Thermoplastic vulcanizate composition comprising a cyclic olefin copolymer

Abstract

Described herein are thermoplastic vulcanizate compositions including a thermoplastic matrix including a cyclic olefin copolymer and an oil and particles dispersed in the thermoplastic matrix and including at least partially crosslinked rubber. The thermoplastic vulcanizate compositions have a tan delta curve including a peak occurring between about -20 °C to about 90 °C and having a peak value of about 0.1 to about 2.0.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to USSN 63 / 147,390, filed February 9, 2021, which is incorporated herein by reference. Technical Field

[0003] Embodiments of the present invention generally relate to thermoplastic vulcanized rubber compositions comprising cyclic olefin copolymers for improving vibration damping performance. Background Technology

[0004] This section is intended to provide relevant background information to better understand the various aspects of the described embodiments. Therefore, it should be understood that these statements should be interpreted accordingly, rather than as an admission of prior art.

[0005] Thermoplastic vulcanizates (TPVs) comprise finely dispersed rubber particles in a thermoplastic matrix. These rubber particles are advantageously cross-linked to enhance elasticity. Generally, the dispersed rubber phase is referred to as the discontinuous phase or rubber phase, and the thermoplastic phase as the continuous phase or plastic phase. These TPVs can be prepared by dynamic vulcanization, a process in which the rubber is cured or vulcanized using a curing agent while the polymers are mixed or pulverized in a blend containing at least one thermoplastic polymer at an elevated temperature, preferably above the melting temperature of the thermoplastic polymer. Therefore, TPVs possess the advantages of elastomeric properties provided by the elastic phase and the processability of thermoplastics provided by the thermoplastic phase.

[0006] Due to their elastomeric properties, TPVs show potential for vibration damping applications. Materials with vibration damping properties are used in a variety of applications, such as building materials, electrical and electronic equipment, optical instruments, audiovisual equipment, railways, and motor vehicles. Typical vibration damping materials include low-hardness products with gel-like properties. In recent years, there has been increasing focus on developing new materials with improved vibration damping properties for electric motors used in hybrid electric vehicles (HVs), plug-in hybrid electric vehicles (PHVs), fuel cell vehicles (FCVs), and electric vehicles (EVs). These vehicles generate very little engine noise during operation. Therefore, noise entering from outside the vehicle can be more noticeable and amplified. Consequently, the need to reduce external environmental noise is increased compared to conventional vehicles. Furthermore, electric vehicles typically operate within a temperature range of 0°C to 90°C. Therefore, TPVs useful for these applications require vibration damping properties within this 0°C to 90°C range.

[0007] TPV has successfully replaced rubber in some areas, but thermosetting rubber still outperforms TPV in terms of compression set. Compression set testing measures the ability of an elastic material to recover its original thickness after prolonged compressive stress at a given temperature and deflection. When an elastic material is compressed for a period of time, it loses its ability to recover its original thickness. Therefore, it is preferable that the elastomer compositions described herein exhibit a relatively low percentage of compression set, as the percentage measurement is a measure of the composition's ability to recover its original thickness. That is, if the composition is compressed and does not recover at all, it has 100% compression set; if it fully recovers to its original thickness, it has 0% compression set. In other words, the lower the compression set value, the longer the lifespan of the composition and its effective use. For TPVs with less than about 90% cured ethylene-propylene-diene (EPDM) rubber polymer, the compression set is often unacceptably high for many applications, especially at high temperatures. Furthermore, the thermoplastic matrix tends to reduce compression set resistance at lower temperatures. The difference between polypropylene (PP) / EPDM TPV and EPDM rubber lies in the semi-crystalline PP matrix. While the PP matrix provides TPV with melt processability and heat resistance, its crystallinity also limits its elastic behavior. Dynamic transitions in the crystalline microstructure of the PP matrix under heating and stress result in TPV exhibiting higher compressive deformation than EPDM rubber. The deformation mechanism of TPV is limited by the yielding of the semi-crystalline PP matrix, thus preventing TPV from fully utilizing the elastic limit of the EPDM phase. In addition to elastic properties (low compressive deformation, tensile deformation, and high elasticity), TPV should also maintain a balance between other mechanical properties, including hardness and tensile properties (e.g., tensile strength, modulus, elongation at break), and extrusion properties, including processability and part surface appearance (e.g., smoothness, no edge tearing, no surface spots, no die-cut lines, no Rococo). The currently used combination of EPDM and thermoplastic polyolefins has proven insufficient to achieve these objectives.

[0008] Therefore, there is a need to develop TPV compositions that have excellent vibration damping performance and excellent elastic properties in the temperature range of 0°C to 90°C. Summary of the Invention

[0009] A thermoplastic vulcanizate composition is disclosed, comprising a thermoplastic matrix and an oil, the thermoplastic matrix including a cyclic olefin copolymer. Crosslinked rubber particles are dispersed in the thermoplastic matrix. This TPV composition has a vibration damping peak appearing between about -20°C and about 90°C.

[0010] A thermoplastic vulcanized rubber composition is also disclosed, comprising a reaction product of a composition comprising rubber, a crosslinking agent, a thermoplastic resin containing a cyclic olefin copolymer, and an oil, which is dynamically cured. The thermoplastic vulcanized rubber composition has a vibration damping peak appearing between about -20°C and about 90°C.

[0011] A thermoplastic vulcanizate composition is also disclosed, comprising: (1) a dynamically cured rubber comprising an ethylene propylene diene (EPDM) polymer or a brominated isobutyl-p-methylstyrene (BIMSM) polymer; (2) a thermoplastic resin comprising about 20 to about 500 parts (about 20 phr to about 500 phr) per 100 parts of rubber, said thermoplastic resin comprising about 1 wt% to about 100 wt% of a cyclic olefin copolymer and up to 99 wt% of a semi-crystalline acyclic polyolefin, said cyclic olefin copolymer having a glass transition temperature (Tg) of at least about 30 °C; and an oil comprising about 50 to about 250 parts (about 50 phr to about 250 phr) per 100 parts of rubber. The tanδ curve of said thermoplastic vulcanizate composition includes a peak of about 0.1 to about 2.0 appearing between about -20 °C and about 90 °C. The thermoplastic vulcanized rubber composition has a compression set of about 15% to about 50% after compression at 70°C for 22 hours, and a hardness of about 15 to about 95 measured on a Shore A hardness tester scale 15 seconds after indentation, and a hardness of about 15 to about 50 measured on a Shore D hardness tester scale 15 seconds after indentation. Attached Figure Description

[0012] Embodiments of thermoplastic vulcanizate compositions comprising cyclic olefin copolymers are described below with reference to the accompanying drawings. The same numerals are used in the drawings to denote similar features and components. Features depicted in the drawings are not necessarily shown to scale. Certain features of the embodiments may be shown to scale or in some graphical form, and for clarity and brevity, certain details of elements may be omitted.

[0013] Figure 1 This is a graph showing the loss tangent (tanδ) of the TPV composition of Example 1 according to one or more embodiments as a function of temperature.

[0014] Figure 2 This is a graph showing the loss tangent as a function of temperature for the TPV composition of Example 2 according to one or more embodiments.

[0015] Figure 3A This is a graph showing the hardness of a TPV composition according to one or more embodiments as a function of the cyclic olefin copolymer content.

[0016] Figure 3B This is a graph showing the glass transition temperature (Tg) of a pure cyclic olefin copolymer and TPV composition according to one or more embodiments as a function of norbornene content.

[0017] Figure 4 This is a photomicrograph of Comparative Example 1.

[0018] Figure 5A , Figure 5B and Figure 5C These are photomicrographs of TPV compositions according to one or more embodiments. Detailed Implementation

[0019] Various specific embodiments and versions of the invention, including the definitions used herein, will now be described. While the following detailed description provides specific embodiments, those skilled in the art will understand that these embodiments are merely exemplary, and portions of the embodiments may be interchanged where appropriate, and the invention may be implemented in other ways. Any reference to "invention" may refer to one or more, but not necessarily all, of the inventions of this application as defined in the claims. The headings are used for convenience only and do not limit the scope of the invention.

[0020] definition

[0021] The term "phr" means "parts per 100 parts rubber" and refers to the amount of a component contained in a thermoplastic vulcanized rubber composition, expressed as parts per 100 parts of rubber, where parts are determined by weight. phr generally indicates the amount of a component prior to any curing process. However, for the purposes of this disclosure, the effect of the curing process on the weight and amount of all components is negligible, such that the phr specified before any curing process is substantially the same as the phr specified during or after any curing process. Therefore, phr in this disclosure can equivalently refer to the phr before, during, or after any curing process.

[0022] "Amorphous cyclic olefin polymers" and similar terms refer to COPs or COCs that exhibit a glass transition temperature but not a crystallization melting temperature, nor do they exhibit a clear X-ray diffraction pattern.

[0023] "COC" and similar terms refer to cyclic olefin copolymers (also referred to herein as cyclic olefin copolymers) prepared by addition copolymerization of acyclic olefin monomers and cyclic olefin monomers.

[0024] "COP" and similar terms refer to cyclic olefin polymers (also referred to herein as cyclic olefin polymers) that are typically prepared solely from cyclic olefin monomers via ring-opening polymerization.

[0025] This article defines cyclic alkenes (also known as cyclic olefins) as alkenes in which at least one double bond is contained in one or more alicyclic rings. Cyclic alkenes may also have acyclic double bonds in their side chains.

[0026] This article defines dienes broadly as any alkene containing at least two acyclic double bonds. They may also contain aromatic substituents. If one or more double bonds of a diene are contained in an alicyclic ring, this article classifies the monomer as a cyclic alkene.

[0027] Δhardness is defined as the difference between the Shore A hardness measured 1 second and 15 seconds after imprinting.

[0028] TPV composition properties

[0029] The inventors have discovered that TPV compositions comprising cyclic olefin copolymers (COCs) prepared from acyclic olefin monomers and cyclic olefin monomers exhibit superior vibration damping and elastic properties compared to COC-free TPVs and conventional EPDM rubbers. These TPV compositions comprise a continuous phase of COC or a PP / COC blend, along with dynamically cured, dispersed, and crosslinked EPDM rubber particles. The TPV compositions also include blends of COCs with different glass transition temperatures. The crosslinked EPDM rubber particles provide elasticity, the semi-crystalline PP provides processability and strength, and the amorphous COC alters the thermal and mechanical behavior of the thermoplastic matrix.

