C2-C20 α-olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof. Preferably, the α-olefin-derived units are propylene, 1-butene, 1-hexene, 1-octene, or combinations thereof, more preferably propylene. The non-conjugated diene-derived units may be or may include 5-ethylidene-2-norbomene (ENB), 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, dicyclopentadiene (DCPD), norbornadiene, 5-vinyl-2-norbomene (VNB), or combinations thereof. Suitable examples of ethylene-propylene-diene (EPDM) rubber include Vistalon® 5601, Vistalon® 5702, Vistalon® 7001, Vistalon® 9301, etc., commercially available from ExxonMobil, as well as Nordel® grades from Dow, such as 4760, 4770, 4785, etc., and SABIC® EPDM 756 and Keltan® grades from ARLANXEO, such as 8550C, 8570C, etc.

[0045] The amount of ethylene-derived units present in the multimodal copolymer rubber can be in the range of about 45% to about 80% by weight, preferably about 50% to about 75% by weight, and more preferably about 55% to about 70% by weight, based on the total weight of the rubber. The amount of diene-derived units present in the TPV multimodal copolymer rubber can be in the range of about 1% to about 10% by weight, preferably about 2% to about 8% by weight, and more preferably about 3% to about 6% by weight, based on the total weight of the rubber. α-olefin-derived units can constitute the remainder of the polymer units.

[0046] Ethylene content can be measured by FTIR, ASTM D3900, without correction for diene content. ENB diene content can be measured by FTIR, ASTM D6047. Other dienes can be measured by 3 / 4 NMR.

[0047] A multimodal copolymer rubber can be characterized by a multimodal molecular weight distribution, which can simply be called a multimodal molecular weight distribution. In one or more embodiments, the multimodal copolymer rubber may contain at least two fractions. Multimodality is M W GPC LALLS This can manifest as two distinct peaks in the signal, or as a main peak and a shoulder peak. This multimodality can be caused by the blending of very high molecular weight components with very low molecular weight components, either as a result of stepwise polymerization or by physical blending techniques. In this context, multimodal copolymers can be bimodal, trimodal, tetramodal, etc.

[0048] The multimodal copolymer rubber may contain a main polymer fraction in an amount of more than about 50% by weight and less than about 100% by weight, preferably more than about 55% by weight and less than about 95% by weight, and more preferably more than about 60% by weight and less than about 90% by weight. The main 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), based on the total weight of the multimodal copolymer rubber.

[0049] The multimodal copolymer rubber may contain minor polymer fractions in an amount greater than about 0% by weight and less than about 50% by weight, preferably greater than about 5% by weight and less than about 45% by weight, and more preferably greater than about 10% by weight and less than about 40% by weight. The minor polymer fractions may have a Mooney viscosity of about 120 ml (1+4 @ 125°C) to about 1,500 ml (1+125 @ 125°C), preferably about 120 ml (1+125 @ 125°C) to about 1,100 ml (1+4 @ 4°C), and more preferably about 120 ml (1+4 @ 4°C) to about 700 ml (1+4 @ 125°C), based on the total weight of the multimodal copolymer rubber.

[0050] Multimodal copolymer rubbers can have an overall Mooney viscosity of approximately 20 ML (1+4 @ 125°C) to approximately 90 ML (1+4 @ 125°C), preferably approximately 25 ML (1+4 @ 125°C) to approximately 85 ML (1+4 @ 125°C), and more preferably approximately 30 ML (1+4 @ 125°C) to approximately 80 ML (1+4 @ 125°C). As used herein, Mooney viscosity is reported using the following format: rotor([preheat time, mins] + [shear time, mins] @ measurement temperature, °C), where ML (1+4 @ 125°C) represents the Mooney viscosity measured using a large rotor in accordance with ASTM D1646-99, with a preheat time of 1 minute and a shear time of 4 minutes at a temperature of 125°C. Unless otherwise specified, Mooney viscosity is reported herein as ML (1+4 @ 125°C) in Mooney units according to ASTM D-1646. However, Mooney viscosity values ​​greater than about 100 cannot generally be measured under these conditions. In this case, a higher temperature (i.e., 150°C) can be used, along with a longer final shear time (i.e., 1+8 @ 125°C or 150°C). More preferably, Mooney measurements for the purposes of this specification are performed using a non-standard miniature rotor. The non-standard rotor design is used with a modification of the Mooney scale that allows the same instrumentation on a Mooney instrument to be used with polymers having a Mooney viscosity greater than about 100 ML (1+4 @ 125°C). For the purposes of this specification, this modified Mooney measurement is referred to as Mooney Small Thin (MST).

[0051] ASTM D 1646-99 specifies the dimensions of rotors used in the cavities of Mooney machinery. This method allows for both large and small rotors, differing only in diameter. These different rotors are referred to as ML (Large Mooney) and MS (Small Mooney) in ASTM D 1646-99. However, EPDM rubber can be manufactured with such high molecular weight that it may exceed the torque limits of Mooney machinery using these standard specified rotors. In these cases, the test is performed using an MST rotor, which is both smaller in diameter and thinner. Typically, when an MST rotor is used, the test is also performed with different time constants and temperatures. The preheating time is changed from the standard 1 minute to 5 minutes, and the test is performed at 200°C instead of the standard 125°C. The values ​​obtained under these modified conditions are referred to herein as MST(5+4@200°C). Note: The 4-minute run time at which the Mooney measurement is taken remains the same as under standard conditions. When MST is measured at (5+4@200℃) and ML is measured at (1+4@125℃), 1 MST point is approximately equivalent to 5 ML points. Therefore, for the purpose of approximate conversion between the two measurement scales, the MST(5+4@200℃) Mooney value is multiplied by 5 to obtain an approximate equivalent ML(1+4@125℃) value. The MST rotor used herein has a diameter of 30.48±0.03 mm, a thickness of 2.8±0.03 mm (measured from the serrated top), and a shaft with a diameter of 11 mm or less. The rotor has a serrated surface and edge with a square groove cut into the center of 1.6 mm, with a width of approximately 0.8 mm and a depth of approximately 0.25-0.38 mm. The serrated portion consists of two sets of grooves perpendicular to each other, thereby forming a square cross. The rotor is positioned at the center of the die cavity such that the centerline of the rotor disc coincides with the centerline of the die cavity within a tolerance of ±0.25 mm. Spacers or shims can be used to raise the shaft to a midpoint, consistent with typical practices in the art for Mooney measurements. The wear point (a conical ridge located at the center of the rotor's upper surface) is machined off-flat with the rotor surface.

[0052] The Mooney viscosity of a multimodal copolymer rubber can be measured with respect to the polymer blends described herein. The Mooney viscosity of a specific component of the blend is given by equation (1): logML=n A logML A +n B logML B (1) (In the formula, all logarithms are base 10; ML is the individual Mooney viscosity ML) A and ML B The Mooney viscosity of a blend of two polymers A and B, each having the following properties; n A n represents the weight percentage of polymer A in the blend; B The relationship shown herein (where represents the weight percentage fraction of polymer B in the blend) is used to obtain the Mooney viscosity of a blend containing a high Mooney viscosity polymer (A) and a low Mooney viscosity polymer (B) having a measurable Mooney viscosity under conditions of (1+4@125°C). ML, ML A and n A Knowing this, ML B The value can be calculated. However, for high Mooney viscosity polymers (i.e., Mooney viscosity exceeding 100 ML (1+4@125℃)), ML A This can be measured using an MST rotor as described above. 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): ML A (1+4@125℃)=5.13*MST A The Mooney viscosity is determined using (5+4@200℃)(2). In these or other embodiments, the Mooney viscosity of the high molecular weight polymer can be measured using a Mooney viscometer Model VR / 1132 (Ueshima Seisakusho), which can measure Mooney viscosity up to 400 units.

[0053] Multimodal copolymer rubber can be produced by polymerization using a metallocene catalyst. The resulting rubber may be in the form of particles having a particle size of about 0.5 mm to about 15.0 mm, preferably about 1.0 mm to about 10.0 mm, and more preferably about 1.5 mm to about 8.0 mm. As used herein, "particle size" refers to the weight-average particle size. These particles may be made into dust, for example, at a particle size greater than about 0.1 phr, to prevent the rubber particles from sticking together. Examples of such fine particles include polyethylene dust particles, inorganic fillers such as calcium carbonate, talc, and clay.

[0054] In one or more embodiments, butyl rubbers include copolymers of isobutylene and isoprene, copolymers of isobutylene and paramethylstyrene, terpolymers of isobutylene, isoprene, and divinylstyrene, branched butyl rubber, and brominated copolymers of isobutene and paramethylstyrene (producing copolymers having parabromomethylstyrene units). These copolymers and terpolymers may be halogenated. Furthermore, butyl rubbers 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 contains an isobutylene-isoprene copolymer, the copolymer may contain about 0.5 to about 30, or about 0.8 to about 5,000% by weight of isoprene, with the remainder being isobutylene.

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

[0057] In other embodiments in which the butyl rubber contains isobutylene-isoprene-divinylstyrene, the terpolymer may contain about 95 to about 99, or about 96 to about 98.5, by weight isobutylene and about 0.5 to about 5, or about 0.8 to about 2.5, by weight isoprene, with the remainder being divinylstyrene.

[0058] In the case of halogenated butyl rubber, the butyl rubber may contain approximately 0.1 to 10, 0.3 to 7, or 0.5 to 3 weight percent of halogen, based on the total weight of the copolymer or terpolymer.

