Thermoplastic vulcanizate and method for producing the same

Abstract

The present invention provides a thermoplastic vulcanizate and a method for making the same. The thermoplastic vulcanizate includes a thermoplastic, crosslinked rubber particles, and a compatibilizing agent, wherein the crosslinked rubber particles are dispersed in the thermoplastic, wherein the crosslinked rubber particles are a crosslinked product of a composition including an ethylene copolymer and a crosslinking agent, and wherein the weight ratio of the thermoplastic to the ethylene copolymer is from 3:17 to 1:1.

Description

Technical Field

[0001] This invention relates to a thermoplastic vulcanized elastomer and its preparation method. Background Technology

[0002] Thermoplastic vulcanizates (TPVs) possess thermoplastic properties with thermosetting elastomers distributed throughout. Compared to traditional thermoplastic elastomers (TPEs), TPVs exhibit thermoplasticity at high temperatures and compressibility and resistance to permanent deformation at room temperatures, making them suitable for numerous applications such as the automotive industry, consumer electronics, packaging materials, and sealing.

[0003] Currently, commercially available thermoplastic vulcanized elastomers (TPVs) are mainly based on ethylene propylene diene monomer (EPDM) / polypropylene (PP) elastomers (EPDM / PP). However, EPDM / PP elastomers have relatively insufficient tensile strength and resilience, and their surface polarity differs significantly from other thermoplastic elastomers (such as thermoplastic polyester elastomers (TPEE), thermoplastic polyurethane elastomers (TPU), or thermoplastic polyamide elastomers (TPAE), resulting in insufficient bonding strength between them.

[0004] Although this field has seen a variety of research and products developed over a long period, there are still many problems in terms of technology and various properties, so there is still a need for improvement for the industry. Summary of the Invention

[0005] This invention provides a thermoplastic vulcanized elastomer. According to embodiments of the invention, the thermoplastic vulcanized elastomer may include a thermoplastic plastic, crosslinked rubber particles, and a compatibilizer. The crosslinked rubber particles are dispersed in the thermoplastic plastic. The crosslinked rubber particles may be a crosslinking product of a composition, which may include an ethylene copolymer and a crosslinking agent, wherein the weight ratio of the thermoplastic plastic to the ethylene copolymer may be from 3:17 to 1:1.

[0006] According to some embodiments of the present invention, the present invention provides a method for preparing a thermoplastic vulcanizate. The method includes: performing a melt-blending process on a composition to obtain a blend; and mixing a crosslinking agent with the blend to subject the ethylene copolymer in the blend to a dynamic crosslinking process, thereby obtaining the thermoplastic vulcanizate. The composition comprises 50-85 parts by weight of ethylene copolymer, 15-50 parts by weight of thermoplastic plastic, and 0.5-10 parts by weight of compatibilizer, wherein the total weight of the ethylene copolymer and the thermoplastic plastic is 100 parts by weight. Furthermore, the amount of crosslinking agent used is 0.2-2 parts by weight. Attached Figure Description

[0007] Figure 1 Scanning electron microscope image of the thermoplastic vulcanized elastomer (2) provided in Embodiment 2 of the present invention; and

[0008] Figure 2 Scanning electron microscope image of blend (6) provided for Comparative Example 6. Detailed Implementation

[0009] The following provides a detailed description of the thermoplastic vulcanized elastomer and its preparation method according to the present invention. It should be understood that the following description provides many different embodiments or examples for implementing different variations of the invention. The specific elements and arrangements described below are merely for illustrative purposes. Of course, these are only examples and not limitations of the invention. In this invention, the term "about" means an amount that can be increased or decreased to a size that is generally considered reasonable by those skilled in the art.

[0010] According to embodiments of the present invention, a thermoplastic vulcanizate is provided. This thermoplastic vulcanizate comprises a thermoplastic plastic as a continuous phase, cross-linked rubber particles as a dispersed phase, and utilizes a compatibilizer to increase the compatibility of the thermoplastic vulcanizate with an ethylene copolymer (which forms cross-linked rubber particles through a cross-linking reaction) in a melt-mixing process, thereby improving the mechanical strength of the resulting thermoplastic vulcanizate. The present invention, through a specific combination and ratio of thermoplastic plastic and ethylene copolymer, and through a melt-mixing process and a dynamic cross-linking process, enables the cross-linked rubber particles (obtained by reacting the ethylene copolymer with a cross-linking agent) to form micro-nano dispersed particles, which are uniformly dispersed within the thermoplastic vulcanizate. Therefore, compared with traditional rubber compounding processes (where plastic and rubber are mixed at low temperatures), the thermoplastic vulcanizate of the present invention exhibits superior tensile strength, resilience, processability, compressibility, resistance to permanent deformation, thermal stability, and foamability. Furthermore, products obtained from the thermoplastic vulcanizate of the present invention through injection molding, extrusion, and foaming can be further applied in fields such as sporting goods and footwear materials.