[0030] The TPV composition of the present invention exhibits a loss tangent (tanδ) peak in a temperature window of about -20 to about 90°C, indicating peak vibration damping performance within this temperature window. The TPV composition of the present invention also exhibits about 15% to about 50% compression deformation, or about 15% to about 45% compression deformation, or about 20% to about 45% compression deformation after compression for 22 hours at 70°C, which is up to 40% higher than conventional PP / EPDM TPV without COC.

[0031] The TPV compositions described herein have potential applications as novel vibration damping materials. Vibration damping can be characterized by the loss tangent (tanδ). A larger tanδ value indicates greater vibration damping, i.e., enhanced energy absorption and dispersion within the material. The loss tangent of a material is highly dependent on temperature and vibration frequency, and the loss tangent of the TPV composition exhibits at least one peak within a certain temperature window. TPV compositions for alternative vehicle applications require vibration damping in the range of approximately -20°C to approximately 90°C, or more specifically, in the range of approximately 0°C to approximately 60°C.

[0032] Compared to conventional TPV compositions without COC, this TPV composition exhibits improved vibration damping. Figure 1 and Figure 2 The vibration damping of the COC-containing TPV compositions of the present invention compared to conventional COC-free TPVs is shown, wherein IEx1, IEx2, and IEx13 are COC-containing TPV compositions of the present invention, while Comparative Examples 1 and 3 are conventional COC-free TPVs, the composition and preparation of which are described in Examples 1 and 2 below. Figure 1 and Figure 2As shown, the TPV composition exhibits a loss tangent peak in a temperature window of about -20°C to about 60°C. In contrast, Comparative Examples 1 and 3 (without COC) exhibit peaks far below 0°C. The TPV composition described herein also has vibration damping peaks appearing at about -20°C to about 90°C, about -10°C to about 55°C, or about 0°C to about 50°C.

[0033] Similarly, Figure 1 and Figure 2 As shown, the TPV composition of the present invention exhibits a higher loss tangent peak value than Comparative Examples 1 and 3. The TPV composition of this disclosure exhibits a vibration damping peak with a peak value of about 0.1 to about 2.0 in a temperature window of -20°C to 90°C, while Comparative Examples 1 and 3 exhibit peak values ​​below 0.1 in the same temperature window. The TPV composition described herein may have a vibration damping peak value of about 0.1 to about 2.5, about 0.1 to about 2.0, about 0.1 to about 1.5, about 0.2 to about 1.0, or about 0.4 to about 0.9.

[0034] Compared to conventional PP / EPDM TPV without COC, the TPV compositions disclosed herein exhibit up to 40% improvement in compression set.

[0035] Compression deformation is influenced by the interactions of the phases in the TPV composition. The rubber phase is a cross-linked, separated, or dispersed phase, while the plastic phase is a continuous phase. Therefore, the thermal and elastic behavior of the TPV composition mainly depends on the thermal behavior of the continuous plastic phase. For TPV compositions containing rigid glassy COC in the continuous phase, the rubber particles are constrained by the glassy COC matrix at operating temperature, making it difficult to recover after deformation, resulting in high compression deformation. In contrast, COC with moderate Tg can be plasticized with processing oil to obtain a wide loss tangent, and the COC can be softened to its elastic state at operating temperature, thus giving the corresponding TPV composition low compression deformation.

[0036] After compression at 70°C for 22 hours, the TPV composition described herein has a compression set of about 15% to 50%, or about 15% to about 45%, or about 20% to about 45%. After compression at 70°C for 22 hours, the thermoplastic vulcanizate composition may have a compression set of about 15% to about 50%, or about 17% to about 49%, or about 25% to about 35%, or less than about 42%.

[0037] The TPV composition described herein has a hardness of about 15 to about 95 as measured on a Shore A hardness scale 15 seconds after imprinting. The thermoplastic sulfur compound may have a hardness of about 30 to about 87, about 40 to about 87, or about 50 to about 72.

[0038] The following discusses a thermoplastic vulcanizate composition comprising a thermoplastic matrix containing a cyclic olefin copolymer and an oil. Particles containing at least partially crosslinked rubber are dispersed in the thermoplastic matrix. Using this composition, the thermoplastic vulcanizate composition exhibits a vibration damping peak appearing from about -20°C to about 90°C.

[0039] thermoplastic matrix

[0040] The TPV compositions described herein include a thermoplastic matrix. This thermoplastic matrix may comprise a polymer that is flowable above its melt temperature. Optionally, the primary component of the thermoplastic matrix may comprise polypropylene (e.g., homopolymer, random copolymer, or impact copolymer, or combinations thereof) or polyethylene. The thermoplastic phase may also comprise an ethylene-based polymer (e.g., polyethylene) or a propylene-based polymer (e.g., polypropylene). The thermoplastic phase may also comprise a 1-butene-based polymer.

[0041] The TPV compositions described herein comprise a thermoplastic matrix in amounts of about 20 parts to about 500 parts by weight (about 20 phr to about 500 phr) per 100 parts of rubber. The thermoplastic vulcanized rubber compositions may comprise a thermoplastic matrix in amounts of about 50 phr to about 450 phr, about 100 phr to about 250 phr, or about 150 phr to about 200 phr.

[0042] Suitable propylene-based polymers for this matrix include solid, typically high-molecular-weight plastic resins that primarily consist of units derived from the polymerization of propylene. At least 75%, at least 90%, at least 95%, or at least 97% of the units of the propylene-based polymer are derived from the polymerization of propylene. These polymers may include homopolymers of propylene. Homopolymer polypropylene may include linear chains and / or chains with long-chain branching.

[0043] Propylene-based polymers may also include units derived from the polymerization of ethylene and / or α-olefins (e.g., 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). Specifically, they include impact-resistant random copolymers of reactants of propylene with ethylene or the aforementioned higher α-olefins or with C10-C20 olefins.

[0044] Propylene-based polymers may include one or more of the following characteristics:

[0045] 1) Propylene-based polymers may include semi-crystalline polymers. These polymers can be characterized by a crystallinity of at least 25 wt% or greater (e.g., about 55 wt% or greater, about 65 wt% or greater, about 70 wt% or greater). Crystallinity can be determined by dividing the heat of fusion (Hf) of the sample by the heat of fusion of 100% crystalline polymer, which is considered to be 209 joules / gram for 100% crystalline polypropylene.

[0046] 2) Hf is about 52.3 J / g or greater (e.g., about 100 J / g or greater, about 125 J / g or greater, about 140 J / g or greater).

[0047] 3) The weight-average molecular weight (Mw) of polystyrene standards determined by GPC is about 50,000 g / mol to about 2,000,000 g / mol (e.g., about 100,000 g / mol to about 1,000,000 g / mol, or about 100,000 g / mol to about 600,000 g / mol, or about 400,000 g / mol to about 800,000 g / mol).

[0048] 4) The number-average molecular weight (Mn) determined by GPC using polystyrene standards is approximately 25,000 g / mol to approximately 1,000,000 g / mol (e.g., approximately 50,000 g / mol to approximately 300,000 g / mol).

[0049] 5)g' vis 1 or less (e.g., 0.9 or less, 0.8 or less, 0.6 or less, 0.5 or less)

[0050] 6) The melt mass flow rate (MFR) (ASTM D 1238, 2.16 kg weight @ 230 °C) is about 0.1 g / 10 min or greater (e.g., about 0.2 g / 10 min or greater). Alternatively, the MFR is about 0.1 g / 10 min to about 50 g / 10 min, such as about 0.5 g / 10 min to about 5 g / 10 min, or about 0.5 g / 10 min to about 3 g / 10 min.

[0051] 7) The melting temperature (Tm) is from about 110°C to about 170°C (e.g., from about 140°C to 168°C, or from about 160°C to about 165°C).

[0052] 8) The glass transition temperature (Tg) is about -50°C to about 10°C (e.g., about -30°C to about 5°C, or about -20°C to about 2°C).

[0053] 9) The crystallization temperature (Tc) is about 75°C or higher (e.g., about 95°C or higher, about 100°C or higher, about 105°C or higher (e.g., about 105°C to about 130°C).

[0054] Propylene-based polymers may include homopolymers of highly crystalline isotactic or syndiotactic polypropylene. This polypropylene may have a density of about 0.89 g / ml to about 0.91 g / ml, with the majority of the isotactic polypropylene having a density of about 0.90 g / ml to about 0.91 g / ml. Furthermore, high molecular weight and ultra-high molecular weight polypropylenes with partial melt flow rates may be used. Polypropylene resins can be characterized by an MFR (ASTM D-1238; 2.16 kg @ 230 °C) of about 10 dg / min or less (e.g., about 1.0 dg / min or less, such as about 0.5 dg / min or less).

[0055] Polypropylene may include homopolymers, random copolymers, or impact copolymers of polypropylene or combinations thereof. Polypropylene may be a high melt strength (HMS) long-chain branched (LCB) homopolymer polypropylene.

[0056] Propylene-based polymers can be synthesized using suitable polymerization techniques known in the art, such as conventional Ziegler-Natta polymerization and catalysis using single-point organometallic catalysts, including metallocene catalysts.

[0057] Examples of polypropylene used as the thermoplastic matrix for the TPV compositions described herein include ExxonMobil. TM PP5341 (purchased from ExxonMobil) TM Achieve TM PP6282NE1 (purchased from ExxonMobil) TM Achieve TM PP6302E1; Waymax TM MFX6 (purchased from Japan Polypropylene Corp.) TM ); Borealis Daploy TM WB140 (purchased from Borealis) TM AG); and Braskem Ampleo TM 1025MA and Braskem Ampleo TM 1020GA (purchased from BraskemAmpleo) TM ).

[0058] The thermoplastic matrix of the TPV composition may also include ethylene-based polymers. Ethylene-based polymers include those solid, typically high-molecular-weight plastic resins that primarily consist of units derived from the polymerization of ethylene. At least 90%, at least 95%, or at least 99% of the units of the ethylene-based polymer are derived from the polymerization of ethylene. These polymers may include homopolymers of ethylene.

[0059] Ethylene-based polymers may also include units derived from the polymerization of α-olefins (e.g., 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).