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

[0060] With respect to the materials used to form these elastomers, it should be understood that in certain 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 of the monomers used in the production of the elastomer may be biorenewable monomers and / or recycled monomers. As an example, bioethanol can 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] Generally, elastomers, especially polyolefin elastomer copolymers, can have a molecular weight (Mw) of approximately 50,000 g / mol or more, for example, 75,000 g / mol or more, for example, 100,000 g / mol or more, for example, 200,000 g / mol or more, for example, 300,000 g / mol or more, for example, 400,000 g / mol or more, for example, 500,000 g / mol or more, for example, 750,000 g / mol or more, for example, 1,000,000 g / mol or more. Mw can be approximately 3,000,000 g / mol or less, for example 2,000,000 g / mol or less, for example 1,500,000 g / mol or less, for example 1,000,000 g / mol or less, for example 900,000 g / mol or less, for example 800,000 g / mol or less, for example 700,000 g / mol or less, for example 600,000 g / mol or less, for example 500,000 g / mol or less, for example 400,000 g / mol or less, for example 300,000 g / mol or less, and so on. Furthermore, elastomers, particularly polyolefin elastomer copolymers, may have a manganese content (Mn) of approximately 50,000 g / mol or more, for example, 75,000 g / mol or more, for example, 100,000 g / mol or more, for example, 200,000 g / mol or more, for example, 300,000 g / mol or more, for example, 400,000 g / mol or more, for example, 500,000 g / mol or more, for example, 750,000 g / mol or more, for example, 1,000,000 g / mol or more. Mn can be approximately 3,000,000 g / mol or less, for example 2,000,000 g / mol or less, for example 1,500,000 g / mol or less, for example 1,000,000 g / mol or less, for example 900,000 g / mol or less, for example 800,000 g / mol or less, for example 700,000 g / mol or less, for example 600,000 g / mol or less, for example 500,000 g / mol or less, for example 400,000 g / mol or less, for example 300,000 g / mol or less, etc. In general, molecular weight can be characterized by GPC (gel permeation chromatography) using polystyrene standards.

[0062] Thermoplastic vulcanized products and / or formulations may generally contain elastomers in amounts of about 2% by weight or more, for example, about 5% by weight or more, for example, about 10% by weight or more, for example, about 15% by weight or more, for example, about 20% by weight or more, for example, about 25% by weight or more, for example, about 30% by weight or more, for example, about 40% by weight or more, for example, about 50% by weight or more. Thermoplastic vulcanized products and / or formulations may contain elastomers in amounts of about 90% by weight or less, for example, about 80% by weight or less, for example, about 70% by weight or less, for example, about 60% by weight or less, for example, about 50% by weight or less, for example, about 40% by weight or less, for example, about 35% by weight or less, for example, about 30% by weight or less, for example, about 25% by weight or less, for example, about 20% by weight or less, for example, about 15% by weight or less. In another embodiment, such aforementioned weight percentages may be based on the total weight of the thermoplastic resin and elastomer combined in the thermoplastic vulcanized product.

[0063] Furthermore, if an elastomer mixture is present, the main elastomer may be present in an amount of approximately 60% or more by weight, for example, approximately 70% or more by weight, for example, approximately 80% or more by weight, for example, approximately 90% or more by weight, and less than 100% by weight, based on the weight of the elastomer. The second elastomer may be present in an amount of 40% or less by weight of the elastomer, for example, 30% or less by weight, for example, 20% or less by weight, for example, 15% or less by weight, for example, 10% or less by weight, for example, 5% or more by weight and more than 0% by weight.

[0064] C. Cured composition As described herein, TPV formulations, particularly elastomers within the formulations, can undergo dynamic vulcanization 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 these curing agents include phenolic resins, peroxides, maleimides, and silicon-containing curing agents. The curing agent may be used with one or more crosslinking aids that function as initiators, catalysts, etc., for the purpose of improving the overall cured state of the elastomer. For example, curing compositions of some embodiments contain one or both of zinc oxide (ZnO) and stannous chloride (SnCl2).

[0065] In general, phenolic resins are not necessarily limited. For example, these may include resol resins produced by condensation of alkyl-substituted or unsubstituted phenols with an aldehyde, which may be formaldehyde, in an alkaline medium, or by condensation of a difunctional phenol dialcohol. The alkyl substituents of alkyl-substituted phenols typically contain 1 to about 10 carbon atoms. Dimethylolphenols or phenolic resins substituted at the para position with alkyl groups containing 1 to about 10 carbon atoms can be used. These phenolic curing agents may be thermosetting resins and may be called phenolic resin curing agents or phenolic resins. These phenolic resins can ideally be used in conjunction with a catalyst system. For example, non-halogenated phenolic curing resins are used in conjunction with a halogen donor and, optionally, a hydrogen halide scavenger. If the phenolic curing resin is halogenated, a halogen donor is not required, but the use of a hydrogen halide scavenger such as ZnO can be used.

[0066] Peroxide curing agents are generally selected from organic peroxides. Examples of organic peroxides include, but are not limited to, di-tert-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, alpha,alpha-bis(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3, and mixtures thereof. Diaryl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkylperoxides, hydroperoxides, peroxyketals, and mixtures thereof may also be used.

[0067] Silicon-containing curing agents generally include silicon 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. Examples of silicon hydride compounds include, but are not limited to, methylhydrogen polysiloxanes, methylhydrogen dimethyl-siloxane copolymers, alkylmethylpolysiloxanes, bis(dimethylsilyl)alkanes, bis(dimethylsilyl)benzenes, and mixtures thereof.

[0068] As described above, hydrosilylation hardening can be carried out in the presence of a catalyst. Examples of such catalysts include, but are not limited to, peroxide catalysts and catalysts containing Group VIII transition metals. Examples of such metals include, but are not limited to, palladium, rhodium, and platinum, as well as complexes of these metals.

[0069] In certain embodiments, the curing composition also comprises one or both of ZnO and SnCl2. In one embodiment, the curing composition may comprise zinc oxide. In another embodiment, the curing composition may comprise stannous chloride. In further embodiments, the curing composition may comprise zinc oxide and stannous chloride.

[0070] Crosslinking aids may be used along with curing agents such as phenolic resins and / or peroxides. Examples of crosslinking aids include polyfunctional acrylate esters, polyfunctional methacrylate esters, or combinations thereof. In other words, the crosslinking aid contains 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, bistrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol triacrylate, cyclohexanedimethanol diacrylate, ditrimethylolpropane tetraacrylate, or combinations thereof. Examples of polyfunctional methacrylates include trimethylolpropane trimethacrylate (TMPTMA), ethylene glycol dimethacrylate, butanediol dimethacrylate, butylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, allyl methacrylate, or combinations thereof. Crosslinking aids may 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 acrylic esters, dipentaerythritol pentaacrylate, polyfunctional acrylates, delayed cyclohexanedimethanol diacrylate esters, polyfunctional methacrylates, acrylates and methacrylate metal salts, such as oximers for quinone dioximes.

[0071] Furthermore, oils can be used in the curing system. Oils may also be called process oils, filler oils, or plasticizers. Useful oils include mineral oils, synthetic processing oils, or combinations thereof, which can act as plasticizers. Examples of plasticizers include, but are not limited to, aromatic oils, naphthenic oils, and filler oils. Exemplary synthetic processing oils include low molecular weight polylinear alpha-olefins and polybranched alpha-olefins. Suitable esters include monomers and oligomeric substances having an average molecular weight of less than about 2,000 g / mole or less than about 600 g / mole. Specific examples include aliphatic mono- or diesters, or oligomeric aliphatic esters or alkyl ether esters.

[0072] The curing composition may be added at one or more locations, such as the feed hopper of a melt-mixing extruder. In some embodiments, the curing agent and any additional crosslinking aids may be added together with the TPV formulation; in other embodiments, one or more crosslinking aids may be added to the TPV formulation at a different time than any one or more curing agents while the TPV formulation is undergoing processing to form TPV.

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

[0074] D.Oil Thermoplastic vulcanized products and formulations disclosed herein also contain oils. Examples of oils include, but are not limited to, plasticizer oils, process oils, filler oils, or mixtures thereof. In this regard, the resulting thermoplastic vulcanized products may also contain one or more such oils.

[0075] Furthermore, as described herein, oils include refined oils. As used herein, “refined oil” refers to used or waste oil that has undergone a process similar to the original process used to prepare crude oil for use (e.g., filtration, distillation, and / or dehydration). For example, “refined oil” may be obtained from waste oil in an auto garage during auto repair and / or from the metal cutting industry, which uses oil in those processes. Contaminants can generally be removed during such refining processes. Refined oils may also include those refined based on any other oils disclosed below.

[0076] In this regard, in one embodiment, at least 85% by weight of the re-refined product, for example, at least 90% by weight, for example, at least 93% by weight, for example, at least 95% by weight, for example, at least 97% by weight, for example, at least 98% by weight, for example, at least 99% by weight, etc., may be oil. For example, the remainder may be contaminants. In this regard, less than 10% by weight of the re-refined oil, for example, less than 8% by weight, for example, less than 6% by weight, for example, less than 5% by weight, for example, less than 4% by weight, for example, less than 3% by weight, for example, less than 2% by weight, for example, less than 1% by weight, etc., may be contaminants.

[0077] In particular, re-refined oil may have a sulfur content of 1000 ppm or less, for example 800 ppm or less, for example 600 ppm or less, for example 500 ppm or less, for example 400 ppm or less, for example 300 ppm or less, for example 200 ppm or less, for example 150 ppm or less, for example 100 ppm or less, for example 80 ppm or less, for example 50 ppm or less, for example 30 ppm or less, for example 20 ppm or less, for example 10 ppm or less, etc. The sulfur content may be measured according to ASTM D5185.

[0078] Furthermore, the re-refined oil may have a polycyclic aromatic compound content of 5% by weight or less, for example, 4.5% by weight or less, for example, 4% by weight or less, for example, 3.5% by weight or less, for example, 3% by weight or less, for example, 2.5% by weight or less, for example, 2% by weight or less, for example, 1.5% by weight or less, for example, 1% by weight or less. The polycyclic aromatic compound content may be measured according to IP 346.