[0011] According to embodiments of the present invention, the Shore A hardness of the thermoplastic vulcanizate of the present invention can be from about 50A to 90A, for example, about 55A, 60A, 65A, 70A, 75A, 80A, or 85A. The Shore A hardness of the thermoplastic vulcanizate of the present invention is determined according to the method specified in ASTM D2240.

[0012] According to embodiments of the present invention, the thermoplastic vulcanized elastomer has a resilience of about 40% to 65%, for example, about 45%, 50%, 55%, or 60%. The resilience of the thermoplastic vulcanized elastomer of the present invention is determined according to the method specified in ASTM D 2632-92.

[0013] According to embodiments of the present invention, the thermoplastic vulcanized elastomer may include a thermoplastic plastic, crosslinked rubber particles, and a compatibilizer, wherein the compatibilizer improves the compatibility between the plastic phase (thermoplastic plastic) and the rubber phase (crosslinked rubber particles), allowing the crosslinked rubber particles to be uniformly dispersed in the thermoplastic plastic. According to embodiments of the present invention, the crosslinked rubber particles are a crosslinking product of a composition comprising an ethylene copolymer and a crosslinking agent. According to embodiments of the present invention, the weight ratio of the thermoplastic plastic to the ethylene copolymer may be from about 3:17 to 1:1, for example, about 4:16, 5:15, 6:14, 7:13, 8:12, or 9:11. If the content of the ethylene copolymer is too low, the content of the crosslinked rubber particles in the resulting thermoplastic vulcanized elastomer will also be too low, resulting in a decrease in the compression set of the resulting thermoplastic vulcanized elastomer. If the content of ethylene copolymer is too high, the resulting thermoplastic vulcanized elastomer will have reduced dispersibility of the crosslinked rubber particles due to the excessive content of crosslinked rubber particles (making them prone to agglomeration in thermoplastic plastics), and will also have reduced mechanical strength.

[0014] According to embodiments of the present invention, the thermoplastic vulcanized elastomer may include a continuous phase, a dispersed phase, and a compatibilizer, wherein the continuous phase includes a thermoplastic plastic, and the dispersed phase comprises a plurality of cross-linked rubber particles. The compatibilizer improves the compatibility between the continuous phase (thermoplastic plastic) and the dispersed phase (cross-linked rubber particles), allowing the cross-linked rubber particles to be uniformly dispersed in the thermoplastic plastic. According to some embodiments of the present invention, the continuous phase may be composed of the thermoplastic plastic, and the dispersed phase may be composed of the plurality of cross-linked rubber particles.

[0015] According to embodiments of the present invention, the particle size of the crosslinked rubber particles can be from 0.2 μm to 5 μm, for example, about 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 2 μm, 3 μm, or 4 μm. According to embodiments of the present invention, if the size of the crosslinked rubber particles in the thermoplastic plastic is not appropriately reduced to the range described herein, the tensile strength, resilience, compression set, and other properties of the resulting thermoplastic vulcanized elastomer will deteriorate.

[0016] According to embodiments of the present invention, the content of the compatibilizer can be from about 0.5 wt% to 10 wt% (e.g., about 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt%), based on the total weight of the thermoplastic plastic and the ethylene copolymer. If the content of the compatibilizer is too low or not added, the compatibility of the thermoplastic plastic and the ethylene copolymer (which forms cross-linked rubber particles through a cross-linking reaction) in the melt mixing process cannot be increased, resulting in the cross-linked rubber particles not being within the range of 0.2 μm to 5 μm, thus deteriorating the properties of the thermoplastic vulcanized elastomer. If the content of the compatibilizer is greater than 10 wt%, it will affect the microphase separation morphology of the thermoplastic plastic and the ethylene copolymer in the melt mixing process, making it impossible to obtain uniformly dispersed cross-linked rubber particles, leading to deterioration of the properties of the thermoplastic vulcanized elastomer.

[0017] According to embodiments of the present invention, the content of the crosslinking agent can be from about 0.2 wt% to 2 wt% (e.g., about 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, or 1.5 wt%), based on the total weight of the thermoplastic plastic and the ethylene copolymer. If the content of the crosslinking agent is too low, the degree of crosslinking of the ethylene copolymer is insufficient, and it is impossible to produce an inversion in the melt mixing process to form crosslinked rubber particles that are uniformly dispersed in the thermoplastic plastic, resulting in deterioration of the properties of the thermoplastic vulcanized elastomer. If the content of the crosslinking agent is too high, the crosslinking rate of the ethylene copolymer is too fast, causing the crosslinked rubber particles to agglomerate, resulting in deterioration of the properties of the thermoplastic vulcanized elastomer.