[0060] Ethylene-based polymers may include one or more of the following characteristics:

[0061] 1) Melt flow index (MI) (ASTM D-12 38, 2.16 kg @ 190 °C) is about 0.1 dg / min to about 1,000 dg / min (e.g., about 1.0 dg / min to about 200 dg / min, or about 7.0 dg / min to about 20.0 dg / min).

[0062] 2) The melting temperature (Tm) is from about 140°C to about 90°C (e.g., from about 135°C to about 125°C, or from about 130°C to about 120°C).

[0063] Ethylene-based polymers can be synthesized using suitable polymerization techniques known in the art, such as conventional Ziegler-Natta polymerization and catalysis using single-point organometallic catalysts, including metallocene catalysts. Ethylene-based polymers are commercially available. For example, polyethylene can be marketed under the trade name ExxonMobil. TM Polyethylene (ExxonMobil) TM Commercial purchase. Ethylene-based copolymers can be traded under the name ExxonMobil. TM Polyethylene (ExxonMobil) TM Commercially available products, including linear low-density polyethylene produced by metallocene, including Exceed TM Enable TM and Exceed TM XP.

[0064] Polyethylene can include low-density, linear low-density, or high-density polyethylene. Polyethylene can be a long-chain branched (LCB) homopolymer polyethylene with high melt strength (HMS).

[0065] The thermoplastic matrix of the TPV composition may also include a 1-butene-based polymer. 1-Butene-based polymers include those solid, typically high molecular weight isotactic 1-butene resins that primarily consist of units polymerized from 1-butene.

[0066] Polymers based on 1-butene may include isotactic poly(1-butene) homopolymers. These may include copolymers copolymerized with comonomers such as ethylene, propylene, 1-butene, 1-hexane, 1-octene, 4-methyl-1-pentene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-hexene, and mixtures of two or more thereof.

[0067] 1-Butene-based polymers may include one or more of the following characteristics:

[0068] 1) At least 90 wt% or more of the units of the 1-butene-based polymer are derived from the polymerization of 1-butene (e.g., about 95 wt% or more, about 98 wt% or more, about 99 wt% or more). These polymers may include homopolymers of 1-butene.

[0069] 2) Melt flow index (MI) (ASTM D-12 38, 2.16 kg @ 190 °C) is about 0.1 dg / min to 800 dg / min (e.g., about 0.3 dg / min to about 200 dg / min, or about 0.3 dg / min to about 4.0 dg / min), or MI is about 500 dg / min or less (e.g., about 100 dg / min or less, or about 10 dg / min or less, or about 5 dg / min or less).

[0070] 3) The melting temperature (Tm) is about 130°C to about 110°C (e.g., about 125°C to about 115°C, or about 125°C to about 120°C).

[0071] 4) The density, as determined by ASTM D 792, is approximately 0.897 g / ml to approximately 0.920 g / ml, or approximately 0.910 g / ml to approximately 0.920 g / ml, or approximately 0.910 g / ml or greater, or approximately 0.915 g / ml or greater, or approximately 0.917 g / ml or greater.

[0072] Polymers based on 1-butene can be synthesized using suitable polymerization techniques known in the art, such as conventional Ziegler-Natta polymerization and catalysis using single-point organometallic catalysts, including metallocene catalysts. Polymers based on 1-butene are commercially available. For example, isotactic poly(1-butene) can be traded under the name Polybutene Resins. TM Or PBTM (Basell) TM Purchased by merchants.

[0073] When included in a TPV composition, the amorphous cyclic olefin copolymer (COC) forms an elastic thermoplastic matrix at operating temperatures. The thermoplastic matrix may comprise a single COC or a composition of a semi-crystalline polyolefin (such as PP) and COC. The thermoplastic matrix may also include blends of COCs with different glass transition temperatures. The inclusion of semi-crystalline PP and amorphous COC in the thermoplastic matrix provides a balance of elasticity and high-temperature properties for the TPV composition, as measured by compression set and dynamic mechanical properties at high temperatures.

[0074] Amorphous cyclic olefin polymers and copolymers

[0075] The synergistic effect of the semi-crystalline phase, rigid amorphous phase, and soft amorphous phase in a thermoplastic matrix can form an elastic structure with both hard and soft segments. In TPV compositions, cross-linked EPDM rubber provides elasticity, semi-crystalline PP provides processability and strength, and the flowability of the amorphous COC phase can be modulated by the microstructure and amount of plasticizer in the TPV composition, thereby altering the behavior of the continuous phase.

[0076] COC can be incorporated into a thermoplastic matrix to modulate the properties of TPV compositions. For example, COC with a Tg near the ambient range (typically room temperature to 200°C) softens at operating temperatures while maintaining a highly elastic state. This different thermal behavior, compared to rigid semi-crystalline PP, allows COC to act as a "soft filler," toughening the PP matrix and locally crystallizing the PP under heat and stress, resulting in very low compressive deformation compared to conventional PP / EPDM TPV compositions. Furthermore, a Tg of COC around room temperature allows TPV compositions to exhibit better damping properties while maintaining excellent elasticity.

[0077] TPV compositions containing COC with low to medium Tg (typically Tg < 100°C) exhibit better tensile strength and lower compressive deformation due to the more flexible and better dispersible polymer chains of EPDM rubber. Including COC with a Tg around ambient temperature in the TPV composition also provides a wide, high tanδ around the operating temperature, thereby enhancing the vibration damping of the TPV composition while maintaining excellent elasticity. The width and position of the loss tangent peak can be further optimized by selecting or combining different COCs and / or by adding plasticizers to modify the Tg of the COC.

[0078] For ethylene-norbornene COCs, the glass transition temperature varies with the inclusion of norbornene in the backbone, thus allowing the chain flexibility and rigidity of the COC (and consequently, the TPV composition) to be tuned by the norbornene content. Due to the steric hindrance of the rigid ring units, COC molecules are difficult to align and crystallize. Consequently, most COCs are amorphous polymers. Norbornene can be included in the polyethylene backbone through several mechanisms, meaning that COCs can form a wide range of microstructures and correspondingly possess unique properties combining soft amorphous segments (individual norbornene units) and rigid amorphous segments (more alternating and block-shaped norbornene units), as well as potentially semi-crystalline polyethylene segments.

[0079] Figure 3A and Figure 3B The ability of COC to modulate the hardness and glass transition temperature of TPV compositions was demonstrated, especially the ability of ethylene-norbornene COC. Figure 3A Showing various TOPAS TM The hardness of the COC TPV composition varies with the COC content. Figure 3B Two curve fits are shown, each with 5 data points. The curve fit above shows the Tg of pure COC not included in the TPV composition. The curve fit below shows the Tg of the TPV composition containing COC. From left to right, the data points represent the following COCs: TOPAS TM 9903, 9506, 8007, 5013, and 6017. Additionally, numbers containing TOPAS are not shown. TM E-140 is a thermoplastic vulcanized rubber composition with a Tg of about 6°C.

[0080] Figure 3A This demonstrates the ability of COC to adjust the hardness of TPV compositions. For example... Figure 3A As shown, with TOPAS TM The 6017 / 6013 / 5013 thermoplastic vulcanizate compositions exhibited little or no change in Shore A hardness with increasing cyclic olefin copolymer content. This can be explained by the fact that the Tg of these pure cyclic olefin copolymers is much higher than room temperature. For TOPAS... TM For 8007 / 9506 / 9903 / E140, the hardness of the corresponding thermoplastic rubber vulcanized compositions decreases significantly with increasing cyclic olefin copolymer content. This indicates that these cyclic olefin copolymers are in a softened state under environmental conditions, making the thermoplastic vulcanized rubber compositions feel softer.

[0081] Figure 3B The ability of COC to regulate the Tg of TPV compositions was demonstrated. For example... Figure 3BAs shown, the glass transition temperature (Tg) of TPV compositions containing COC is lower than that of pure COC (without plasticizing oil). The amorphous COC is plasticized by the oil in the EPDM rubber, thereby lowering the Tg. The more COC contained in the TPV composition, the more significant the Tg change is observed due to the greater distribution of oil in the plastic phase. Therefore, the Tg of a TPV composition can be adjusted by the COC content, the selection of COC, or the plasticization of COC (adding a plasticizer to the formulation).

[0082] Figure 3B It is also shown that the glass transition temperature of the cyclic olefin copolymer increases with the addition of norbornene. The Tg range of the TPV composition of the present invention is from about 0°C to about 120°C, while the Tg range of the cyclic olefin copolymer in its pure state is from about 30°C to about 180°C, and is always higher than the Tg of the TPV composition.

[0083] The cyclic olefin copolymers of the TPV compositions described herein have a glass transition temperature (Tg) of about 30°C to about 200°C in the pure state. The cyclic olefin copolymers may have a glass transition temperature of about 30°C to about 100°C, about 30°C to about 90°C, about 35°C to about 70°C, about 40°C to about 60°C, or greater than about 30°C in the pure state.

[0084] The thermoplastic matrix of the TPV composition comprises about 1 wt% to about 100 wt% of a cyclic olefin copolymer and up to 99 wt% of a semi-crystalline polyolefin. The thermoplastic matrix may comprise about 10 wt% to about 90 wt%, about 20 wt% to about 80 wt%, about 30 wt% to about 70 wt%, or about 40 wt% to about 60 wt% of a cyclic olefin copolymer. The thermoplastic matrix may comprise about 0 wt% to about 99 wt%, about 10 wt% to about 90 wt%, about 20 wt% to about 80 wt%, about 30 wt% to about 70 wt%, about 40 wt% to about 60 wt%, or up to 99 wt% of a semi-crystalline polyolefin.

[0085] Cyclic alkenes are monounsaturated or polyunsaturated polycyclic systems, such as cyclic alkenes, bicyclic alkenes, tricyclic alkenes, or tetracyclic alkenes. The cyclic system can be monosubstituted or polysubstituted. Suitable cyclic alkenes for use in COC include norbornene, tricyclic decene, dicyclopentadiene, tetracyclic dodecene, hexacyclic heptadecene, tricyclic undecene, pentacyclic hexadecene, ethylidene norbornene (ENB), vinyl norbornene (VNB), norbornene, alkyl norbornene, cyclopentene, cyclopropylene, cyclobutene, cyclohexene, cyclopentadiene (CP), cyclohexadiene, cycloocttriene, indene, any Diels-Alder adduct of cyclopentadiene with acyclic alkenes, cyclic alkenes, or dienes; and any Diels-Alder adduct of butadiene with acyclic alkenes, cyclic alkenes, or dienes; vinylcyclohexene (VCH); vinylcyclobutane (VCB); alkyl derivatives of cyclic alkenes; and aromatic derivatives of cyclic alkenes. Cycloolefin monomers are contained in the COC or COP material used in this TPV composition and can be prepared using a transition metal catalyst (e.g., metallocene).