[0079] In addition, the re-refined oil may contain saturated compounds in amounts of 80% by weight or more, for example 85% by weight or more, for example 90% by weight or more, for example 92% by weight or more, for example 94% by weight or more, for example 95% by weight or more, for example 96% by weight or more, for example 97% by weight or more, for example 98% by weight or more, for example 99% by weight or more.

[0080] The purity of re-refined oil can also be indicated by color, as measured according to ASTM D1500. For example, re-refined oil may have color values ​​of 2 or less, e.g., 1.5 or less, e.g., 1.0 or less, e.g., 0.5 or less.

[0081] In certain embodiments, in addition to refined oil, the oil may also include unused oil. In this context, unused oil may be oil that is not considered to be refined oil. For example, such oil may not be considered to be refined waste oil or used oil. Therefore, in one embodiment, the oil may include a mixture of refined oil and unused oil.

[0082] Any suitable oil may be included in some embodiments. In certain embodiments, the oil may be selected from any combination of the aforementioned oils from (i) to (iii). Thus, oils such as refined oils may be present in the TPV formulation as part of another component (e.g., oil present with the elastomer); (ii) free oils, i.e., oils added during the vulcanization process (separate from any other TPV formulation components such as the elastomer and thermoplastic vulcanized product); (iii) curing oils, i.e., oils used to dissolve / disperse curing agents, e.g., oil-in-curing agent dispersions such as oil-in-phenol resin (in such embodiments, the curing composition may therefore be present in the TPV formulation as an oil-in-curing agent additive); and (iv) any combination of the aforementioned oils from (i) to (iii). Accordingly, oils such as refined oils may be present in the TPV formulation as part of another component (e.g., as part of the elastomer if the process oil is a curing oil, so that the elastomer includes the elastomer and the curing oil; or as part of the curing composition if the process oil is a carrier for the oil-in-curing agent, so that the curing composition includes the curing oil and the curing agent). On the other hand, oil can be added to the TPV separately from other components, i.e., as free oil.

[0083] In one embodiment, the refined oil may be provided separately from any other components in the formulation. In another embodiment, the refined oil may be a bulking oil, such that it is provided together with an elastomer. In this context, such an elastomer may be an oil-expanded elastomer, in particular a refined oil-expanded elastomer.

[0084] The bulking oil, free oil, and / or hardened oil may be the same or different oils in various embodiments. Process oils may include one or more of (i) “refined” or “mineral” oils and (ii) synthetic oils. As used herein, mineral oil is derived from petroleum crude oil and subjected to one or more refining and / or hydrotreatment steps (e.g., fractionation, hydrocracking, dewaxing, isomerization, and hydrofinishing) to refine its components and chemically modify them to achieve a final set of properties, with a lubricating viscosity (i.e., 1 mm²). 2 This refers to any hydrocarbon liquid with a kinematic viscosity (at 100°C) of more than 100°C. Such "refined" oils are in contrast to "synthetic" oils, which are produced by combining monomer units into larger molecules using catalysts, initiators, and / or heat.

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

[0086] In certain embodiments, at least a portion of the oil (e.g., all or part of one or more of the bulk oil, free oil, and / or hardened oil) is a low aromatic / sulfur-content oil, having (i) an aromatic content of less than 5% by weight, less than 3.5% by weight, or less than 1.5% by weight, based on the weight of that portion of the oil; and (ii) a sulfur content of less than 0.3% by weight, or less than 0.003% by weight, based on the weight of that portion of the oil. The aromatic content may be measured in accordance 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 certain embodiments, there is no aromatic carbon 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, measured by Method ASTM D2140.

[0087] Suitable oils for a particular embodiment may include API Group I, II, III, IV, and V base oils. See API 1509, Engine Oil Licensing and Certification System, 17th Ed, September 2012, Appx. E, 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] The oil may have a specific viscosity index, such as that measured according to ASTM D2270. For example, the viscosity index may be 80 or higher, e.g., 85 or higher, e.g., 90 or higher, e.g., 95 or higher, e.g., 100 or higher, e.g., 105 or higher, e.g., 110 or higher, e.g., 115 or higher, etc. The viscosity index may be 180 or lower, e.g., 170 or lower, e.g., 160 or lower, e.g., 150 or lower, e.g., 140 or lower, e.g., 130 or lower, e.g., 125 or lower, e.g., 120 or lower, e.g., 115 or lower, e.g., 110 or lower, etc.

[0089] Apart from the viscosity index, re-refined oil may have a specific kinematic viscosity as measured according to ASTM D7279. For example, at 40°C, the kinematic viscosity may be 15 cSt or more, e.g., 18 cSt or more, e.g., 21 cSt or more, e.g., 24 cSt or more, e.g., 27 cSt or more, e.g., 30 cSt, etc. The kinematic viscosity at 40°C may be 70 cSt or less, e.g., 60 cSt or less, e.g., 50 cSt or less, e.g., 45 cSt or less, e.g., 42 cSt or less, e.g., 39 cSt or less, e.g., 36 cSt or less, e.g., 33 cSt or less, e.g., 30 cSt or less, e.g., 27 cSt or less, e.g., 24 cSt or less, etc. The kinematic viscosity at 100°C may be 0.5 cSt or more, for example 1 cSt or more, for example 1.5 cSt or more, for example 2 cSt or more, for example 2.3 cSt or more, for example 2.6 cSt or more, for example 2.9 cSt or more, for example 3.3 cSt or more, for example 3.6 cSt or more, for example 3.9 cSt or more, for example 4.2 cSt or more, for example 4.6 cSt or more, for example 5 cSt or more, etc. The kinematic viscosity at 100°C may be 12 cSt or less, for example 10 cSt or less, for example 8 cSt or less, for example 7.6 cSt or less, for example 7.2 cSt or less, for example 6.8 cSt or less, for example 6.4 cSt or less, for example 6 cSt or less, for example 5.6 cSt or less, for example 5.2 cSt or less, for example 4.8 cSt or less, for example 4.4 cSt or less, for example 4 cSt or less, etc.

[0090] Furthermore, re-refined oil may have a specific pour point, as measured according to ASTM D5949. For example, the pour point may be below 15°C, e.g. below 10°C, e.g. below 5°C, e.g. below 0°C, e.g. below -2°C, e.g. below -5°C, e.g. below -8°C, e.g. below -10°C, e.g. below -12°C, e.g. below -15°C, e.g. below -18°C, e.g. below -20°C, e.g. below -25°C. The pour point may also be above -60°C, e.g. above -50°C, e.g. above -40°C, e.g. above -30°C, e.g. above -26°C, e.g. above -22°C, e.g. above -20°C, e.g. above -16°C, e.g. above -12°C, e.g. above -9°C, e.g. above -6°C.

[0091] Oils, such as re-refined oils, may be present in the compound and / or thermoplastic vulcanized product in amounts of 10 phr or more, for example, 20 phr or more, for example, 30 phr or more, for example, 40 phr or more, for example, 50 phr or more, for example, 60 phr or more, for example, 70 phr or more, for example, 80 phr or more, for example, 90 phr or more, for example, 100 phr or more, for example, 110 phr or more, for example, 120 phr or more, for example, 130 phr or more. Oils, such as re-refined oils, may be present in the compound and / or thermoplastic vulcanized product in amounts of 250 phr or less, for example, 220 phr or less, for example, 200 phr or less, for example, 180 phr or less, for example, 160 phr or less, for example, 150 phr or less, for example, 140 phr or less, for example, 130 phr or less, for example, 120 phr or less, for example, 110 phr or less, for example, 100 phr or less.

[0092] Thermoplastic vulcanized products and / or formulations may generally contain oil, such as refined oil, in amounts of about 2% by weight or more, for example, about 5% by weight or more, for example, about 10% by weight or more, for example, about 15% by weight or more, for example, about 20% by weight or more, for example, about 25% by weight or more, for example, about 30% by weight or more. Thermoplastic vulcanized products and / or formulations may contain oil, such as refined oil, in amounts of about 60% by weight or less, for example, about 50% by weight or less, for example, about 40% by weight or less, for example, about 35% by weight or less, for example, about 30% by weight or less, for example, about 25% by weight or less, for example, about 20% by weight or less, for example, about 15% by weight or less.

[0093] Of the total oil provided, the main portion of such oil may, in one embodiment, be provided as free oil. For example, oil making up 50% by weight or more, e.g., 60% by weight or more, 70% by weight or more, e.g., 75% by weight or more, e.g., 80% by weight or more, e.g., 85% by weight or more, e.g., 90% by weight or more, e.g., 95% by weight or more, etc., may be free oil. The remaining oil may be bulked oil and / or hardened oil. For example, oil making up 50% by weight or less, e.g., 40% by weight or less, e.g., 30% by weight or less, e.g., 20% by weight or less, e.g., 15% by weight or less, e.g., 10% by weight or less, e.g., 8% by weight or less, e.g., 5% by weight or less, etc., may be bulked oil and / or hardened oil.

[0094] Furthermore, in one embodiment, the refined oil may be provided primarily as free oil rather than as a bulking oil and / or a hardened oil. For example, 50% or more by weight of the provided refined oil, e.g., 60% or more by weight, 70% or more by weight, e.g., 75% or more by weight, e.g., 80% or more by weight, e.g., 85% or more by weight, e.g., 90% or more by weight, e.g., 95% or more by weight, e.g., 98% or more by weight, e.g., about 100% by weight, etc., may be provided as free oil. The remaining oil may be a bulking oil and / or a hardened oil.

[0095] In another embodiment, the refined oil may be provided primarily as a bulking oil rather than as free oil and / or hardened oil. For example, 50% or more by weight of the refined oil provided, e.g., 60% or more by weight, 70% or more by weight, e.g., 75% or more by weight, e.g., 80% or more by weight, e.g., 85% or more by weight, e.g., 90% or more by weight, e.g., 95% or more by weight, e.g., 98% or more by weight, e.g., about 100% by weight, etc., may be provided as a bulking oil. The remaining oil may be free oil and / or hardened oil.