[0018] According to embodiments of the present invention, the ethylene copolymer may be one or more of the following: ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate rubber (EVM), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate copolymer (EBA). Here, the vinyl acetate content (i.e., the content of repeating units derived from vinyl acetate) of the ethylene-vinylacetate copolymer (EVA) may be less than 40 wt%, for example, about 15 wt% and less than 40 wt%. Furthermore, the vinyl acetate content (i.e., the content of repeating units derived from vinyl acetate) of the ethylene-vinyl acetate rubber (EVM) is also no more than 40 wt%, for example, about 15 wt% and less than 40 wt%. According to embodiments of the invention, the number-average molecular weight (Mn) of the ethylene copolymer can be from about 2000 g / mol to 500000 g / mol, for example 3000 g / mol, 4000 g / mol, 5000 g / mol, 8000 g / mol, 10000 g / mol, 20000 g / mol, 30000 g / mol, 50000 g / mol, 80000 g / mol, 100000 g / mol, 150000 g / mol, 200000 g / mol, or 300000 g / mol. The number-average molecular weight (Mn) of the ethylene copolymer described in this invention can be determined by gel permeation chromatography (GPC) (using polystyrene as a standard to prepare the calibration curve).

[0019] According to embodiments of the present invention, the thermoplastic plastic may be one or more of polypropylene, polyethylene, polyurethane, polyethylene terephthalate, and polyamide. According to embodiments of the present invention, the number-average molecular weight (Mn) of the thermoplastic plastic may be from about 10,000 g / mol to 5,000,000 g / mol, for example, 20,000 g / mol, 30,000 g / mol, 40,000 g / mol, 50,000 g / mol, 80,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, 500,000 g / mol, 800,000 g / mol, 1,000,000 g / mol, 1,500,000 g / mol, 2,000,000 g / mol, 3,000,000 g / mol, or 4,000,000 g / mol. The number-average molecular weight (Mn) of the thermoplastic plastic described in this invention can be determined by gel permeation chromatography (GPC) (using polystyrene as a standard to prepare the calibration curve).

[0020] According to embodiments of the present invention, the thermoplastic plastic used in the present invention is not further modified to make it reactive. In other words, the thermoplastic plastic does not have reactive functional groups to avoid the thermoplastic plastic reacting with the ethylene copolymer during melt mixing or dynamic crosslinking processes, thereby affecting the crosslinking density of the crosslinked rubber particles and the properties of the resulting thermoplastic vulcanized elastomer. According to embodiments of the present invention, the aforementioned reactive functional groups may be, for example, acrylate group, methacrylate group, glycidyl group, oxiranyl group, oxetanyl group, or (3,4-epoxycyclohexyl)methyl group. According to embodiments of the present invention, the thermoplastic plastic does not contain thermoplastic silane plastics or thermoplastic siloxane plastics. In other words, the thermoplastic plastic of the present invention is a polymer that does not contain silane moiety or siloxane moiety.

[0021] According to embodiments of the present invention, the compatibilizer may be a maleic anhydride-grafted polymer or a maleic anhydride-grafted copolymer, wherein the maleic anhydride grafting rate of the maleic anhydride-grafted polymer or the maleic anhydride-grafted copolymer may be from about 0.3% to 2.0% (e.g., about 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, or 1.8%). Here, the maleic anhydride grafting rate refers to the percentage of hydrogen atoms on all repeating units of the polymer or copolymer that are replaced by maleic anhydride groups. According to embodiments of the present invention, the compatibilizer may be one or more of the following: maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride grafted ethylene-vinyl acetate copolymer (EVA-g-MAH), maleic anhydride grafted polyethylene-octene copolymer (POE-g-MAH), maleic anhydride grafted ethylene-propylene-diene monomer (EPDM-g-MAH), and maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer (SEBS-g-MAH). According to embodiments of the present invention, the number-average molecular weight (Mn) of the maleic anhydride-grafted polymer or the maleic anhydride-grafted copolymer can be from about 2000 g / mol to 100000 g / mol, for example 3000 g / mol, 4000 g / mol, 5000 g / mol, 8000 g / mol, 10000 g / mol, 20000 g / mol, 30000 g / mol, 50000 g / mol, or 80000 g / mol. The number-average molecular weight (Mn) of the ethylene copolymer of the present invention can be determined by gel permeation chromatography (GPC) (using polystyrene as a standard to prepare a calibration curve).

[0022] According to an embodiment of the present invention, the compatibilizer may be manufactured by Dow Chemical Company and has the product number AMPLIFY. TM TY 1053H,AMPLIFY TM TY 1057H,AMPLIFY TMTY 1052H, and AMPLIFY TM The compatibilizer of TY 1151; the compatibilizer may be a compatibilizer manufactured by DuPont with product numbers BYNEL 41E710, BYNEL 4033, BYNEL4140, FUSABOND E series and M series; and the compatibilizer may be a compatibilizer manufactured by Arkema with product number OREVAC OE825.

[0023] According to an embodiment of the present invention, the crosslinking agent may be a peroxide. According to embodiments of the present invention, the crosslinking agent may be benzoyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylcyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-cyclohexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, tert-butyl hydroperoxide, tert-butyl peroxide, or tert-butylperoxybenzoic acid. One or more of the following: peroxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, and lauroyl peroxide.