[0086] Particularly preferred cyclic olefin copolymers include cyclic olefin monomers copolymerized with acyclic olefin monomers. Suitable acyclic olefins for use in COCs include α-olefins (1-olefins), isobutylene, 2-butene, and vinyl aromatics. Examples of such acyclic olefins include ethylene, propylene, 1-butene, isobutylene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, styrene, p-methylstyrene, p-tert-butylstyrene, p-phenylstyrene, 3-methyl-1-pentene, vinylcyclohexane, 4-methyl-1-pentene, alkyl derivatives of acyclic olefins, aromatic derivatives of acyclic olefins, and combinations thereof.

[0087] The cyclic olefin copolymers of the TPV compositions described herein may include ethylene-norbornene copolymers containing about 40 wt% to about 90 wt% norbornene. Cyclic olefin copolymers may include ethylene-norbornene copolymers containing about 50 wt% to about 80 wt% norbornene, about 60 wt% to about 70 wt% norbornene, or about 66 wt% to about 68 wt% norbornene. Alternatively, preferred COCs comprise about 10 mol% to about 80 mol% of a cyclic olefin monomer moiety and about 20 wt% to about 90 wt% of an acyclic olefin moiety (e.g., ethylene). Cyclic olefin copolymers suitable for the purposes of this TPV composition typically have an average molecular weight Mw greater than about 200 g / mol to about 400,000 g / mol. COCs can be characterized by their glass transition temperature Tg, which is typically about 20°C to about 200°C, preferably about 30°C to about 130°C. The cyclic olefin polymer can be a copolymer, such as... 8007F-04, which comprises approximately 36 mol% norbornene and the balance ethylene. 8007F-04 has a glass transition temperature of approximately 78°C. Other preferred COCs include melt blends of partially crystalline cyclic olefin elastomers and amorphous COC materials with low glass transition temperatures. A preferred material for blending with partially crystalline cyclic olefin elastomers is one with a Tg of approximately 68°C. 9506F-04. Another preferred amorphous COC for blending with partially crystalline cycloolefin elastomers is one with a glass transition temperature of about 33°C. 9903D-10.

[0088] Furthermore, the COC may contain suitable dienes, such as 1,4-hexadiene; 1,5-hexadiene; 1,5-heptadiene; 1,6-heptadiene; 1,6-octadiene; 1,7-octadiene; 1,9-decadiene; butadiene; 1,3-pentadiene; isoprene; 1,3-hexadiene; 1,4-pentadiene; alkyl derivatives of divinylbenzene: dienes; and aromatic derivatives of dienes.

[0089] Combining these elements, suitable COCs for TPV compositions include ethylene-norbornene copolymers; ethylene-dicyclopentadiene copolymers; ethylene-norbornene-dicyclopentadiene terpolymers; ethylene-norbornene-ethylenenorbornene terpolymers; ethylene-norbornene-vinylnorbornene terpolymers; ethylene-norbornene-1,7-octadiene terpolymers; ethylene-cyclopentene copolymers; ethylene-indene copolymers; ethylene-tetracyclododecene copolymers; ethylene-norbornene-vinylcyclohexene terpolymers; ethylene-norbornene-7-methyl-1,6-octadiene terpolymers; and propylene-norbornene copolymers. ; propylene-dicyclopentadiene copolymer; ethylene-norbornene-styrene terpolymer; ethylene-norbornene-p-methylstyrene terpolymer; functionalized ethylene-dicyclopentadiene copolymer; functionalized propylene-dicyclopentadiene copolymer; functionalized ethylene-norbornene-diene copolymer; maleic anhydride-grafted cycloolefin copolymer; silane-grafted cycloolefin copolymer; hydrogenated ethylene-dicyclopentadiene copolymer; epoxidized ethylene-dicyclopentadiene copolymer; epoxidized ethylene-norbornene-dicyclopentadiene terpolymer; grafted cycloolefin copolymer; short-chain branched cycloolefin copolymer; long-chain branched cycloolefin copolymer; and crosslinked cycloolefin copolymer.

[0090] COC can be prepared by copolymerizing at least one cyclic olefin with at least one acyclic olefin and optionally one or more dienes. The total amount of all cyclic olefins in the COC is from about 20 wt% to about 99 wt% of the copolymer. Furthermore, residual double bonds in the cyclic olefin copolymer may be unreacted or have been hydrogenated, crosslinked, or functionalized. Cyclic olefin copolymers can also be grafted using free radical addition reactions or in-reactor copolymerization. COC can be a block copolymer prepared using a chain shuttle. COC can also be prepared using vanadium, Ziegler-Natta, and metallocene catalysts. Norbornene is prepared by the Diels-Alder addition reaction of cyclopentadiene and ethylene.

[0091] The cyclic olefin copolymers suitable for the purposes of this TPV composition have an average molecular weight (Mw) typically greater than 200 g / mol to 400,000 g / mol. The COC can be characterized by a glass transition temperature (Tg) of about 20°C to about 200°C, preferably about 30°C to about 130°C. Ethylene-norbornene copolymers are available from Topas Advanced Polymers. TM and Mitsui Chemicals TM Ethylene / norbornene copolymers prepared using metallocene catalysts can be TOPAS TM The copolymer was purchased from Topas Advanced Polymers TM GmbH. Cycloolefin polymers can be copolymers, such as TOPAS. TM 8007F-04, which comprises approximately 36 mol% norbornene and the balance ethylene. TOPAS TM 8007F-04 has a glass transition temperature of approximately 78°C. COC can be used for TOPAS. TM 9903D-10 has a glass transition temperature of approximately 33°C. COC can be used for TOPAS. TM 9506F-04 has a Tg of approximately 68°C. Cycloolefin polymers can be used as TOPAS. TM 6015 or 6017, each having a Tg of approximately 160°C and approximately 180°C. The TPV composition may also include melt blends of amorphous COC materials with different glass transition temperatures.

[0092] Cycloolefin copolymer elastomer

[0093] The thermoplastic matrix of the TPV composition may contain a COC elastomer. Such a COC elastomer is available from TOPAS. TMAdvanced Polymers commercially available as E-140 is an elastic cyclic olefin copolymer. E-140 polymer is characterized by having two glass transition temperatures, one at approximately 6°C and the other below -90°C. E-140 polymer has a crystalline melting point of approximately 84°C. It is comparable to fully amorphous TOPAS. TM Depending on the COC grade, COC elastomers typically contain approximately 10 wt% to approximately 30 wt% crystallinity. E-140 has a crystallinity of 940 kg / m³. 3 Density (ISO 1183), 3cm³ 3 Melt volumetric rate (MVR) per 10 min (ISO 1133 @ 2.16 kg / 190 °C), 12 cm 3 The melt volumetric rate (MVR) is approximately 10 °C / min (ISO 1133 @ 2.16 kg / 260 °C), and the Shore A hardness is approximately 89. The thermal properties of E-140 include a glass transition temperature (DSC) of approximately 6 °C / min (at 10 °C / min) and a melting temperature of approximately 84 °C. E-140 has multiple glass transition temperatures (Tg): one occurs below -90 °C, and another occurs in the range of -10 °C to 15 °C.

[0094] For E-140 copolymer elastomers with a norbornene content of approximately 8-9 mol%, partially crystalline COC elastomers have been observed to exhibit a rubber modulus stability period between approximately 10-20 °C and 80-90 °C. Partially crystalline ethylene / norbornene copolymer elastomers can have a norbornene content ranging from 1 mol% to 20 mol%.

[0095] The COC elastomers suitable for TPV compositions have very low norbornene-ethylene-norbornene ternary content and two distinct block moieties. One set of polymer blocks contains a relatively high norbornene content and remains amorphous, while the other set of polymer block copolymers is considered to have a relatively low norbornene content and is partially crystalline.

[0096] Typically, suitable partially crystalline elastomers of norbornene and ethylene comprise 0.1 mol% to 20 mol% norbornene, having at least one glass transition temperature of less than 30 °C, a crystallization melting temperature of less than 125 °C, and a crystallinity of 40% or less. Particularly preferred elastomers exhibit crystallization melting temperatures of less than 90 °C and greater than 60 °C.

[0097] Cross-linked rubber

[0098] As described above, the TPV composition comprises particles containing at least partially crosslinked rubber dispersed in a thermoplastic matrix. These crosslinked rubber particles include polymers crosslinked from phenolic resins or hydrogenated silanizing curing agents (e.g., silane-containing curing agents), peroxides with additives, wet-curing via silane grafting, metal oxide / phenolic resins, or azide compounds. References to rubber may include mixtures of more than one type of rubber. Non-limiting examples of rubber include olefin elastomer terpolymers and mixtures thereof. Olefin elastomer terpolymers include ethylene-based elastomers, such as ethylene-propylene-non-conjugated diene rubber. Other non-limiting examples of rubber may include olefin elastomer terpolymers, butyl rubbers (e.g., isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), isobutylene-p-methylstyrene rubber (BIMSM), halogenated copolymers of C4 to C7 isomonoolefins and p-alkylstyrene), and combinations and mixtures thereof.

[0099] 1. Ethylene-propylene rubber

[0100] The term ethylene-propylene rubber refers to a rubbery terpolymer (e.g., ethylene-propylene-diene terpolymer or EPDM terpolymer) polymerized from ethylene, at least one other α-olefin monomer, and at least one diene monomer. The α-olefin monomer may include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof. The diene monomer may include 5-ethylidene-2-norbornene (ENB); 5-vinyl-2-norbornene (VNB); divinylbenzene; 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; or combinations thereof. If multiple α-olefin monomers or diene monomers are used, the polymer prepared from ethylene, α-olefin monomers and diene monomers can be called a terpolymer or even a quaternary copolymer.