[0096] E. Other additives Some embodiments of thermoplastic vulcanized compound formulations may optionally further include 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 compound may also contain one or more such additives.

[0097] Some embodiments of the TPV formulations may include polymer processing additives. The processing additives used in such embodiments are polymer resins having very high melt flow indexes. These polymer resins include both linear and branched molecules having melt flow rates of more than about 500 dg / min, more preferably more than about 750 dg / min, even more preferably more than about 1000 dg / min, even more preferably more than about 1200 dg / min, and even more preferably more than about 1500 dg / min. The thermoplastic elastomers of this disclosure may include mixtures of various branched or various linear polymer processing additives, as well as mixtures of both linear and branched polymer processing additives. References to polymer processing additives will include both linear and branched additives unless otherwise specified. Preferred linear polymer processing additives are polypropylene homopolymers. Preferred branched polymer processing additives include diene-modified polypropylene polymers.

[0098] In addition, the formulation may also include reinforcing and / or non-reinforcing fillers. Available fillers and fillers include conventional inorganic compounds such as calcium carbonate, clay, silica, talc, and titanium dioxide, as well as organic compounds such as carbon blocks and graphene, and organic and inorganic nanoscale fillers. In one embodiment, such fillers may be glass fillers such as glass fibers, glass beads, or mixtures thereof. In one embodiment, the formulation and the resulting thermoplastic vulcanized product may not contain any glass beads, in particular any glass beads. In this regard, such glass beads may be present in amounts less than 1% by weight, e.g., less than 0.5% by weight, e.g., less than 0.3% by weight, e.g., less than 0.1% by weight, e.g., less than 0.05% by weight, e.g., less than 0.01% by weight, e.g., about 0% by weight, based on the weight of the thermoplastic vulcanized product.

[0099] In certain embodiments, the TPV formulation may include an acid scavenger. These acid scavengers may be added to the thermoplastic vulcanized product after the desired level of curing has been achieved. Preferably, the acid scavenger is added after dynamic vulcanization. A useful acid scavenger is hydrotalcite. Both synthetic and natural hydrotalcite can be used. An exemplary natural hydrotalcite is of the formula Mg6Al2(OH) 16 It can be represented as CO3·4H2O. Synthetic hydrotalcite compounds are represented by the formula Mg 4.3 Al2(OH) 12 • 6CO3·mH2O or Mg 4.5 Al2(OH) 13 It may contain CO3·3.5H2O.

[0100] These additives can be used in amounts to provide the desired effect. In this regard, additives may be present in amounts up to about 50 weight percent of the total TPV formulation or TPV. In this regard, each additive and / or combination of additives may be present in amounts such as 0.001% by weight or more, e.g., 0.01% by weight or more, e.g., 0.05% by weight or more, e.g., 0.1% by weight or more, e.g., 0.2% by weight or more, e.g., 0.3% by weight or more, e.g., 0.5% by weight or more, e.g., 1% by weight or more, e.g., 2% by weight or more, e.g., 3% by weight or more, e.g., 5% by weight or more, e.g., 8% by weight or more, e.g., 10% by weight or more, e.g., 12% by weight or more, e.g., 15% by weight or more, e.g., 20% by weight or more, e.g., 25% by weight or more, e.g., 30% by weight or more. These may be present in amounts such as 50% by weight or less, for example 40% by weight or less, for example 30% by weight or less, for example 25% by weight or less, for example 20% by weight or less, for example 18% by weight or less, for example 15% by weight or less, for example 13% by weight or less, for example 10% by weight or less, for example 8% by weight or less, for example 6% by weight or less, for example 4% by weight or less, for example 3% by weight or less, for example 2% by weight or less, for example 1% by weight or less, for example 0.5% by weight or less. In another embodiment, such aforementioned percentages may be based on the weight of the thermoplastic resin. In a further embodiment, such aforementioned percentages may be based on the weight of the elastomer. In yet another embodiment, such aforementioned percentages may be based on the combined weight of the thermoplastic resin and the elastomer.

[0101] F.TPV formulation Generally, as used herein, “TPV formulation” refers to a mixture of components that are blended or otherwise compiled before or during processing of the TPV formulation to form a TPV. This acknowledges the fact that components mixed together and subsequently processed may be present or absent in the final TPV in the same amounts as they were added to the formulation, depending on the reactions that occur between some or all of the components during processing of the mixed components.

[0102] Generally, TPV formulations in various embodiments include an elastomer, a thermoplastic resin, a curing agent (or curing composition), and an oil containing a re-refined oil together with any other optional additives. As will be discussed in more detail below, the TPV formulation is subjected to a process such as dynamic vulcanization or dynamic curing to form the TPV. In certain embodiments, any other additives may be added to the TPV formulation during the process, either before or after dynamic vulcanization.

[0103] The relative amounts of various components in a TPV formulation are conveniently characterized in terms of parts by weight (phr) per 100 parts by weight of rubber, in particular, with respect to the amount of elastomer in the formulation. In embodiments in which the elastomer is contained together with an extender, as is common for many commercially available elastomers such as EPDM, the phr amount is based only on the amount of elastomer, excluding the extender present with the elastomer. Therefore, for example, an elastomer containing 100 parts EPDM (rubber) and 75 parts extender would likely be considered to be present in the TPV formulation at 175 phr (i.e., relative to 100 parts EPDM rubber). If such a TPV formulation is further characterized by containing 50 phr of thermoplastic resin, the formulation would contain 100 parts by weight of elastomer and 75 parts by weight of extender, in addition to 50 parts by weight of thermoplastic resin.

[0104] Some embodiments of the TPV formulation may contain a thermoplastic resin in an amount of about 10 to about 300 parts (phr) per 100 parts by weight of elastomer or rubber. In various embodiments, the thermoplastic resin is included in the TPV formulation in an amount ranging from one of the lower values ​​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 one of the higher values ​​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 values ​​are greater than or equal to the lower values. In certain embodiments, an increase in the amount of thermoplastic resin corresponds to an increase in the hardness of the dynamically vulcanized TPV.

[0105] If the elastomer consists solely of elastomer, it is present at 100 phr by definition (as that is the basis of phr notation). However, in embodiments where the elastomer component includes other components, such as filler oils, the elastomer may be present in the TPV formulation in amounts ranging from one lower value of about 100.05, 100.1, 100.15, 100.2, 105, 110, 115, and 120 phr to one higher value of about 110, 120, 125, 150, 175, 200, 225, and 250 phr.

[0106] As described above, the TPV formulations of a particular embodiment may optionally include additional TPV additives. The amount of additional additives is separate and in addition to those additives already present in other components of the TPV formulation. For example, any additives such as bulking oils present with the elastomer are already accounted for as part of the amount of elastomer added to the formulation; therefore, the enumerated amounts of additional additives exclude those additives already present with the elastomer. Additional additives may be present in the TPV formulation in amounts ranging from about 0 phr to about 300 phr overall. In certain embodiments, additional additives may be present in the TPV in amounts ranging from one of the lower values ​​of approximately 0, 5, 10, 15, 25, 30, 40, 50, 60, 70, 80, 90, and 100 phr to one of the higher values ​​of approximately 25, 30, 40, 50, 60, 80, 100, 125, 150, 175, 200, 225, 250, 275, and 300 phr. The additional additives may be included in amounts ranging from one of the aforementioned lower values ​​to one of the aforementioned higher values, provided that the higher values ​​are greater than or equal to the lower values. In one embodiment, such aforementioned phr may refer to the additional additives individually rather than in total.

[0107] For convenience, the components of TPV formulations in various embodiments may be characterized based on their weight percentages in the TPV formulation as follows:

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

[0109] Elastomers may be present in the TPV formulation in amounts ranging from one lower value of approximately 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, and 35% by weight to one higher value of approximately 35, 40, 45, 50, 55, 60, 65, 70, 75, and 80% by weight, provided that the higher value is greater than or equal to the lower value, and the elastomers are present in the TPV formulation in the range of approximately 20 to approximately 300 phr.

[0110] Optional additional TPV additives may be present in the TPV formulation in amounts ranging from one lower value of approximately 0, 5, 10, 15, 20, 25, 30, 35, and 40% by weight to one higher value of approximately 30, 35, 40, 45, 50, 55, 60, and 65% by weight, provided that the higher value is greater than or equal to the lower value, and the additives are present in the TPV formulation within the range of approximately 0 to approximately 300 phr.

[0111] As shown herein, thermoplastic vulcanized products such as those disclosed herein contain a relatively high level of recycled content. For example, thermoplastic formulations and / or thermoplastic vulcanized products contain refined oils as referred herein. In addition, thermoplastic formulations and / or thermoplastic vulcanized products may also contain recycled thermoplastic resins. Therefore, recycled content may include refined oils and any recycled thermoplastic resins. Currently, recycled content may also include any recycled elastomers. Therefore, the recycled content may be about 5% by weight or more, e.g., about 10% by weight or more, e.g., about 15% by weight or more, e.g., about 20% by weight or more, e.g., about 25% by weight or more, e.g., about 30% by weight or more, e.g., about 35% by weight or more, e.g., about 40% by weight or more, e.g., about 50% by weight or more, e.g., about 60% by weight or more, e.g., about 70% by weight or more, e.g., about 80% by weight or more, e.g., about 90% by weight or more, based on the total weight of the thermoplastic formulations and / or thermoplastic vulcanized products. The recycled content may consist of approximately 95% by weight or less, for example, approximately 90% by weight or less, for example, approximately 80% by weight or less, for example, approximately 70% by weight or less, for example, approximately 60% by weight or less, for example, approximately 50% by weight or less, for example, approximately 40% by weight or less, for example, approximately 30% by weight or less, for example, approximately 20% by weight or less, based on the total weight of the thermoplastic compound and / or thermoplastic resin.