[0024] According to embodiments of the invention, the composition used to carry out the crosslinking reaction to form the crosslinked rubber particles may further comprise a crosslinking aid, wherein the content of the crosslinking aid is from 0.1 wt% to 2 wt% (e.g., about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, or 1.8%), based on the total weight of the thermoplastic plastic and the ethylene copolymer. According to embodiments of the present invention, the crosslinking aid may be one or more of triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl phosphate (TAP), triallyl borate (TAB), trimethallyl isocyanurate (TMAIC), trimethylolpropane triacrylate (TMPTA), and trimethylolpropane trimethacrylate.

[0025] According to an embodiment of the present invention, the crosslinked rubber particles are crosslinked ethylene copolymers. According to an embodiment of the present invention, the composition used to form the crosslinked rubber particles is composed of an ethylene copolymer and a crosslinking agent. According to an embodiment of the present invention, the composition used to form the crosslinked rubber particles is composed of an ethylene copolymer, a crosslinking agent, and a crosslinking aid. According to an embodiment of the present invention, the composition used to form the crosslinked rubber particles does not contain any other polymers or copolymers participating in the crosslinking reaction besides the ethylene copolymer. According to an embodiment of the present invention, the thermoplastic vulcanized elastomer does not contain polyisobutylene (PIB), ethylene propylene rubber (EPR), or ethylene propylene diene monomer (EPDM).

[0026] According to embodiments of the present invention, the composition used to form crosslinked rubber particles can undergo a crosslinking reaction in the presence of an antioxidant, wherein the content of the antioxidant is from 0.1 wt% to 5 wt% (e.g., about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 2%, 3%, or 4%), based on the total weight of the thermoplastic plastic and the ethylene copolymer. According to embodiments of the present invention, the antioxidant may be a hindered phenolic oxidant, a thioester oxidant, or a phosphite oxidant.

[0027] According to embodiments of the present invention, the present invention also provides a method for preparing a thermoplastic vulcanized elastomer, for preparing the above-mentioned thermoplastic vulcanized elastomer. According to embodiments of the present invention, the method for preparing the thermoplastic vulcanized elastomer includes a melt-blending process of a composition to obtain a blend; and mixing 0.2-2 parts by weight of a crosslinking agent with the blend to subject the ethylene copolymer in the blend to a dynamic crosslinking process, thereby obtaining the thermoplastic vulcanized elastomer.

[0028] According to embodiments of the present invention, the composition may comprise 50-85 parts by weight (e.g., about 55, 60, 65, 70, 75, or 80 parts by weight) of an ethylene copolymer, 15-50 parts by weight (e.g., about 20, 25, 30, 35, 40, or 45 parts by weight) of a thermoplastic, and 0.5-10 parts by weight (e.g., about 1, 2, 3, 4, 5, 6, 7, 8, or 9 parts by weight) of a compatibilizer, wherein the total weight of the ethylene copolymer and the thermoplastic is 100 parts by weight.

[0029] In this invention, "mixing" refers to the process of uniformly mixing rubber or plastic with reagents (e.g., crosslinking agents, crosslinking aids, and antioxidants) through mechanical action (e.g., an extruder). The mixing step can be performed discontinuously or in batches. "Dynamic crosslinking" in this invention refers to the process of kneading the crosslinking agent (and crosslinking aids) and mixture during the melt mixing of the ethylene copolymer and thermoplastic plastic in the composition, thereby forming crosslinks between the ethylene copolymers. The term "dynamic" indicates that the mixture is subjected to shear force during the crosslinking step.

[0030] According to embodiments of the present invention, to better melt blend the ethylene copolymer and the thermoplastic, the temperature of the melt blending process can be adjusted to be between the melting point and decomposition temperature of the thermoplastic used. According to embodiments of the present invention, the temperature of this melt blending process can be approximately 170°C-200°C. According to embodiments of the present invention, the temperature of this dynamic crosslinking process can be approximately 170°C-200°C.

[0031] According to an embodiment of the present invention, in the preparation method of the thermoplastic vulcanized elastomer of the present invention, the composition can be subjected to a melt blending process by a Banbury mixer, a kneader, a single-screw extruder or a twin-screw extruder, and the ethylene copolymer in the blend can be subjected to a dynamic crosslinking process.

[0032] According to an embodiment of the present invention, when performing melt mixing and dynamic crosslinking processes using a twin-screw extruder, the screw speed of the twin-screw extruder can be approximately 150 rpm to 400 rpm. According to an embodiment of the present invention, after obtaining the thermoplastic vulcanized elastomer through the dynamic crosslinking process, the thermoplastic vulcanized elastomer can be further subjected to drying (drying at a temperature of 80°C to 100°C for 6 to 8 hours), granulation, or foaming processes.