[0101] When the diene monomer includes 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB), the ethylene-propylene rubber may include at least about 1 wt%, such as at least about 3 wt%, such as at least about 4 wt%, such as at least about 5 wt%, such as at least about 10 wt% of the diene monomer based on the total weight of the ethylene-propylene rubber. When the diene includes ENB or VNB, the ethylene-propylene rubber may include about 1 wt% to about 15 wt%, such as about 3 wt% to about 15 wt%, such as about 5 wt% to about 12 wt%, such as about 7 wt% to about 11 wt% of the diene monomer based on the total weight of the ethylene-propylene rubber.

[0102] Ethylene-propylene rubber may include one or more of the following:

[0103] 1) Based on the total weight of the ethylene-propylene rubber, the ethylene derivative may be from about 10 wt% to about 99.9 wt%, such as from about 10 wt% to about 90 wt%, such as from about 12 wt% to about 90 wt%, such as from about 15 wt% to 90 wt%, such as from about 20 wt% to 80 wt%, such as from about 40 wt% to 70 wt%, such as from about 45 wt% to about 65 wt%. Based on the total weight of the ethylene-propylene rubber, the ethylene derivative may be from about 40 wt% to about 85 wt%, such as from about 40 wt% to about 85 wt%.

[0104] 2) Based on the total weight of the ethylene-propylene rubber, the diene derivative may be from about 0.1 wt% to about 15 wt%, such as from about 0.1 wt% to about 5 wt%, such as from about 0.2 wt% to about 10 wt%, such as from about 2 wt% to about 8 wt%, or from about 4 wt% to about 12 wt%, such as from about 4 wt% to about 9 wt%. Based on the total weight of the ethylene-propylene rubber, the diene derivative may be from about 3 wt% to about 15 wt%.

[0105] 3) The balance of ethylene-propylene rubber may be α-olefin derivatives, such as C2 to C40, C3 to C20, C3 to C10 olefins, such as propylene.

[0106] 4) Weight-average molecular weight (Mw) can be about 100,000 g / mol or greater, such as about 200,000 g / mol or greater, such as about 400,000 g / mol or greater, such as about 600,000 g / mol or greater. Mw can also be about 1,200,000 g / mol or less, such as about 1,000,000 g / mol or less, such as about 900,000 g / mol or less, such as about 800,000 g / mol or less. Mw can be from about 400,000 g / mol to about 3,000,000 g / mol, such as from about 400,000 g / mol to about 2,000,000 g / mol, such as from about 500,000 g / mol to about 1,500,000 g / mol, such as from about 600,000 g / mol to about 1,200,000 g / mol, such as from about 600,000 g / mol to about 1,000,000 g / mol. Mw is determined using polystyrene standards according to GPC.

[0107] 5) The number-average molecular weight (Mn) can be about 20,000 g / mol or greater (e.g., about 60,000 g / mol or greater, about 100,000 g / mol or greater, about 150,000 g / mol or greater). Mn can also be less than about 500,000 g / mol, such as about 400,000 g / mol or less, about 300,000 g / mol or less, or about 250,000 g / mol or less. Mn is determined using polystyrene standards according to GPC.

[0108] 6) The Z-average molecular weight (Mz) can be from about 10,000 g / mol to about 7,000,000 g / mol, from about 50,000 g / mol to about 3,000,000 g / mol, from about 70,000 g / mol to about 2,000,000 g / mol, from about 75,000 g / mol to about 1,500,000 g / mol, from about 80,000 g / mol to about 700,000 g / mol, or from about 100,000 g / mol to about 500,000 g / mol. Mz is determined using polystyrene standards according to GPC.

[0109] 7) The polydispersity index (Mw / Mn; PDI) can be from about 1 to about 10, such as from about 1 to about 5, such as from about 1 to about 4, such as from about 2 to about 4 or from about 1 to about 3, such as from about 1.8 to about 3 or from about 1 to about 2, or from about 1 to about 2.5, as determined by GPC using polystyrene standards.

[0110] 8) The dry Mooney viscosity (ML(1+4), 125°C) according to ASTM D-1646 is about 10 MU to about 500 MU or about 50 MU to about 450 MU. The Mooney viscosity is about 250 MU or greater, such as 350 MU or greater, such as 450 MU or less.

[0111] 9) The glass transition temperature (Tg) determined by differential scanning calorimetry (DSC) according to ASTM E 1356 may be about -20°C or lower, such as about -30°C or lower, such as -50°C or lower. Tg may be about -20°C to about -60°C.

[0112] Ethylene-propylene rubber (EPDM) can be manufactured or synthesized using various technologies. For example, these terpolymers can be synthesized using solution, slurry, or gas-phase polymerization techniques or combinations thereof, employing various catalyst systems including Ziegler-Natta systems with vanadium catalysts, and occurring in various phases such as solution, slurry, or gas. Exemplary catalysts may include single-point catalysts, including catalysts with restricted geometries containing group IV-VI metallocenes. EPDM can be produced using conventional Ziegler-Natta catalysts in slurry processes, particularly those involving vanadium compounds and metallocene catalysts. Other catalyst systems, such as Brookhart catalyst systems, can also be used. Alternatively, such EPDM can be prepared using the aforementioned catalyst systems in solution processes.

[0113] Some elastomer terpolymers can be marketed under the trade name Vistalon. TM (ExxonMobil Chemical Co. TM Houston, Tex.), Keltan TM (Arlanxeo Performance Elastomers TM Orange, TX, and Nordel TM IP (Dow) TM NORDEL MG TM (Dow TM Royalene TM (Lion Elastomers TM ), KEP TM (Kumho Polychem TM ) and Suprene TM (SK Global Chemical TM Purchased commercially. Specific examples include Vistalon. TM 3666, Vistalon TM 1696, Vistalon TM 9600, Keltan TM 9950C, Keltan TM 8550C, KEP TM 8512, KEP TM 9590, Keltan TM 5469Q, Keltan TM 4969Q, Keltan TM 5469C, Keltan TM 4869C, Royalene TM 694. RoyaleneTM 677, Suprene TM 512F, Nordel TM 6555, Nordel TM 4571XFM, Royalene TM 515.

[0114] Ethylene propylene rubber can be obtained in the form of oil increments, with processing oils ranging from about 50 phr to about 200 phr based on 100 phr rubber, such as processing oils ranging from about 75 phr to about 120 phr.

[0115] 2. Butyl rubber

[0116] Butyl rubber may comprise copolymers and terpolymers of isobutylene and at least one other comonomer. Available comonomers may include isoprene, divinyl aromatic monomers, alkyl-substituted vinyl aromatic monomers, and mixtures thereof. Example divinyl aromatic monomers may include vinylstyrene. Example alkyl-substituted vinyl aromatic monomers may include α-methylstyrene and p-methylstyrene. These copolymers and terpolymers may be halogenated butyl rubbers (also known as halogenated butyl rubbers), such as chlorinated butyl rubber and brominated butyl rubber. These halogenated polymers may be derived from monomers such as p-bromomethylstyrene.

[0117] Butyl rubber may include copolymers of isobutylene and isoprene, copolymers of isobutylene and p-methylstyrene, terpolymers of isobutylene, isoprene, and vinylstyrene, branched butyl rubber, and brominated copolymers of isobutylene and p-methylstyrene (resulting in copolymers having p-bromomethylstyrene monomer units). These copolymers and terpolymers may be halogenated. Exemplary butyl rubbers may include isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), chlorinated isobutylene-isoprene rubber (CIIR), isobutylene-p-methylstyrene rubber (BIMSM), halogenated copolymers of C4 to C7 isomonoolefins and p-alkylstyrene, or combinations thereof.

[0118] Butyl rubber may include one or more of the following characteristics:

[0119] 1) In the case where the butyl rubber includes isobutylene-isoprene rubber, the rubber may include an amount of about 0.5 wt% to about 30 wt% based on the total weight of the rubber, such as about 0.8 wt% to about 5 wt% of isoprene, with the remainder being isobutylene.

[0120] 2) In the case where the butyl rubber includes isobutylene-p-methylstyrene rubber, based on the total weight of the rubber, the rubber may include an amount of about 0.5 wt% to about 25 wt%, such as about 2 wt% to about 20 wt% of p-methylstyrene, with the remainder being isobutylene.

[0121] 3) In the case of isobutylene-p-methylstyrene rubber being halogenated with bromine and / or chlorine, based on the total weight of the rubber, these halogenated rubbers may have a halogenation weight percentage of about 0 wt% to about 10 wt%, such as about 0.3 wt% to about 7 wt%, with the remainder being isobutylene.

[0122] 4) In the case of isobutylene-isoprene rubber being halogenated with bromine and / or chlorine, based on the total weight of the rubber, these halogenated rubbers may have a halogenation weight percentage of about 0 wt% to about 10 wt%, such as about 0.3 wt% to about 7 wt%, with the remainder being isobutylene.

[0123] 5) In the case where the butyl rubber comprises isobutylene-isoprene-divinylbenzene, based on the total weight of the rubber, the butyl rubber may comprise an amount of about 95 wt% to about 99 wt% of isobutylene, such as about 96 wt% to about 98.5 wt% of isobutylene, and an amount of about 0.5 wt% to about 5 wt% of isoprene, such as about 0.8 wt% to about 2.5 wt% of isoprene, with the balance being divinylbenzene.

[0124] 6) In the case where the butyl rubber includes halogenated butyl rubber, the butyl rubber may include about 0.1 wt% to about 10 wt%, such as about 0.3 wt% to about 7 wt%, such as about 0.5 wt% to about 3 wt% of halogen, based on the total weight of the rubber.

[0125] 7) The weight-average molecular weight (Mw) can be about 100,000 g / mol or greater, such as about 200,000 g / mol or greater, such as about 400,000 g / mol or greater, such as about 600,000 g / mol or greater. Mw can also be about 1,200,000 g / mol or less, such as about 1,000,000 g / mol or less, such as about 900,000 g / mol or less, such as about 800,000 g / mol or less. Mw can be from about 500,000 g / mol to about 3,000,000 g / mol, from about 500,000 g / mol to about 2,000,000 g / mol, from about 500,000 g / mol to about 1,500,000 g / mol, from about 600,000 g / mol to about 1,200,000 g / mol, or from about 600,000 g / mol to about 1,000,000 g / mol. Mw is determined using polystyrene standards according to GPC.