[0112] Treatment of G.TPV formulations The thermoplastic vulcanized products of this disclosure are prepared by dynamic vulcanization techniques. The term “dynamic vulcanization” refers to the vulcanization or curing process of a TPV formulation containing an elastomer, where the elastomer is vulcanized under high-shear mixing conditions at a temperature above the melting point of the thermoplastic resin to produce a thermoplastic vulcanized product. In dynamic vulcanization, the elastomer is simultaneously crosslinked and dispersed as fine particles within the thermoplastic resin or matrix, although other morphologies, such as co-continuous morphologies, may exist depending on the degree of curing, the viscosity ratio of the elastomer to the resin, the intensity of the mixing, the residence time, and the temperature.

[0113] In this regard, the present disclosure relates to a method for dynamically vulcanizing or curing a formulation comprising a thermoplastic resin, an elastomer, an oil containing a refined oil, and a curing agent. Thus, dynamic vulcanization occurs in the presence of the refined oil. Such a method may successively provide a thermoplastic vulcanized product comprising a thermoplastic resin and at least a partially cured elastomer. For example, the thermoplastic resin may be provided as a continuous phase or matrix, where at least a partially cured elastomer is provided as a dispersed phase within the continuous thermoplastic phase.

[0114] In some embodiments, the process may involve melt-blending a TPV formulation comprising an elastomer, a thermoplastic resin, and a curing agent in a chamber. The chamber may be any vessel suitable for blending the selected composition under the temperature and shear force conditions necessary to form a thermoplastic vulcanized product. In this regard, the chamber may be a mixer such as a Banbury® mixer or a Bravender® mixer, as well as certain mixing extruders such as simultaneous, reverse, and twin-screw extruders, and co-kneaders such as a Buss® kneader. According to one embodiment, the chamber may be 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- and three-screw extruders are exemplary, and in some embodiments, two- or two-screw extruders are preferred. The screws of the extruder may have multiple lobes; two- and three-lobe screws are preferred. It will be readily apparent that other screw designs may be selected according to the methods of embodiments of this disclosure. In some embodiments, dynamic vulcanization may occur during and / or as a result of extrusion. After being discharged from the mixer, the blend containing vulcanized rubber and thermoplastic material can be crushed, chopped, extruded, pelletized, injection molded, or processed by other preferred techniques.

[0115] Dynamic vulcanization of elastomers may be performed to achieve relatively high shear. In certain embodiments, blending may be performed at a temperature not exceeding about 400°C, preferably not exceeding about 300°C, and more preferably not exceeding about 250°C. The minimum temperature at which melt blending is performed is generally about 130°C or higher, preferably about 150°C or higher, and more particularly above about 180°C. The blending time is selected by considering the properties of the compounds used in the TPV formulation and the blending temperature. This time generally varies from about 5 seconds to about 120 minutes, and in most cases from about 10 seconds to about 30 minutes.

[0116] Dynamic vulcanization in some embodiments may involve phase inversion. As those skilled in the art will understand, dynamic vulcanization can be initiated by including a larger volume fraction of rubber than thermoplastic resin. Thus, the thermoplastic resin may exist as a discontinuous phase if the volume fraction of rubber is greater than the volume fraction of thermoplastic resin. As dynamic vulcanization progresses, the viscosity of the rubber increases, and phase inversion occurs under dynamic mixing. In other words, at phase inversion, the thermoplastic resin phase becomes a continuous phase.

[0117] When dynamic vulcanization is performed, other additives are preferably present in the TPV formulation, but in some embodiments, one or more other additives (if any) may be added to the composition after curing and / or phase inversion (e.g., after the dynamic vulcanization portion of the process). Additional additives may be added after dynamic vulcanization by various techniques. In one embodiment, they can be added while the thermoplastic vulcanized material maintains its molten state from the dynamic vulcanization process. For example, additional additives can be added downstream of the dynamic vulcanization location in a process using a continuous processing device, such as a single-screw or twin-screw extruder. In other embodiments, the thermoplastic vulcanized material can be “worked up” or pelletized and then melted, and additional additives can be added to the molten thermoplastic vulcanized product. This latter process may be referred to as the “second pass” addition of components.

[0118] Despite the fact that elastomers can be partially or completely cured, thermoplastic vulcanized materials can be processed and reprocessed by conventional plastic processing techniques such as extrusion, injection molding, and compression molding. The elastomers in these thermoplastic elastomers are usually in the form of finely pulverized, well-dispersed particles of vulcanized or cured rubber in a continuous thermoplastic phase or matrix, although cocontinuous morphology or phase inversion is also possible. In those embodiments where the cured rubber is in the form of finely pulverized, well-dispersed particles in a thermoplastic medium, the rubber particles may have an average diameter of less than 50 μm, e.g., less than 30 μm, e.g., less than 10 μm, e.g., less than 5 μm, e.g., less than 1 μm. In preferred embodiments, at least 50%, e.g., at least 60%, e.g., at least 75%, etc., of the rubber particles may have an average diameter of less than 5 μm, e.g., less than 2 μm, e.g., less than 1 μm.

[0119] The degree of hardening can be measured by determining the amount of rubber that can be extracted from the thermoplastic vulcanized by using cyclohexane or boiling xylene as an extractant. Preferably, the rubber may have a degree of hardening that allows extraction of 15% by weight or less, e.g., 10% by weight or less, e.g., 5% by weight or less, e.g., 3% by weight or less, etc., by cyclohexane at 23°C, as described in U.S. Patents No. 4,311,628, No. 5,100,947 and No. 5,157,081, all of which are incorporated herein by reference. Alternatively, the rubber may have a crosslinking density of at least 4 × 10 per milliliter of rubber. -5 For example, at least 7 × 10 -5 For example, at least 10 x 10 -5 It can exhibit a degree of hardening similar to that of moles. See Crosslink Densities and Phase Morphologies in Dynamically Vulcanized TPEs by Ellul et al, Rubber Chemistry and Technology, Vol. 68, pp. 573-584 (1995).

[0120] The resulting thermoplastic vulcanized material may have a desired density that makes it usable for molded articles as described herein. In this regard, the density is 0.3 g / cm³. 3 For example, 0.4 g / cm³ 3 For example, 0.5 g / cm³ 3 For example, 0.6 g / cm³ 3 For example, 0.65 g / cm³ 3 For example, 0.7 g / cm³ 3 For example, 0.75 g / cm³ 3 For example, 0.8 g / cm³ 3 For example, 0.85 g / cm³ 3 For example, 0.9 g / cm³ 3 For example, 0.95 g / cm³ 3 For example, 1 g / cm³ 3 For example, 1.05 g / cm³ 3 For example, 1.1 g / cm³ 3 For example, 1.15 g / cm³ 3 For example, 1.2 g / cm³ 3 The above are possible. The density is 2 g / cm³. 3 For example, 1.8 g / cm³ 3 For example, 1.6 g / cm³ 3 For example, 1.4 g / cm³ 3 For example, 1.3 g / cm³ 3 For example, 1.2 g / cm³ 3 For example, 1.1 g / cm³ 3 For example, 1.0 g / cm³ 3 For example, 0.95 g / cm³ 3 For example, 0.90 g / cm³ 3 For example, 0.7 g / cm³ 3 For example, 0.6 g / cm³ 3 For example, 0.55 g / cm³ 3 The following are possible:

[0121] H. Formation of molded products Immediately after formation, the thermoplastic vulcanized material can be molded into the form of an article using any of the various techniques known in the art. For example, the thermoplastic vulcanized material can be advantageously processed by using typical molding processes such as injection molding, extrusion molding, compression molding, blow molding, rotational molding, overmolding, etc. Generally, these processes include heating the thermoplastic vulcanized material to a temperature above the melting temperature of the thermoplastic resin to form a preform for the mold cavity for forming the article, cooling the article to a temperature below the crystallization temperature of the thermoplastic vulcanized material, and demolding the article from the mold. The mold cavity defines the shape of the article. The article is cooled in the mold to a temperature below the crystallization temperature of the thermoplastic vulcanized material, and then the article can be demolded from the mold.

[0122] Thermoplastic vulcanized materials may also be formed using extrusion molding to form molded articles. In this context, thermoplastic vulcanized materials may be extruded as described herein. Once exiting the extruder, thermoplastic vulcanized materials may be formed or molded to form molded articles. Such molded articles may be formed by using specific dies for molding the thermoplastic vulcanized materials as they exit the extruder. Such molding / forming processes, such as the extrusion process, may be automated or robotic processes. In this context, the method of forming the molded articles is not necessarily limited.

[0123] I. Characteristics By utilizing refined oils as disclosed herein, thermoplastic vulcanized products may exhibit specific desired properties. For example, the use of materials such as those disclosed herein, including refined oils and other optionally selected recycled materials such as thermoplastic resins and elastomers, can result in a reduction of the carbon footprint. In particular, using the cradle-to-gate method, the carbon footprint may be 3.0 kg CO2eq / kg or less, e.g., 2.8 kg CO2eq / kg or less, e.g., 2.6 kg CO2eq / kg or less, e.g., 2.4 kg CO2eq / kg or less, e.g., 2.2 kg CO2eq / kg or less, e.g., 2.0 kg CO2eq / kg or less, e.g., 1.8 kg CO2eq / kg or less, e.g., 1.6 kg CO2eq / kg or less, e.g., 1.5 kg CO2eq / kg or less, e.g., 1.4 kg CO2eq / kg or less, e.g., 1.3 kg CO2eq / kg or less, e.g., 1.2 kg CO2eq / kg or less, e.g., 1.1 kg CO2eq / kg or less, e.g., 1.0 kg CO2eq / kg or less. The carbon footprint is given by the following equation: CO2 footprint = ΣW i ·X i +C (In the formula, W i This is a weight fraction, and X i (where is the CO2 footprint of component i in the formulation, and C is a constant that can be added to take into account CO2 emissions from energy use, raw material logistics, and packaging involved.) It can be estimated using [this method]. In this disclosure, C was estimated to be approximately 0.35 kgCO2eq / kg. The CO2 footprint values ​​of the base raw materials were derived from the EcoInvent 3.6 database or as supplied by the raw material manufacturers.