[0033] According to embodiments of the present invention, the composition may further comprise 0.2-2 parts by weight of a crosslinking aid. According to embodiments of the present invention, the composition may further comprise 0.1-5 parts by weight of an antioxidant. According to embodiments of the present invention, the composition may consist of an ethylene copolymer, a thermoplastic plastic, and a compatibilizer. According to embodiments of the present invention, the composition may consist of an ethylene copolymer, a thermoplastic plastic, a compatibilizer, and a crosslinking aid. According to embodiments of the present invention, the composition may consist of an ethylene copolymer, a thermoplastic plastic, a compatibilizer, a crosslinking aid, and an antioxidant. According to embodiments of the present invention, the composition does not contain any other polymers or copolymers besides the ethylene copolymer and the thermoplastic plastic. According to embodiments of the present invention, the composition does not contain polyisobutylene (PIB), ethylene propylene rubber (EPR), or ethylene propylene diene monomer (EPDM).

[0034] To make the above-mentioned and other objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings.

[0035] Preparation of thermoplastic vulcanized elastomers

[0036] Example 1

[0037] 69.07 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K), 30.93 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), 1.03 parts by weight of compatibilizer (maleic anhydride grafted ethylene / vinyl acetate copolymer (EVA-g-MAH), manufactured and sold by Exxon, product number VA1801), and 1.55 parts by weight of crosslinking aid (triallyl cyanuric acid (TAC), manufactured and sold by Mitsubishi Chemical) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and melt-blended (temperature 200°C, screw speed 300 rpm). After mixing for 1 minute, add 0.52 parts by weight of the crosslinking agent (manufactured and sold by Arkema, product number: [product number missing]). 101) Add to the extruder for dynamic crosslinking (temperature 200℃, screw speed 300rpm). After 1 minute, granulate using a granulator (model GZML-110L-150) to obtain thermoplastic vulcanized elastomer (1). The composition and amount used to prepare thermoplastic vulcanized elastomer (1) are shown in Table 1.

[0038] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (1) were measured, and the results are shown in Table 2. Surface hardness was measured according to the method specified in ASTM D 2240; tensile strength was measured according to the method specified in ASTM D 412; and resilience was determined according to the method specified in ASTM D 2632-92.

[0039] Example 2

[0040] Example 2 was carried out in accordance with the method described in Example 1, except that the ethylene / vinyl acetate copolymer was reduced from 69.07 parts by weight to 67.74 parts by weight, the thermoplastic polyurethane was increased from 30.93 parts by weight to 32.26 parts by weight, the maleic anhydride-grafted ethylene / vinyl acetate copolymer was increased from 1.03 parts by weight to 5.38 parts by weight, the crosslinking agent was increased from 0.52 parts by weight to 0.54 parts by weight, and the crosslinking aid was increased from 1.55 parts by weight to 1.61 parts by weight, to obtain a thermoplastic vulcanized elastomer (2). The components and amounts used to prepare the thermoplastic vulcanized elastomer (2) are shown in Table 1.

[0041] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (2) were measured, and the results are shown in Table 2.

[0042] Example 3

[0043] Example 3 was carried out in accordance with the method described in Example 1, except that the ethylene / vinyl acetate copolymer was increased from 69.07 parts by weight to 78.49 parts by weight, the thermoplastic polyurethane was decreased from 30.93 parts by weight to 21.51 parts by weight, the maleic anhydride-grafted ethylene / vinyl acetate copolymer was increased from 1.03 parts by weight to 5.38 parts by weight, the crosslinking agent was increased from 0.52 parts by weight to 0.54 parts by weight, and the crosslinking aid was increased from 1.55 parts by weight to 1.61 parts by weight, to obtain a thermoplastic vulcanized elastomer (3). The components and amounts used to prepare the thermoplastic vulcanized elastomer (3) are shown in Table 1.

[0044] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (3) were measured, and the results are shown in Table 2.

[0045] Example 4

[0046] 67.74 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA7470K), 32.26 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S190A), 5.38 parts by weight of compatibilizer (maleic anhydride grafted polyethylene (PE-g-MAH), manufactured and sold by DuPont, product number fusabond E100), and 1.61 parts by weight of crosslinking aid (trimethylene cyanic acid (TAC), manufactured and sold by Mitsubishi Chemical) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and melt-blended (temperature 200°C, screw speed 300 rpm). After mixing for 1 minute, add 0.54 parts by weight of crosslinking agent (manufactured and sold by Arkema, product number: [product number missing]). 101) Add to the extruder and perform dynamic crosslinking (temperature 200℃, screw speed 300rpm). After 1 minute, granulate using a granulator (model GZML-110L-150) to obtain thermoplastic vulcanized elastomer (4). The composition and amount used to prepare thermoplastic vulcanized elastomer (4) are shown in Table 1.

[0047] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (4) were measured, and the results are shown in Table 2.