[0126] Butyl rubber is available from various commercial sources listed in Rubber World Blue Book. For example, halogenated and non-halogenated rubbers / polymers of isobutylene and isoprene can be traded under the name Exxon Butyl.TM (ExxonMobil Chemical Co. TM The halogenated and non-halogenated copolymers of isobutylene and p-methylstyrene can be obtained under the trade name EXXPRO. TM (ExxonMobil Chemical Co. TM Star-branched butyl rubber, available under the trade name STARBRANCHED BUTYL, can be obtained. TM (ExxonMobil Chemical Co. TM The copolymer containing p-bromomethylstyrene monomer units can be obtained under the trade name EXXPRO. TM 3745 (ExxonMobil Chemical Co.) TM (This is an example of obtaining halogenated and non-halogenated terpolymers of isobutylene, isoprene, and divinylstyrene, which can be traded under the name Polysar Butyl.) TM (Lanxess TM (Germany) obtained.

[0127] The rubber (e.g., ethylene-propylene rubber or butyl rubber) can be highly cured. The rubber can be partially or fully cured. The degree of cure is determined by determining the amount of rubber extractable from the TPV composition using cyclohexane or boiling xylene as an extractant. The rubber can have a degree of cure of no more than about 5.9 wt%, such as no more than about 5 wt%, no more than about 4 wt%, or no more than about 3 wt%, extractable by cyclohexane at 23°C. The rubber can be cured to a degree to which more than about 94 wt%, such as more than about 95 wt%, such as more than about 96 wt%, or for example more than about 97 wt%, by weight is insoluble in cyclohexane at 23°C. Alternatively, the rubber can have a crosslinking density of at least about 4 × 10⁻⁶. -5 Moles per milliliter of rubber, such as at least about 7 × 10⁻⁶ -5 Moles per milliliter of rubber, such as at least about 10 × 10 -5 Curing degree of rubber in moles per milliliter. See also “Crosslink Densities and Phase Morphologies in Dynamically Vulcanized TPEs,” Ellul et al., RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 68, pp. 573-584 (1995).

[0128] Although the rubber can be partially or fully cured, the compositions disclosed herein can be processed and reprocessed using conventional plastics processing techniques such as extrusion, injection molding, blow molding, and compression molding. The rubber in these thermoplastic elastomers can be in the form of finely and well-dispersed vulcanized or cured rubber particles in a continuous thermoplastic phase or matrix. Co-continuous or inverse morphologies are possible. In the case where the cured rubber is finely and well-dispersed particles in a thermoplastic medium, the average diameter of the rubber particles can be about 50 μm or less (e.g., about 30 μm or less, about 10 μm or less, about 5 μm or less, about 1 μm or less). At least about 50% of the particles, such as about 60% of the particles, such as about 75% of the particles, can have an average diameter of about 5 μm or less, such as about 2 μm or less, such as about 1 μm or less.

[0129] Oil

[0130] TPV compositions also include oils, such as mineral oils, synthetic oils, or combinations thereof. These oils are also known as plasticizers or extenders. Mineral oils may include aromatic oils, naphthenic oils, paraffinic oils, isoparaffinic oils, synthetic oils, and combinations thereof. Mineral oils may be treated or untreated. Available mineral oils may be marketed under the trade name SUNPAR. TM (Sun Chemicals TM (Other options include the product name PARALUX) TM (Chevron™ and PARAMOUNT) TM (Chevron™) Available. Other usable oils include hydrocarbon oils and plasticizers such as organic esters and synthetic plasticizers. Many additive oils are derived from petroleum fractions and have specific ASTM names depending on whether they belong to the category of paraffinic oils, naphthenic oils, or aromatic oils. Other types of additive oils include alpha-olefin synthetic oils, such as liquid polybutene. Additive oils other than petroleum-based oils are also available, such as those derived from coal tar and pine tar, as well as synthetic oils, such as those for polyolefin materials.

[0131] The oil contained in TPV compositions can be a base oil. According to the American Petroleum Institute... TM According to the API (American Petroleum Institute) classification, base oils are divided into five categories based on their saturated hydrocarbon content, sulfur level, and viscosity index (Table 3). Lubricating oil base oils are typically produced on a large scale from non-renewable petroleum sources. Group I, II, and III base oils are all extracted from crude oil through extensive processing, such as solvent extraction, solvent or catalytic dewaxing, as well as hydroisomerization, hydrocracking and isomerization dewaxing, isomerization dewaxing, and hydrorefining.

[0132] Group III base oils can also be produced from synthetic hydrocarbon liquids derived from natural gas, coal, or other fossil resources. Group IV base oils are polyalphaolefins (PAOs) and are produced through the oligomerization of alpha-olefins (e.g., 1-decene). Group V base oils include all base oils that do not belong to Groups I through IV, such as cycloalkanes, polyalkylene glycols (PAGs), and esters.

[0133] Table 1. API Base Oil Classification

[0134]

[0135] Synthetic oils comprise polymers and oligomers of butene (including isobutene, 1-butene, 2-butene, butadiene, and mixtures thereof). These oligomers can be characterized by a number-average molecular weight (Mn) of about 300 g / mol to 9000 g / mol, or about 700 g / mol to 1300 g / mol. These oligomers comprise isobutene-based monomer units. Exemplary synthetic oils include polyisobutene, poly(isobutene-co-butene), and mixtures thereof. Synthetic oils may include polylinear α-olefins, polybranched α-olefins, hydrogenated polyα-olefins, and mixtures thereof.

[0136] Synthetic oils may include synthetic polymers or copolymers with a viscosity of about 20 cp or greater, such as about 100 cp or greater, such as about 190 cp or greater, wherein the viscosity is determined by a Brookfield viscometer at 38°C according to ASTM D-4402. These oils may also have a viscosity of about 4000 cp or less, such as about 1000 cp or less.

[0137] Available synthetic oils can be traded under the name Polybutene. TM (Soltex TM (Houston, Tex.) and Indopol TM (Ineos TM Obtained commercially. Synthetic white oil can be traded under the name SPECTRASYN. TM (ExxonMobil TM ), originally SHFFluids TM (Mobil TM ), Elevast TM (ExxonMobil TM ), and white oils produced by gas-to-liquid conversion technology, such as Risella. TM X415 / 420 / 430 (Shell) TM ) or Primol TM (ExxonMobil TM White oil series, such as Primol TM 352, Primol TM382, Primol TM 542, or Marcol TM 82, Marcol TM 52, (Pencero TM White oil series, such as 34 or a combination thereof. Oils described in U.S. Patent No. 5,936,028 may also be used.

[0138] The TPV composition includes oil in amounts of about 30 parts to about 450 parts (about 100 to about 450 phr) per 100 parts of rubber. The thermoplastic vulcanized rubber composition may contain oil in amounts of about 50 to about 450 phr, about 100 to about 350 phr, about 150 to about 300 phr, or about 150 to about 250 phr.

[0139] Other components

[0140] TPV compositions may also include optional polymer processing additives. Processing additives may be polymer resins with extremely high melt flow indices. These polymer resins include linear and branched polymers with melt flow rates of about 500 dg / min or greater, such as about 750 dg / min or greater, about 1000 dg / min or greater, about 1200 dg / min or greater, or about 1500 dg / min or greater. Mixtures of various branched or linear polymer processing additives, as well as mixtures of both linear and branched polymer processing additives, may be used. Unless otherwise stated, references to polymer processing additives may include both linear and branched additives. Linear polymer processing additives include polypropylene homopolymers, and branched polymer processing additives include diene-modified polypropylene polymers.

[0141] In addition to rubber, thermoplastic resin, and optional processing additives, the thermoplastic vulcanized rubber compositions disclosed herein may optionally include reinforcing and unreinforced fillers, compatibilizers, antioxidants, stabilizers, rubber processing oils, lubricants, antiblocking agents, antistatic agents, waxes, foaming agents, dyes, flame retardants, nucleating agents, and other processing aids known in the field of rubber compounding. These additives may comprise approximately 50 wt% of the total composition.

[0142] Fillers and extenders that can be used in TPV compositions may include conventional inorganic materials such as calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, nucleating agents, mica, wood flour, etc., as well as blends thereof, and inorganic and organic nanoscale fillers.

[0143] Preparation of TPV Compositions

[0144] Crosslinked rubber can be cured or crosslinked via dynamic vulcanization. The term "dynamic vulcanization" refers to the vulcanization or curing process of rubber contained in a blend of thermoplastic resins, wherein the rubber is crosslinked or vulcanized via reaction under high shear conditions at a temperature above the melting point of the thermoplastic. Rubber can be cured using a variety of curing agents. Exemplary curing agents include phenolic resin curing systems, metal oxide / resin curing systems, metal oxide, peroxide curing systems, and silicone-containing curing systems, such as hydrosilylation and silane grafting / wet curing. Dynamic vulcanization can be carried out in the presence of COC and semi-crystalline PP, or COC and / or semi-crystalline PP can be added after dynamic vulcanization (i.e., added later), or both (i.e., some COC and semi-crystalline PP can be added before dynamic vulcanization, and some COC and semi-crystalline PP can be added after dynamic vulcanization). Rubber can be simultaneously crosslinked and dispersed in a fine particulate form within a thermoplastic matrix, but other forms are also possible.

[0145] Dynamic vulcanization can be achieved at high temperatures by compounding thermoplastic elastomer components in conventional mixing equipment (e.g., roll mills, stabilizers, Banbury mills, Brabender mills, continuous mills, compound extruders, etc.). Methods employing low shear rates can also be used. Multi-step processes can also be employed, allowing the addition of components such as other thermoplastic resins after dynamic vulcanization. Those skilled in the art can readily determine a sufficient or effective amount of vulcanizing agent to be used without excessive calculations or experiments.

[0146] The TPV compositions prepared according to this disclosure can be dynamically vulcanized by various methods, including using phenolic resin curing systems, metal oxide / resin curing systems, metal oxide / peroxide curing systems, maleimide curing systems, silicon-based curing systems (including hydrogen silanization curing systems, silane-based systems, such as silane grafting followed by wet curing), sulfur curing systems, or combinations thereof.