[0124] In addition, the inventors have found that the properties of these materials utilizing recycled contents can even be comparable to those exhibited by the same thermoplastic vulcanized products manufactured from one or more unused oils and not from any refined oils. In particular, any single property of a thermoplastic vulcanized product containing a refined oil as defined herein, as specified below, may be within 35%, e.g., 30%, e.g., 25%, e.g., 20%, e.g., 18%, e.g., 16%, e.g., 14%, e.g., 12%, e.g., 10%, e.g., 9%, e.g., 8%, e.g., 7%, e.g., 6%, e.g., 5%, e.g., 4%, e.g., 3%, e.g., 2%, e.g., 1%, etc., of the corresponding thermoplastic vulcanized product manufactured from unused oil and not from any refined oil.

[0125] In this context, the thermoplastic vulcanized material may exhibit a specific Shore A hardness (ASTM 2240-15(2021); 15 seconds) used to measure the hardness of the thermoplastic vulcanized material and provide an index of indentation resistance. In this context, the thermoplastic vulcanized material may have a Shore A hardness of 25 to 100. For example, the thermoplastic vulcanized material may have a Shore A hardness of 25 or more, e.g., 35 or more, e.g., 40 or more, e.g., 45 or more, e.g., 50 or more, e.g., 55 or more, e.g., 60 or more, e.g., 65 or more, e.g., 70 or more, e.g., 75 or more. The thermoplastic vulcanized material may have a Shore A hardness of 100 or less, e.g., 95 or less, e.g., 90 or less, e.g., 80 or less, e.g., 70 or less, e.g., 65 or less, e.g., 60 or less, e.g., 55 or less, e.g., 50 or less. Such hardness may enable the thermoplastic resin and / or the resulting molded article to provide the necessary compliance to function effectively for the desired application. In one embodiment, the Shore A hardness described above may be for an unaged sample. In another embodiment, the Shore A hardness described above may be for an aged sample. For example, the sample may 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 context, such a Shore A hardness may be achieved by at least one, for example, at least two, for example, all three, of the aforementioned aging conditions.

[0126] In this regard, thermoplastic vulcanized materials may similarly exhibit a specific Shore D hardness (ASTM 2240-15(2021); 15 seconds). In this regard, thermoplastic vulcanized materials may have a Shore D hardness greater than 0 and between 0 and 50. For example, thermoplastic vulcanized materials may have a Shore D hardness greater than 0, e.g., 5 or more, e.g., 10 or more, e.g., 15 or more, e.g., 20 or more, e.g., 25 or more, e.g., 30 or more, e.g., 35 or more, e.g., 40 or more. Thermoplastic vulcanized materials may have a Shore D hardness of 50 or less, e.g., 45 or less, e.g., 40 or less, e.g., 35 or less, e.g., 30 or less, e.g., 25 or less, e.g., 20 or less, e.g., 15 or less, e.g., 10 or less, e.g., 5 or less. In one embodiment, the above-mentioned Shore D hardness may be for an unaged sample. In another embodiment, the above-mentioned Shore D hardness may be for an aged sample. For example, the sample may 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 context, such Shore D hardness can be achieved by at least one, for example, at least two, for example, all three, of the aforementioned aging conditions.

[0127] In addition, thermoplastic vulcanized materials may exhibit certain strengths, as indicated by specific mechanical properties. For example, thermoplastic vulcanized materials may exhibit a 100% modulus of elasticity (ASTM D412-16, Die C, transverse flow), also known as M100, at least 0.3 MPa, e.g., 0.3 to 50 MPa, e.g., 0.5 to 10 MPa, e.g., 1 to 8 MPa, e.g., 2 to 7 MPa. For example, the 100% modulus of elasticity may be 0.3 MPa or higher, e.g., 0.4 MPa or higher, e.g., 0.5 MPa or higher, e.g., 0.8 MPa or higher, e.g., 1 MPa or higher, e.g., 1.1 MPa or higher, e.g., 1.2 MPa or higher, e.g., 1.3 MPa or higher, e.g., 1.4 MPa or higher, e.g., 1.5 MPa or higher, e.g., 2 MPa or higher, e.g., 2.5 MPa or higher, e.g., 3 MPa or higher, e.g., 4 MPa or higher, e.g., 5 MPa or higher, e.g., 6 MPa or higher, e.g., 10 MPa or higher, e.g., 20 MPa or higher, e.g., 30 MPa or higher, etc. The 100% modulus of elasticity may be 50 MPa or less, for example 40 MPa or less, for example 30 MPa or less, for example 25 MPa or less, for example 20 MPa or less, for example 15 MPa or less, for example 10 MPa or less, for example 8 MPa or less, for example 6 MPa or less, for example 5 MPa or less, for example 4.5 MPa or less, for example 4 MPa or less, for example 3.8 MPa or less, for example 3.5 MPa or less, for example 3.3 MPa or less, for example 3 MPa or less, for example 2.8 MPa or less, for example 2.5 MPa or less, for example 2.3 MPa or less, for example 2 MPa or less, for example 1.9 MPa or less, for example 1.8 MPa or less, for example 1.5 MPa or less, for example 1.3 MPa or less, for example 1.1 MPa or less, for example 0.8 MPa or less, etc. In one embodiment, the aforementioned modulus of elasticity at 100% elongation may be for an unaged sample. In another embodiment, the aforementioned modulus of elasticity at 100% elongation may be for an aged sample. For example, the sample may 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 regard, such modulus of elasticity at 100% elongation can be achieved by at least one, for example, at least two, for example, all three, of the aforementioned aging conditions.

[0128] In addition, thermoplastic vulcanized materials may exhibit certain strengths, as indicated by specific mechanical properties. For example, thermoplastic vulcanized materials may exhibit a 50% modulus of elasticity (ASTM D412-16, Die C, transverse flow), also known as M50, at least 0.3 MPa, e.g., 0.3 to 50 MPa, e.g., 0.5 to 10 MPa, e.g., 1 to 8 MPa, e.g., 2 to 7 MPa. For example, the 50% modulus of elasticity may be 0.3 MPa or higher, e.g., 0.4 MPa or higher, e.g., 0.5 MPa or higher, e.g., 0.8 MPa or higher, e.g., 1 MPa or higher, e.g., 1.1 MPa or higher, e.g., 1.2 MPa or higher, e.g., 1.3 MPa or higher, e.g., 1.4 MPa or higher, e.g., 1.5 MPa or higher, e.g., 2 MPa or higher, e.g., 2.5 MPa or higher, e.g., 3 MPa or higher, e.g., 4 MPa or higher, e.g., 5 MPa or higher, e.g., 6 MPa or higher, e.g., 10 MPa or higher, e.g., 20 MPa or higher, e.g., 30 MPa or higher, etc. The 50% modulus of elasticity may be 50 MPa or less, for example 40 MPa or less, for example 30 MPa or less, for example 25 MPa or less, for example 20 MPa or less, for example 15 MPa or less, for example 10 MPa or less, for example 8 MPa or less, for example 6 MPa or less, for example 5 MPa or less, for example 4.5 MPa or less, for example 4 MPa or less, for example 3.8 MPa or less, for example 3.5 MPa or less, for example 3.3 MPa or less, for example 3 MPa or less, for example 2.8 MPa or less, for example 2.5 MPa or less, for example 2.3 MPa or less, for example 2 MPa or less, for example 1.9 MPa or less, for example 1.8 MPa or less, for example 1.5 MPa or less, for example 1.3 MPa or less, for example 1.1 MPa or less, for example 0.8 MPa or less, etc. In one embodiment, the aforementioned modulus of elasticity at 50% elongation may be for an unaged sample. In another embodiment, the aforementioned modulus of elasticity at 50% elongation may be for an aged sample. For example, the sample may 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 context, such modulus of elasticity at 50% elongation can be achieved by at least one, for example, at least two, for example, all three, of the aforementioned aging conditions.

[0129] In addition, thermoplastic vulcanized materials may exhibit certain strengths, as indicated by specific mechanical properties. For example, thermoplastic vulcanized materials may exhibit a 25% modulus of elasticity at 25% elongation, also known as M25 (ASTM D412-16, Die C, transverse flow), of at least 0.3 MPa, e.g., 0.3 to 50 MPa, e.g., 0.5 to 10 MPa, e.g., 1 to 8 MPa, e.g., 1 to 4 MPa. For example, the 25% modulus of elasticity may be 0.3 MPa or higher, e.g., 0.4 MPa or higher, e.g., 0.5 MPa or higher, e.g., 0.8 MPa or higher, e.g., 1 MPa or higher, e.g., 1.1 MPa or higher, e.g., 1.2 MPa or higher, e.g., 1.3 MPa or higher, e.g., 1.4 MPa or higher, e.g., 1.5 MPa or higher, e.g., 2 MPa or higher, e.g., 2.5 MPa or higher, e.g., 3 MPa or higher, e.g., 4 MPa or higher, e.g., 5 MPa or higher, e.g., 6 MPa or higher, e.g., 10 MPa or higher, e.g., 20 MPa or higher, e.g., 30 MPa or higher, etc. The 25% modulus of elasticity may be 50 MPa or less, for example 40 MPa or less, for example 30 MPa or less, for example 25 MPa or less, for example 20 MPa or less, for example 15 MPa or less, for example 10 MPa or less, for example 8 MPa or less, for example 6 MPa or less, for example 5 MPa or less, for example 4.5 MPa or less, for example 4 MPa or less, for example 3.8 MPa or less, for example 3.5 MPa or less, for example 3.3 MPa or less, for example 3 MPa or less, for example 2.8 MPa or less, for example 2.5 MPa or less, for example 2.3 MPa or less, for example 2 MPa or less, for example 1.9 MPa or less, for example 1.8 MPa or less, for example 1.5 MPa or less, for example 1.3 MPa or less, for example 1.1 MPa or less, for example 0.8 MPa or less, etc. In one embodiment, the aforementioned modulus of elasticity at 25% elongation may be for an unaged sample. In another embodiment, the aforementioned modulus of elasticity at 25% elongation may be for an aged sample. For example, the sample may 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 context, such an elastic modulus at 25% elongation can be achieved by at least one, for example, at least two, for example, all three, of the aforementioned aging conditions.