[0048] Example 5

[0049] Example 5 was carried out in accordance with the method described in Example 1, except that the ethylene / vinyl acetate copolymer was reduced from 69.07 parts by weight to 67.57 parts by weight, the thermoplastic polyurethane was increased from 30.93 parts by weight to 32.43 parts by weight, the maleic anhydride-grafted ethylene / vinyl acetate copolymer was increased from 1.03 parts by weight to 5.41 parts by weight, the crosslinking agent was increased from 0.52 parts by weight to 1.08 parts by weight, and the crosslinking aid was increased from 1.55 parts by weight to 1.62 parts by weight, to obtain a thermoplastic vulcanized elastomer (5). The components and amounts used to prepare the thermoplastic vulcanized elastomer (5) are shown in Table 1.

[0050] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (5) were measured, and the results are shown in Table 2.

[0051] Example 6

[0052] Example 6 was carried out in accordance with the method described in Example 1, except that the ethylene / vinyl acetate copolymer was reduced from 69.07 parts by weight to 67.57 parts by weight, the thermoplastic polyurethane was increased from 30.93 parts by weight to 32.43 parts by weight, the maleic anhydride-grafted ethylene / vinyl acetate copolymer was increased from 1.03 parts by weight to 5.41 parts by weight, the crosslinking agent was increased from 0.52 parts by weight to 0.54 parts by weight, and the crosslinking aid was increased from 1.55 parts by weight to 2.16 parts by weight, to obtain a thermoplastic vulcanized elastomer (6). The components and amounts used to prepare the thermoplastic vulcanized elastomer (6) are shown in Table 1.

[0053] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (6) were measured, and the results are shown in Table 2.

[0054] Example 7

[0055] Example 7 was carried out in accordance with the manner described in Example 1, except that the ethylene / vinyl acetate copolymer was reduced from 69.07 parts by weight to 67.74 parts by weight, the thermoplastic polyurethane was increased from 30.93 parts by weight to 32.26 parts by weight, the maleic anhydride-grafted ethylene / vinyl acetate copolymer was increased from 1.03 parts by weight to 5.38 parts by weight, and 0.52 parts by weight... 101 was replaced with 0.54 parts by weight of DCP (dicumyl peroxide, manufactured and sold by Chien Hsin Company), and the crosslinking aid was increased from 1.55 parts by weight to 1.61 parts by weight to obtain thermoplastic vulcanized elastomer (7). The components and amounts used to prepare thermoplastic vulcanized elastomer (7) are shown in Table 1.

[0056] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (7) were measured, and the results are shown in Table 2.

[0057] Example 8

[0058] Example 8 was carried out in accordance with the method described in Example 1, except that the ethylene / vinyl acetate copolymer was reduced from 69.07 parts by weight to 56.99 parts by weight, the thermoplastic polyurethane was increased from 30.93 parts by weight to 43.01 parts by weight, the maleic anhydride-grafted ethylene / vinyl acetate copolymer was increased from 1.03 parts by weight to 5.38 parts by weight, the crosslinking agent was increased from 0.52 parts by weight to 0.54 parts by weight, and the crosslinking aid was increased from 1.55 parts by weight to 1.61 parts by weight, to obtain a thermoplastic vulcanized elastomer (8). The components and amounts used to prepare the thermoplastic vulcanized elastomer (8) are shown in Table 1.

[0059] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (8) were measured, and the results are shown in Table 2.

[0060] Example 9

[0061] Example 9 was carried out in accordance with the method described in Example 1, except that the ethylene / vinyl acetate copolymer was reduced from 69.07 parts by weight to 67.57 parts by weight, the thermoplastic polyurethane was increased from 30.93 parts by weight to 32.43 parts by weight, the maleic anhydride-grafted ethylene / vinyl acetate copolymer was increased from 1.03 parts by weight to 5.41 parts by weight, the crosslinking agent was increased from 0.52 parts by weight to 1.62 parts by weight, and the crosslinking aid was reduced from 1.55 parts by weight to 0.54 parts by weight, to obtain a thermoplastic vulcanized elastomer (9). The components and amounts used to prepare the thermoplastic vulcanized elastomer (9) are shown in Table 1.

[0062] Next, the hardness, tensile strength, and resilience of the thermoplastic vulcanized elastomer (9) were measured, and the results are shown in Table 2.

[0063] Comparative Example 1

[0064] 68.42 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K), 31.58 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), and 5.26 parts by weight of compatibilizer (maleic anhydride-grafted ethylene / vinyl acetate copolymer (EVA-g-MAH), manufactured and sold by Exxon, product number VA1801) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and mixed (temperature 190°C, screw speed 300 rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain blend (1). The components and amounts used to prepare blend (1) are shown in Table 1.

[0065] Next, the hardness, tensile strength, and resilience of the blend (1) were measured, and the results are shown in Table 2.

[0066] Comparative Example 2

[0067] 70 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K) and 30 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and mixed (temperature 190°C, screw speed 300 rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain blend (2). The composition and amount used to prepare blend (2) are shown in Table 1.

[0068] Next, the hardness, tensile strength, and resilience of the blend (2) were measured, and the results are shown in Table 2.