[0147] The phenolic resin curing system for dynamic vulcanization employs a phenolic resin curing agent, including a methyl phenolic resin, which can be prepared by the condensation of an alkyl-substituted phenol or an unsubstituted phenol with an aldehyde (e.g., formaldehyde) in an alkaline medium or by the condensation of a bifunctional phenolic glycol. The alkyl substituent of the alkyl-substituted phenol may contain about 1 to about 10 carbon atoms, such as a dimethylphenol or phenolic resin with an alkyl group containing about 1 to about 10 carbon atoms in the para-position. Blends of octylphenol-formaldehyde and nonylphenol-formaldehyde resins can be used. Such blends comprise about 25 wt% to about 40 wt% octylphenol-formaldehyde and about 75 wt% to about 60 wt% nonylphenol-formaldehyde, such as about 30 wt% to about 35 wt% octylphenol-formaldehyde and about 70 wt% to about 65 wt% nonylphenol-formaldehyde. The blend may comprise about 33 wt% octylphenol-formaldehyde and about 67 wt% nonylphenol-formaldehyde resin, wherein each of the octylphenol-formaldehyde and nonylphenol-formaldehyde comprises hydroxymethyl. The blend may be soluble in paraffin oil with about 30% solids without phase separation.

[0148] Suitable phenolic resins are available from the trade name SP-1044. TM SP-1045 TM (SchenectadyInternational TM Phenolic resins (Schenectady, NY) are also known as alkylphenol-formaldehyde resins. Examples of phenolic resin curing agents include those defined according to the following general formula:

[0149]

[0150] Where Q is a divalent free radical selected from -CH2-, -CH2-O-CH2-; m is a positive integer from 0 to 20; and R' is an organic group. Q can be a divalent free radical -CH2-O-CH2-, m is a positive integer from 0 to 10, and R' is an organic group with fewer than 20 carbon atoms. Optionally, m is a positive integer from 0 to 10, and R' is an organic free radical having 4 to 12 carbon atoms.

[0151] Phenolic resins can be used in combination with halogen sources (e.g., stannous chloride) and metal oxides or reducing compounds (e.g., zinc oxide). The amount of phenolic resin used can be from about 2 parts by weight to about 6 parts by weight per 100 parts by weight of rubber, such as from about 3 parts by weight to about 5 parts by weight, or from about 4 parts by weight to about 5 parts by weight. The amount of stannous chloride supplemented can be from about 0.5 parts by weight to about 2.0 parts by weight per 100 parts by weight of rubber, such as from about 1.0 parts by weight to about 1.5 parts by weight, or from about 1.2 parts by weight to about 1.3 parts by weight. In conjunction with this, zinc oxide can be used from about 0.1 parts by weight to about 6.0 parts by weight, such as from about 1.0 parts by weight to about 5.0 parts by weight, or from about 2.0 parts by weight to about 4.0 parts by weight. Olefin rubbers used with phenolic curing agents can include diene units derived from 5-ethylidene-2-norbornene.

[0152] As described above, dynamic vulcanization of the TPV composition can be carried out using a peroxide curing system. Suitable peroxide curing agents include organic peroxides. Examples of organic peroxides include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, α,α-bis(tert-butylperoxide)diisopropylbenzene, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane (DBPH), 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxide)valerate, benzoyl peroxide, lauroyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexyn-3, and mixtures thereof. Additionally, diaryl peroxides, ketone peroxides, dicarbonates peroxide, peroxide esters, dialkyl peroxides, hydroperoxides, peroxyketals, and mixtures thereof can be used.

[0153] Peroxide curing agents can be used in combination with additives. Examples of additives include triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, sulfur, N-phenylbismaleimide, zinc diacrylate, zinc dimethacrylate, divinylbenzene, 1,2-polybutadiene, trimethylolpropane trimethacrylate, tetramethylene glycol diacrylate, trifunctional acrylates, dipentaerythritol pentaacrylate, polyfunctional acrylates, retarded cyclohexanediol diacrylate, polyfunctional methacrylates, acrylates and methacrylate metal salts, and oximes such as benzoquinone dioxime. To maximize the efficiency of peroxide / additive crosslinking, mixing and dynamic vulcanization can be carried out under a nitrogen atmosphere.

[0154] As described above, dynamic vulcanization of the TPV composition can be carried out using a silicon-containing curing system. The silicon-containing curing system may include a hydrogenated silicon compound having at least two Si-H groups. Hydrogenated silicon compounds used in carrying out the present invention include methylhydropolysiloxanes, methylhydrodimethylsiloxane copolymers, alkylmethyl-co-methylhydropolysiloxanes, bis(dimethylsilyl)alkanes, bis(dimethylsilyl)benzenes, and mixtures thereof. Catalysts that can be used for hydrogenated silylation include Group VIII transition metals. These metals include palladium, rhodium, and platinum, as well as complexes of these metals.

[0155] Silane-based systems can also be used for dynamic vulcanization. The amount of silane compound used can be from about 0.5 parts by weight to about 5.0 parts by weight per 100 parts by weight of rubber (e.g., from about 1.0 parts by weight to about 4.0 parts by weight, or from about 2.0 parts by weight to about 3.0 parts by weight). The amount of catalyst added can include from about 0.5 parts by weight of metal to about 20.0 parts by weight of metal per 1,000,000 parts by weight of rubber (e.g., from about 1.0 part by weight to about 5.0 parts by weight, or from about 1.0 part by weight of metal to about 2.0 parts by weight of metal). Olefin rubber used with hydrogenated silanizing curing agents can include diene units derived from 5-vinyl-2-norbornene.

[0156] Those skilled in the art can readily determine the sufficient or effective amount of vulcanizing agent to be used without excessive calculation or experimentation. For example, the amount of phenolic resin may be from about 2 parts by weight to about 10 parts by weight per 100 parts by weight of rubber (e.g., from about 3.5 parts by weight to about 7.5 parts by weight, or from about 5 parts by weight to about 6 parts by weight). The phenolic resin may be used in combination with stannous chloride and optionally zinc oxide. The amount of stannous chloride may be from about 0.2 parts by weight to about 10 parts by weight per 100 parts by weight of rubber (e.g., from about 0.3 parts by weight to about 5 parts by weight, or from about 0.5 parts by weight to about 3 parts by weight). The amount of zinc oxide may be from about 0.25 parts by weight to about 5 parts by weight per 100 parts by weight of rubber (e.g., from about 0.5 parts by weight to about 3 parts by weight, or from about 1 part by weight to about 2 parts by weight).

[0157] Alternatively, the amount of peroxide used as a vulcanizing agent may be approximately 1 × 10⁻⁶ per 100 parts by weight of rubber. -5 moles to approximately 1×10 -1 mole, approximately 1 × 10 -4 moles to approximately 9 × 10 -2 mole, approximately 1 × 10 -2 moles to approximately 4 × 10 -2The amount is expressed in moles. This quantity can also be expressed as the weight of 100 parts by weight of rubber. However, this amount may vary depending on the curing agent used. For example, in the case of using 4,4-bis(tert-butylperoxide)diisopropylbenzene, the amount may include about 0.5 parts by weight to about 12 parts by weight per 100 parts by weight of rubber, such as about 1 part by weight to about 6 parts by weight. Those skilled in the art can readily determine a sufficient or effective amount of additives that can be used with peroxides without excessive calculation or experimentation. The amount of additives used may be similar in molarity to the number of moles of the curing agent used. The amount of additives may also be expressed as the weight of 100 parts by weight of rubber. For example, in the case of using triallyl cyanurate additives, the amount may include about 0.25 phr to about 20 phr based on 100 parts by weight of rubber, such as about 0.5 phr to about 10 phr.

[0158] The TPV composition may include reaction products formed by the above-described reactive dynamic vulcanization curing process. This curing process may be used alone or in combination with any suitable dynamic vulcanization method for thermoplastic vulcanizates. The TPV composition may include reaction products from a composition comprising rubber, a crosslinking agent, a thermoplastic resin containing a cyclic olefin copolymer, and an oil, which are then dynamically cured. The thermoplastic vulcanizate composition has a vibration damping peak that appears between about -20°C and about 60°C.

[0159] application

[0160] The TPV compositions described herein have potential applications in building materials, electrical and electronic equipment (e.g., personal computers, office automation equipment, audiovisual equipment, and cellular phones), optical instruments, precision instruments, toys, and components and housings for home / office appliances, particularly in parts and molding materials for the transportation industry (e.g., rail vehicles, automobiles, ships, and aircraft). In addition to general material properties such as impact resistance, heat resistance, strength, and dimensional stability, these applications also require vibration damping and sound insulation properties. TPV compositions have further applications for damping vibrations generated by engine or tire pattern noise. More specifically, thermoplastic vulcanizate compositions can be used in automobiles with electric motors, such as hybrid vehicles, plug-in hybrid vehicles, fuel cell vehicles, or electric vehicles. The TPV compositions described herein can block transmitted vibrational sound represented by the low-frequency range. Furthermore, TPV compositions are also effective at blocking sound in the high-frequency range of 1 kHz to 6 kHz, which is sensitive to human hearing.

[0161] Example

[0162] General Procedure

[0163] The thermoplastic vulcanizate compositions of Examples 1 and 2 below were prepared using several common raw materials as shown below:

[0164] PP1: Commercial purchase of ExxonMobil TM A low melt flow rate polypropylene homopolymer with a melt flow rate of 0.83 g / 10 min (ASTM D 1238, 230℃ / 2.16 kg) and a melt flow rate of 0.9 g / cm³. 3 The density.

[0165] PP2: Commercial purchase Braskem TM Polypropylene homopolymer with a melt flow rate of 17 g / 10 min (ASTM D 1238, 230 °C / 2.16 kg).

[0166] COC1: TOPAS TM 8007. Commercially available cyclic olefin copolymer with a strength of 1010 kg / m³. 3 Density (ISO 1183), 2cm³ 3 Melt volume rate per 10 min (ISO 1133, 190℃ / 2.16kg), glass transition temperature of 78℃ (10℃ / min, ISO11357-1,-2,-3), and norbornene content of 66-68wt%.

[0167] MB1: Carbon black masterbatch containing polypropylene homopolymer and carbon black pigment (41 wt%).

[0168] MB2: Anhydrous SnCl2 masterbatch containing polypropylene homopolymer and SnCl2 (45wt%).

[0169] PO1: Group II paraffin oil, kinematic viscosity 108 cst @ 40℃ (by trade name Paramount) TM 6001R purchased from Chevron Philips TM ).