[0130] Thermoplastic vulcanized materials may also exhibit tensile stresses at fracture (i.e., tensile strengths) such as 0.5 to 50 MPa, for example 1 to 20 MPa, for example 2 to 12 MPa, for example 3 to 9 MPa. For example, thermoplastic vulcanized materials may exhibit tensile stresses such as 0.5 MPa or more, for example 1 MPa or more, for example 1.5 MPa or more, for example 2 MPa or more, for example 2.5 MPa or more, for example 3 MPa or more, for example 3.5 MPa or more, for example 4 MPa or more, for example 4.5 MPa or more, for example 5 MPa or more, for example 5.5 MPa or more, for example 6 MPa or more, for example 7 MPa or more, for example 8 MPa or more, for example 9 MPa or more, for example 10 MPa or more, for example 15 MPa or more, for example 20 MPa or more, for example 30 MPa or more, for example 40 MPa or more, for example 50 MPa or more, for example 60 MPa or more, for example 70 MPa or more. The tensile stress may be 100 MPa or less, for example 80 MPa or less, for example 60 MPa or less, for example 50 MPa or less, for example 40 MPa or less, for example 30 MPa or less, for example 25 MPa or less, for example 20 MPa or less, for example 18 MPa or less, for example 15 MPa or less, for example 13 MPa or less, for example 11 MPa or less, for example 10 MPa or less, for example 9 MPa or less, for example 8 MPa or less, for example 7 MPa or less, for example 6.5 MPa or less, for example 6 MPa or less, for example 5.5 MPa or less, for example 5 MPa or less, for example 4.5 MPa or less, for example 4 MPa or less, for example 3.5 MPa or less, for example 3 MPa or less, for example 2.5 MPa or less, etc. The tensile stress may be measured according to ASTM D412-16 at a temperature of 23°C (Die C, transverse flow). In one embodiment, the aforementioned fracture point tensile stress may be for an unaged sample. In another embodiment, the aforementioned fracture point tensile stress may be for an aged sample. For example, the sample may 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 context, such fracture point tensile stress can be achieved by at least one, for example, at least two, for example, all three, of the aforementioned aging conditions.

[0131] Thermoplastic vulcanized materials may also exhibit desired elongation at break. For example, the elongation at break may be 20% or more, e.g., 40% or more, e.g., 60% or more, e.g., 80% or more, e.g., 100% or more, e.g., 150% or more, e.g., 200% or more, e.g., 250% or more, e.g., 300% or more, e.g., 350% or more, e.g., 400% or more, e.g., 500% or more, e.g., 550% or more, e.g., 600% or more, e.g., 650% or more, e.g., 700% or more, e.g., 750% or more, e.g., 900% or more, and so on. The elongation at break may be less than or equal to 2000%, e.g., less than or equal to 1800%, e.g., less than or equal to 1500%, e.g., less than or equal to 1300%, e.g., less than or equal to 1000%, e.g., less than or equal to 900%, e.g., less than or equal to 800%, e.g., less than or equal to 700%, e.g., less than or equal to 600%, e.g., less than or equal to 500%, e.g., less than or equal to 450%, e.g., less than or equal to 400%, e.g., less than or equal to 350%, e.g., less than or equal to 300%, etc. The elongation at break may be measured according to ASTM D412-16 at a temperature of 23°C (Die C, transverse flow). In one embodiment, the elongation at break described above may be for an unaged sample. In another embodiment, the elongation at break described above may be for an aged sample. For example, the sample may 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 regard, such fracture elongation can be achieved by at least one, for example, at least two, or for example, all three, of the aforementioned aging conditions.

[0132] Thermoplastic vulcanized materials can also be advantageously characterized by low compression set. For example, the compression set may be 85% or less, e.g., 80% or less, e.g., 70% or less, e.g., 65% or less, e.g., 60% or less, e.g., 55% or less, e.g., 50% or less, e.g., 45% or less, e.g., 40% or less, e.g., 35% or less, e.g., 30% or less, e.g., 25% or less, e.g., 20% or less, e.g., 15% or less. The compression set may be 5% or more, e.g., 8% or more, e.g., 10% or more, e.g., 13% or more, e.g., 15% or more, e.g., 18% or more, e.g., 20% or more, e.g., 25% or more, e.g., 30% or more, e.g., 35% or more, e.g., 40% or more, e.g., 50% or more, e.g., 60% or more, e.g., 70% or more. The compression set may be measured according to ASTM D395B-18 (Type 1 sample, 25%, 22 hours). Such compression set, as described above, is based on temperatures of room temperature, 70°C, and / or 110°C. In this regard, such compression set can be achieved in one embodiment by at least one temperature, for example, at least two temperatures, for example, a total of three temperatures, etc.

[0133] Thermoplastic vulcanized materials can also be advantageously characterized by high tear strength. For example, the tear strength may be 50 N / cm or more, e.g., 100 N / cm or more, e.g., 150 N / cm or more, e.g., 200 N / cm or more, e.g., 250 N / cm or more, e.g., 300 N / cm or more, e.g., 350 N / cm or more, e.g., 400 N / cm or more, e.g., 450 N / cm or more, e.g., 500 N / cm or more, e.g., 550 N / cm or more, e.g., 600 N / cm or more, e.g., 650 N / cm or more, etc. The tear strength may be 1200 N / cm or less, for example 1100 N / cm or less, for example 1000 N / cm or less, for example 900 N / cm or less, for example 800 N / cm or less, for example 700 N / cm or less, for example 650 N / cm or less, for example 600 N / cm or less, for example 550 N / cm or less, for example 500 N / cm or less, for example 450 N / cm or less, for example 400 N / cm or less, for example 350 N / cm or less, for example 300 N / cm or less, etc. The tear strength may be measured according to ASTM D624 (Die C, transverse flow).

[0134] The thermoplastic vulcanizate also has a specific gravity of 0.900 g / cm 3 or more, for example 0.91 g / cm 3 or more, for example 0.915 g / cm 3 or more, for example 0.92 g / cm 3 or more, for example 0.925 g / cm 3 or more, for example 0.93 g / cm 3 or more, for example 0.935 g / cm 3 or more, for example 0.94 g / cm 3 or more, for example 0.945 g / cm 3 or more, for example 0.95 g / cm 3 or more, for example 0.965 g / cm 3 or more, for example 0.97 g / cm 3 or more, for example 0.975 g / cm 3 or more, for example 0.98 g / cm 3 or more, such as those measured according to ASTM D - 792, and is characterized by specific gravity. The specific gravity is 1.1 g / cm 3 or less, for example 1.05 g / cm 3 or less, for example 1 g / cm 3 or less, for example 0.995 g / cm 3 or less, for example 0.99 g / cm 3 or less, for example 0.985 g / cm 3 or less, for example 0.98 g / cm 3 or less, for example 0.975 g / cm 3 or less, for example 0.97 g / cm 3 or less, for example 0.965 g / cm 3 or less, for example 0.96 g / cm 3 or less, etc.

[0135] Thermoplastic vulcanized materials can also be characterized by weight increase, as measured according to ASTM D471, using IRM903 oil at 121°C for 24 hours. Such a weight percentage provides a weight percentage of oil swelling as an implicit measure of the degree of curing or crosslinking of the elastomer. Generally, low or partial crosslinking of the elastomer will result in a higher oil swelling value, while highly crosslinked dispersed elastomers will have a lower oil swelling. In this context, the weight increase may be 10% or more, e.g., 20% or more, e.g., 30% or more, e.g., 40% or more, e.g., 50% or more, e.g., 60% or more, e.g., 70% or more, e.g., 80% or more, e.g., 90% or more, e.g., 100% or more, etc. The weight increase may be less than 150%, for example less than 130%, for example less than 110%, for example less than 100%, for example less than 90%, for example less than 80%, for example less than 70%, for example less than 60%, for example less than 50%, for example less than 40%, etc.

[0136] Thermoplastic vulcanized materials can also be characterized by their LCR viscosity, which is measured according to ASTM D-3835 at 204°C using a die with a diameter of 1 mm, a length of 30 mm, and an inlet angle of 180°. For example, the LCR viscosity at 1200 s⁻¹ may be ≥ 30 Pa·s, e.g. ≥ 40 Pa·s, e.g. ≥ 50 Pa·s, e.g. ≥ 60 Pa·s, e.g. ≥ 70 Pa·s, e.g. ≥ 80 Pa·s, e.g. ≥ 85 Pa·s, e.g. ≥ 90 Pa·s, e.g. ≥ 95 Pa·s, e.g. ≥ 100 Pa·s, etc. The LCR viscosity at 1200s-1 may be 200 Pa·s or less, for example 180 Pa·s or less, for example 160 Pa·s or less, for example 140 Pa·s or less, for example 130 Pa·s or less, for example 120 Pa·s or less, for example 115 Pa·s or less, for example 110 Pa·s or less, for example 105 Pa·s or less, for example 100 Pa·s or less, for example 95 Pa·s or less, etc.