[0069] Comparative Example 3

[0070] 78.95 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K), 21.05 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), and 5.26 parts by weight of compatibilizer (maleic anhydride-grafted ethylene / vinyl acetate copolymer (EVA-g-MAH), manufactured and sold by Exxon, product number VA1801) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and mixed (temperature 190°C, screw speed 300 rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain the blend (3). The components and amounts used to prepare blend (3) are shown in Table 1.

[0071] Next, the hardness, tensile strength, and resilience of the blend (3) were measured, and the results are shown in Table 2.

[0072] Comparative Example 4

[0073] 68.42 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K), 31.58 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), and 5.26 parts by weight of compatibilizer (maleic anhydride grafted polyethylene (PE-g-MAH), manufactured and sold by DuPont, product number fusabond E100) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and mixed (temperature 190°C, screw speed 300 rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain the blend (4). The components and amounts used to prepare blend (4) are shown in Table 1.

[0074] Next, the hardness, tensile strength, and resilience of the blend (4) were measured, and the results are shown in Table 2.

[0075] Comparative Example 5

[0076] 67.91 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K), 32.09 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), 5.35 parts by weight of compatibilizer (maleic anhydride grafted ethylene / vinyl acetate copolymer (EVA-g-MAH), manufactured and sold by Exxon, product number VA1801), and 1.60 parts by weight of crosslinking aid (triallyl cyanuric acid (TAC), manufactured and sold by Mitsubishi Chemical) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and mixed (temperature 190°C, screw speed 300 rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain blend (5). The components and amounts used to prepare blend (5) are shown in Table 1.

[0077] Next, the hardness, tensile strength, and resilience of the blend (5) were measured, and the results are shown in Table 2.

[0078] Comparative Example 6

[0079] The mixture comprises 68.25 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K), 31.75 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), 5.29 parts by weight of compatibilizer (maleic anhydride-grafted ethylene / vinyl acetate copolymer (EVA-g-MAH), manufactured and sold by Exxon, product number VA1801), and 0.53 parts by weight of crosslinking agent (manufactured and sold by Arkema, product number...). 101) The mixture was added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26mm, L / D=60) and mixed (temperature 190℃, screw speed 300rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain blend (6). The composition and amount used to prepare blend (6) are shown in Table 1.

[0080] Next, the hardness, tensile strength, and resilience of the blend (6) were measured, and the results are shown in Table 2.

[0081] Comparative Example 7

[0082] 43.01 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA 7470K), 56.99 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), and 5.38 parts by weight of compatibilizer (maleic anhydride-grafted ethylene / vinyl acetate copolymer (EVA-g-MAH), manufactured and sold by Exxon, product number VA1801) were added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26 mm, L / D = 60) and mixed (temperature 190°C, screw speed 300 rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain the blend (7). The components and amounts used to prepare blend (7) are shown in Table 1.

[0083] Next, the hardness, tensile strength, and resilience of the blend (7) were measured, and the results are shown in Table 2.

[0084] Comparative Example 8

[0085] The mixture comprises 43.01 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured and sold by Taisox, product number EVA7470K), 56.99 parts by weight of thermoplastic polyurethane (TPU) (manufactured and sold by Lubrizol, product number S385A), 5.38 parts by weight of compatibilizer (maleic anhydride grafted ethylene / vinyl acetate copolymer (EVA-g-MAH), manufactured and sold by Exxon, product number VA1801), 1.61 parts by weight of crosslinking aid (triallyl cyanuric acid (TAC), manufactured and sold by Mitsubishi Chemical), and 0.54 parts by weight of crosslinking agent (manufactured and sold by Arkema, product number...). 101) The mixture was added to a twin-screw extruder (model Coperion ZSK26) (screw diameter 26mm, L / D=60) and mixed (temperature 190℃, screw speed 300rpm). After 1 minute, the mixture was granulated using a granulator (model GZML-110L-150) to obtain blend (8). The composition and amount used to prepare blend (8) are shown in Table 1.

[0086] Next, the hardness, tensile strength, and resilience of the blend (8) were measured, and the results are shown in Table 2.

[0087] Table 1

[0088]

[0089] Table 2

[0090]

[0091]

[0092] As shown in Table 2, the thermoplastic vulcanizing elastomers (the thermoplastic vulcanizing elastomers (1)-(9)) obtained by the present invention through the specific combination and ratio of thermoplastic vulcanizing elastomers and ethylene copolymers, and through melt mixing and dynamic crosslinking processes, have high hardness (between 81 and 89) and tensile strength (between 150 kg / cm²). 2 -184kg / cm 2 The elasticity is between 52% and 57%. In addition, the materials obtained by the compounding process (mixing plastics and rubber at low temperature) (the blends (1)-(4) of Comparative Examples 1-4) or the blends obtained by adding crosslinking agents or crosslinking aids in the compounding process (the blends (5) and (6) of Comparative Examples 5 and 6) have significantly insufficient elasticity (less than 50%).

[0093] Next, the cross-section of the thermoplastic vulcanized elastomer (1) described in Example 2 was observed using a scanning electron microscope (SEM), and the results are as follows: Figure 1 As shown. Furthermore, the cross-section of the blend (6) described in Comparative Example 6 was observed using a scanning electron microscope (SEM), and the results are as follows. Figure 2 As shown. By Figure 1 It can be seen that, through melt mixing and dynamic crosslinking processes, the crosslinked rubber particles of the thermoplastic vulcanized elastomer (1) of the present invention are dispersed as a dispersed phase in the thermoplastic plastic as a continuous phase, and the particle size of the crosslinked rubber particles can be reduced to 5 μm or less. Conversely... Figure 2 Since EVA and PU are mixed at low temperatures, even in the presence of a crosslinking agent, the crosslinked EVA is simply mixed with PU and cannot be uniformly dispersed in the resulting polyester material in a particulate manner (it cannot form particles with a particle size of less than or equal to 5μm).

[0094] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A thermoplastic vulcanized elastomer, characterized in that, The product comprises a thermoplastic elastomer, crosslinked rubber particles, and a compatibilizer, wherein the thermoplastic elastomer is polyurethane, and the crosslinked rubber particles are dispersed in the thermoplastic elastomer, wherein the crosslinked rubber particles have a particle size of 0.2 μm to 5 μm, wherein the crosslinked rubber particles are a crosslinking product of a composition comprising an ethylene copolymer, a crosslinking aid, and a crosslinking agent, wherein the weight ratio of the thermoplastic elastomer to the ethylene copolymer is 3:17 to 1:1, wherein the content of the crosslinking aid is 0.1 wt% to 2 wt% based on the total weight of the thermoplastic elastomer and the ethylene copolymer, wherein the resilience of the thermoplastic vulcanized elastomer is 52% to 57%, and the resilience is determined according to the method specified in ASTM D 2632-92.

2. The thermoplastic vulcanized elastomer according to claim 1, characterized in that, The compatibilizer has a content of 0.5 wt% to 10 wt%, and the crosslinking agent has a content of 0.2 wt% to 2 wt%, based on the total weight of the thermoplastic plastic and the ethylene copolymer.

3. The thermoplastic vulcanized elastomer according to claim 1, characterized in that, The ethylene copolymer is one or more of the following: ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, and ethylene / acrylate copolymer.

4. The thermoplastic vulcanized elastomer according to claim 1, characterized in that, The compatibilizer is one or more of the following: maleic anhydride-grafted polyethylene, maleic anhydride-grafted ethylene / vinyl acetate copolymer, maleic anhydride-grafted ethylene octene copolymer, maleic anhydride-grafted ethylene propylene diene monomer (EPDM) rubber, and maleic anhydride-grafted styrene-(ethylene-butene)-styrene block copolymer.

5. The thermoplastic vulcanized elastomer according to claim 1, characterized in that, The crosslinking agent is a peroxide.

6. The thermoplastic vulcanized elastomer according to claim 1, characterized in that, The crosslinking aid is one or more of triallyl cyanate, triallyl isocyanate, triallyl phosphate, triallyl borate, trimethylallyl isocyanurate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.

7. A method for preparing a thermoplastic vulcanizate as described in any one of claims 1 to 6, characterized in that, include: A composition is subjected to a melt-blending process to obtain a blend, wherein the composition comprises 50-85 parts by weight of an ethylene copolymer, 15-50 parts by weight of a thermoplastic plastic, 0.5-10 parts by weight of a compatibilizer, and 0.1-2 parts by weight of a crosslinking aid, wherein the total weight of the ethylene copolymer and the thermoplastic plastic is 100 parts by weight, and wherein the thermoplastic plastic is polyurethane. as well as Mix 0.2-2 parts by weight of crosslinking agent with the blend to subject the ethylene copolymer in the blend to a dynamic crosslinking process, thereby obtaining a thermoplastic vulcanized elastomer.

8. The method for preparing the thermoplastic vulcanized elastomer according to claim 7, wherein the temperature of the melt mixing process is 170℃-200℃, and the temperature of the dynamic crosslinking process is 170℃-200℃.

9. The method for preparing the thermoplastic vulcanizate according to claim 7, characterized in that, The ethylene copolymer is one or more of the following: ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, and ethylene / acrylate copolymer.

10. The method for preparing the thermoplastic vulcanizate according to claim 7, characterized in that, The compatibilizer is one or more of the following: maleic anhydride-grafted polyethylene, maleic anhydride-grafted ethylene / vinyl acetate copolymer, maleic anhydride-grafted ethylene octene copolymer, maleic anhydride-grafted ethylene propylene diene monomer (EPDM) rubber, and maleic anhydride-grafted styrene-(ethylene-butene)-styrene block copolymer.

11. The method for preparing the thermoplastic vulcanizate according to claim 7, characterized in that, The crosslinking agent is a peroxide.

12. The method for preparing the thermoplastic vulcanizate according to claim 7, characterized in that, The crosslinking aid is one or more of triallyl cyanate, triallyl isocyanate, triallyl phosphate, triallyl borate, trimethylallyl isocyanurate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.

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