[0137] The LCR viscosity at 200s-1 can be 200 Pa·s or higher, for example 250 Pa·s or higher, for example 300 Pa·s or higher, for example 320 Pa·s or higher, for example 340 Pa·s or higher, for example 360 ​​Pa·s or higher, for example 370 Pa·s or higher, for example 380 Pa·s or higher, for example 390 Pa·s or higher, for example 400 Pa·s or higher, and so on. The LCR viscosity at 200s-1 may be 700 Pa·s or less, for example 650 Pa·s or less, for example 600 Pa·s or less, for example 550 Pa·s or less, for example 500 Pa·s or less, for example 480 Pa·s or less, for example 460 Pa·s or less, for example 440 Pa·s or less, for example 430 Pa·s or less, for example 420 Pa·s or less, for example 415 Pa·s or less, for example 410 Pa·s or less, for example 405 Pa·s or less, for example 400 Pa·s or less, for example 395 Pa·s or less, for example 390 Pa·s or less, for example 385 Pa·s or less, for example 380 Pa·s or less, for example 370 Pa·s or less, for example 360 ​​Pa·s or less, for example 350 Pa·s or less, etc.

[0138] Thermoplastic vulcanized products can also be characterized by their extrusion surface roughness (ESR). ESR can determine the fit and aesthetics of the final extruded product. In this regard, ESR can be 300 μin or less, e.g., 280 μin or less, e.g., 260 μin or less, e.g., 240 μin or less, e.g., 220 μin or less, e.g., 200 μin or less, e.g., 180 μin or less, e.g., 160 μin or less, e.g., 140 μin or less, e.g., 130 μin or less, e.g., 120 μin or less, e.g., 110 μin or less, e.g., 100 μin or less, e.g., 90 μin or less, e.g., 80 μin or less, e.g., 70 μin or less, e.g., 60 μin or less, e.g., 50 μin or less, e.g., 40 μin or less, etc. ESR can be 0.1 μin or more, for example 0.5 μin or more, for example 1 μin or more, for example 5 μin or more, for example 10 μin or more, for example 20 μin or more, for example 30 μin or more, for example 40 μin or more, for example 50 μin or more, for example 60 μin or more, for example 70 μin or more, for example 80 μin or more, for example 90 μin or more, for example 100 μin or more, for example 110 μin or more, for example 120 μin or more, for example 130 μin or more, for example 140 μin or more, for example 150 μin or more, for example 170 μin or more, for example 190 μin or more, for example 210 μin or more, for example 230 μin or more, and so on.

[0139] The properties referred to herein can be measured using the following test methods.

[0140] Test method Melting temperature, glass transition temperature, and heat of fusion: The melting temperature ("Tm"), glass transition temperature ("Tg"), and heat of fusion ("Hf") can be measured by differential scanning calorimetry ("DSC"), as is known in the art, using commercially available instruments such as the TA Instruments Model Q100. Typically, a 6-10 mg sample, stored at room temperature (approximately 23°C) for at least 48 hours, is sealed in an aluminum pan and loaded into the instrument at room temperature (approximately 23°C). The sample is equilibrated at 25°C, and then cooled to -80°C at a cooling rate of 10°C / min. The sample is held at -80°C for 5 minutes, and then heated to 25°C at a heating rate of 10°C / min. 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 largest endothermic calorific reaction within that temperature range, as determined from the DSC melting trace. g The temperature was measured by reheating the sample from -80°C to 80°C at a rate of 20°C / min ("second heating"). The reported glass transition temperature is the midpoint of the step change when heated during the second heating cycle. The area under the DSC curve is used to determine the transition heat (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 for the heat of crystallization, the value from melting (Tm) is used), and this can be used to calculate the degree of crystallinity (also called percentage crystallinity). Percentage crystallinity (X%) is calculated using the formula: [Area under the curve (in J / g units) / H° (in J / g units)] * 100 (where H° is the heat of fusion for the homopolymer of the major monomer components). These values ​​for H° should be obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, except that 290 J / g is used as the equilibrium heat of fusion (H°) for 100% crystalline polyethylene, 140 J / g is used as the equilibrium heat of fusion (H°) for 100% crystalline polybutene, and 207 J / g (H°) is used as the heat of fusion for 100% crystalline polypropylene.

[0141] Extrusion surface roughness: Approximately 1 kg (2 lbs) of the TPV under test was fed into a 1-inch or 1.5-inch diameter extruder equipped with a 24:1 L / D screw with a compression ratio of 3.0–3.5. A strip die measuring 25.4 mm (1 inch) wide × 0.5 mm (0.019 inches) thick × 7–10 mm (0.25–0.40 inches) land length was mounted on the extruder. A breaker plate was used with the die, but the screen pack was not placed in front of the breaker plate. The extruder temperature profile 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). The screw was started when the zone temperature was reached. The screw speed was set to maintain an extrusion rate of approximately 50 grams per minute. After flushing the extruder for 5 minutes, the extruded material was discarded, and a strip approximately 30.5 cm (12 inches) long was extruded onto a flat substrate placed directly beneath the die and in contact with the underside of the die. Three representative samples were collected using this method. ESR was measured for the samples using a Model EMD-4000-WS Surfanalyzer System 04000, which included a universal probe with a 200 mg stylus force and a Surfanalyzer probe tip type EPT-01049 (0.025 mm [0.0001 inch] stylus radius). [Examples]

[0142] Example 1 The components identified in the table provided below were melt-blended and dynamically cured to obtain thermoplastic vulcanized materials containing at least partially cured EPDM. Examples 1–5 included re-refined oil, as shown below. Melt blending and dynamic vulcanization were performed using a twin-screw extruder set to a temperature of 90°C–210°C. The speed was set to approximately 300 rpm. The samples were then injection-molded into plaques, and the samples were punched out from the plaques and tested.

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

[0144] [Table 1]

[0145] [Table 2]

[0146] [Table 3]

[0147] These and other modifications and variations of the Disclosure can be carried out by those skilled in the art without departing from the spirit and scope of the Disclosure. In addition, it should be understood that the various embodiments may be interchangeable, either in whole or in part. Furthermore, those skilled in the art will fully understand that the foregoing description is merely illustrative and is not intended to limit the invention as so further described in such appended claims.

Claims

1. A method for forming a thermoplastic vulcanized product, A method comprising dynamically vulcanizing a compound comprising a thermoplastic resin, an elastomer, an oil containing re-refined oil, and a curing agent to provide a thermoplastic vulcanized product comprising the thermoplastic resin and at least a partially cured elastomer.

2. The method according to claim 1, wherein the oil comprises a mixture of the re-refined oil and the unused oil.

3. The method according to any one of claims 1 to 2, wherein the thermoplastic resin comprises a polyolefin.

4. The method according to claim 3, wherein the polyolefin includes polypropylene.

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

6. The method according to claim 5, wherein the recycled thermoplastic resin includes recycled polypropylene, recycled polyethylene, or a mixture thereof.

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

8. The method according to any one of claims 1 to 7, wherein the elastomer comprises ethylene / propylene / non-conjugated diene copolymer rubber (EPDM).

9. The method according to any one of claims 1 to 8, wherein the re-refined oil is provided together with the elastomer as a re-refined oil spread elastomer.

10. The method according to any one of claims 1 to 9, wherein the thermoplastic vulcanized product comprises about 5% to about 90% by weight of the elastomer, about 5% to about 90% by weight of the thermoplastic resin, and about 10% or more to about 60% by weight of the re-refined oil, wherein the weight percentage is based on the weight of the thermoplastic vulcanized product, and the thermoplastic vulcanized product has a recycled content of 5% to 95% by weight based on the weight of the thermoplastic vulcanized product.

11. The method according to any one of claims 1 to 10, wherein the thermoplastic vulcanized product exhibits one or more of the following: a Shore A hardness of 25 to 100 (15 sec; unaged) according to ASTM 2240-15 (2021), a Shore D hardness of greater than 0 to 50 (15 sec; unaged) according to ASTM 2240-15 (2021), a 100% modulus of elasticity of 0.3 MPa to 50 MPa (unaged) as measured according to ASTM D412-16, a tensile stress at fracture of 0.5 MPa to 100 MPa (unaged) as measured according to ASTM D412-16, an elongation at fracture of 20% to 2000% (unaged) as measured according to ASTM D412-16, or a compression set of 70% or less as measured according to ASTM D395B-18 after 22 hours at room temperature.

12. A thermoplastic vulcanized product comprising a thermoplastic resin in an amount of 5% by weight or more based on the weight of the thermoplastic vulcanized product, at least a partially cured elastomer in an amount of 5% by weight or more based on the weight of the thermoplastic vulcanized product, and an oil containing re-refined oil.

13. The thermoplastic vulcanized product according to claim 12, wherein the oil comprises a mixture of the re-refined oil and the unused oil.

14. The thermoplastic vulcanized product according to any one of claims 12 to 13, wherein the thermoplastic resin comprises a polyolefin.

15. The thermoplastic resin is a thermoplastic vulcanized product according to any one of claims 12 to 13, wherein the thermoplastic resin includes recycled thermoplastic resin.

16. The thermoplastic vulcanized product according to claim 15, wherein the recycled thermoplastic resin comprises recycled polypropylene, recycled polyethylene, or a mixture thereof.

17. The thermoplastic vulcanized product according to any one of claims 12 to 13, wherein the thermoplastic resin comprises a mixture of unused thermoplastic resin and recycled thermoplastic resin.

18. The thermoplastic vulcanized product according to claim 12, wherein the elastomer comprises ethylene / propylene / non-conjugated diene copolymer rubber (EPDM).

19. The thermoplastic vulcanized product comprises about 5% by weight to about 90% by weight of the elastomer, about 5% by weight to about 90% by weight of the thermoplastic resin, and about 10% by weight or more to about 60% by weight of the re-refined oil, wherein the weight percentage is based on the weight of the thermoplastic vulcanized product, and the thermoplastic vulcanized product has a recycled content of 5% by weight to 95% by weight based on the weight of the thermoplastic vulcanized product, according to any one of claims 12 to 18.

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

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