[0170] ZnO: sold under the brand name Kadox TM 911 obtained commercially available ZnO curing retardant / acid remover.

[0171] RIO1: A mixture of phenolic resins in oil, octyl and isononyl phenolic resins, with 30 wt% of the resin dispersed in a type II paraffin oil (70 wt%).

[0172] Clay: under the trade name Icecap TM Calcined clay obtained by K Clay (from Burgess) TM ).

[0173] The thermoplastic vulcanized rubber compositions of Examples 1 and 2 below were also tested using several common procedures, as follows:

[0174] Shore A hardness was measured 15 seconds and 1 second after indentation. The test was performed according to ASTM D2240.

[0175] Tensile properties (100% modulus, tensile strength, ultimate elongation) were measured according to ASTM D412 at 500 mm / min.

[0176] Compression deformation was measured according to ASTM D395, Method B (25% compression, 22 hours @ 70°C; 25% compression, 22 hours @ 23°C).

[0177] Oil swelling was measured according to ASTM D471 (24 hours, 121°C) and expressed as an increment in wt%.

[0178] Specific gravity was measured at 23°C according to ASTM D792.

[0179] LCR capillary viscosity is measured using a laboratory capillary rheometer (such as the Ceast "Smart Rheo" rheometer). TM A capillary die with a 30 / 1L / D ratio and a circular orifice with a diameter of 1 mm (0.040") was used to measure the results at 204°C and a shear rate of 1200 l / s.

[0180] DMTA: Tanδ properties were determined by dynamic mechanical temperature analysis in torsion mode using a heating rate of 2 °C / min, a frequency of 10 Hz, and an amplitude of 0.15% to 1%. Dynamic viscoelasticity was measured under these conditions using an ARES viscoelasticity analyzer. The ratio of the measured storage modulus (G') to the loss modulus (G”) was defined as the loss tangent tanδ. A convex curve or peak was obtained when tanδ was plotted against temperature. The temperature at the peak apex was defined as the glass transition temperature, and the maximum tanδ value at that temperature was determined. When two peaks were observed in tanδ within a temperature window of -20 °C to 100 °C, the peaks were defined as the first and second peaks, and the Tg values ​​and the maximum tanδ values ​​of these two peaks were recorded.

[0181] Example 1: EPDM-based thermoplastic vulcanized rubber composition

[0182] This embodiment demonstrates that the EPDM-based thermoplastic vulcanizate composition of the present invention exhibits better vibration damping performance than conventional thermoplastic vulcanizate compositions. Specifically, compared with the comparative composition, the EPDM-based thermoplastic vulcanizate composition of the present invention exhibits (1) a higher tanδ peak value and (2) a wider and higher tanδ peak temperature window.

[0183] The thermoplastic vulcanizate composition is prepared using a plastic phase comprising (1) a cyclic olefin copolymer or (2) a blend of a cyclic olefin copolymer and a polypropylene homopolymer. The polypropylene homopolymer is PP1 or PP2 (as described above). ExxonMobil is a commercially available option. TM EPDM, as a crosslinked rubber in a thermoplastic vulcanized rubber composition, has a phr of 75 (42.86 wt% oil), a Mooney viscosity of 52 MU (measured by ASTM D1646, ML 1+4, 125 °C), an ethylene content of 64 wt% (the remainder being propylene), and an ethylene norbornene (ENB) content of 4.5 wt%.

[0184] These thermoplastic vulcanizate compositions were produced on a twin-screw extruder. Coperion was used. TM The company (Ramsey NJ) provides a co-rotating, fully intermeshing twin-screw extruder for using a similar method described in U.S. Patent Application Publication No. 2011 / 0028637, which is incorporated herein by reference for all purposes (except for variations specified herein). EPDM is fed to a ZSK extruder with an L / D (extruder length / diameter) of approximately 44. TM 53. Extruder feed inlet. Thermoplastic resin (polypropylene) is fed into the feed inlet along with other reaction rate control agents (such as zinc oxide and stannous chloride). Fillers such as clay and black MB are also added to the extruder feed inlet. Processing oil is injected into the extruder at two different locations along the extruder. After the rubber, thermoplastic, and filler have begun to blend, a curing agent is injected into the extruder at approximately 18.7 L / D, but a first processing oil (pre-cured oil) is introduced at approximately 6.5 L / D prior to this. In some embodiments, the curing agent is injected along with the processing oil, which may be the same as or different from other oils introduced into the extruder or oils used for rubber increments. After the curing agent injection, a second processing oil (post-cured oil) is injected into the extruder at approximately 26.8 L / D. The rubber crosslinking reaction is initiated and controlled by balancing the combination of viscous heat generation due to applied shear, barrel temperature setpoint, catalyst use, and residence time.

[0185] Unless otherwise specified, feed the extruded material into the extruder at a rate of 70 kg / hr and perform extrusion mixing at 325 rpm. Use a barrel metal temperature profile in degrees Celsius, starting from barrel section 2 and moving downwards towards the die to barrel section 12 at 160 / 160 / 160 / 165 / 165 / 165 / 165 / 165 / 180 / 180 / 180 / 180°C (where the last value is for the die). Low molecular weight contaminants, reaction byproducts, residual moisture, etc., are removed by effluent discharge through one or more outlets (usually under vacuum if necessary). Filter the final product using a melt gear pump and a filter with the desired mesh size. Employ a screw design with multiple mixing sections (including combinations of forward conveying, neutral, left-hand kneading blocks, and left-hand conveying elements) to mix the processing oil, curing agent, and provide sufficient residence time and shear to complete the curing reaction without slippage or fluctuation within the extruder.

[0186] Tables 2A and 2B below show the composition of the thermoplastic vulcanizate compositions. Tables 3A and 3B below further show the physical properties of the same thermoplastic vulcanizate compositions.

[0187] Table 2A: EPDM-based thermoplastic vulcanizate compositions (unless otherwise specified, all units are in phr)

[0188]

[0189]

[0190] Table 2B: EPDM-based thermoplastic vulcanizate compositions (unless otherwise specified, all units are in phr)

[0191]

[0192] Table 3A Physical properties of EPDM-based thermoplastic vulcanized rubber compositions

[0193]

[0194] Table 3B Physical properties of EPDM-based thermoplastic vulcanized rubber compositions

[0195]

[0196]

[0197] Figure 1 Tables 3A and 3B show that the thermoplastic vulcanized rubber compositions of the present invention exhibit a broad tanδ peak with the largest peak value in a temperature window of -20 to 60°C. Figure 1As shown, compared to Comparative Example 1, this thermoplastic vulcanizate composition exhibits a higher and wider temperature window for the tanδ peak. As shown in Tables 3A and 3B, IEx3 reaches a maximum tanδ peak value of 1.08.

[0198] Δhardness is another property that can be used to determine the damping properties of these thermoplastic rubber vulcanized compositions. A higher Δhardness indicates better damping properties. All the thermoplastic rubber vulcanized compositions of the present invention exhibit higher Δhardness than Comparative Example 1 (and thus better damping properties). The thermoplastic rubber vulcanized compositions exhibiting improved damping properties also possess comparable tensile properties, compression set (or elastic properties), and processability. Scratch-healing ability has also been observed in these thermoplastic rubber vulcanized compositions. Once a scratch is formed on the thermoplastic rubber vulcanized composition, the scratch disappears over time.

[0199] Figure 4 , Figure 5A , Figure 5B and Figure 5C This indicates that, compared to Comparative Example 1, the thermoplastic vulcanized rubber composition exhibits improved morphology and dispersibility of rubber particles, even though the plastic phase is entirely composed of cyclic olefin copolymers and contains no polypropylene homopolymer. Figure 5A , Figure 5C (For filming) Figure 4 , Figure 5A , Figure 5B and Figure 5C The images shown are from Comparative Example 1 and samples prepared from thermoplastic vulcanizate compositions IEx1, IEx2, and IEx3. Samples were cut and loaded into an atomic force microscope (AFM) sample holder (Leica, part number 16702448), and then cryosectioned at -120°C on the desired plane using a Leica microtome. All samples were cleaned with N2 in a desiccator prior to AFM imaging. (Based on ExxonMobil) TM Method 120, Revision 10, was established using Bruker. TM AFM images were acquired using a Dimension Icon atomic force microscope. Scanning was performed using a Bruker TESPAW-V2 cantilever (spring constant ~42 N / m, resonant frequency ~320 kHz). Imaging was performed using free air amplitude (Af) and setpoint to maintain net repulsive tip-sample interaction. The monitored data channels were “height” and “phase”, with Af at 1 V.

[0200] Example 2: BIMS-based thermoplastic vulcanized rubber composition

[0201] This embodiment demonstrates that the BIMS-based thermoplastic vulcanizate composition of the present invention exhibits better vibration damping performance than conventional thermoplastic vulcanizate compositions. Furthermore, this embodiment shows that the EPDM-based thermoplastic vulcanizate composition of Example 1 and the BIMS-based thermoplastic vulcanizate composition of Example 2 possess similar damping, tensile, and elastic properties.

[0202] Thermoplastic vulcanized rubber compositions were prepared and tested in a similar manner to those in Example 1. ExxonMobil was commercially available. TM The specialty elastomer is a brominated copolymer of isobutylene and p-methylstyrene, selected as the crosslinked rubber (BIMSM1). This rubber has a Mooney viscosity of 45 (ML1+8, 125°C, ASTM D1646) and contains 1.2 mol% benzyl bromide. Stearic acid is used as the curing agent. Maglite is added... TM D purchased MgO.

[0203] Table 4 below shows the components of the thermoplastic vulcanized rubber composition. Table 5 below further shows the physical properties of the same thermoplastic vulcanized rubber composition.

[0204] Table 4. BIMS-based thermoplastic vulcanizate compositions (unless otherwise specified, all units are phr)

[0205]

[0206] Table 5 Physical properties of thermoplastic vulcanized rubber compositions based on BIMS

[0207]

[0208]

[0209] Figure 2 Table 5 shows that the thermoplastic vulcanized rubber composition of the present invention exhibits a broad tanδ peak with the largest peak value in a temperature window of 0 to 60°C. Figure 2 As shown, compared to Comparative Examples 2 and 3, IEx13 exhibits a higher and wider temperature window for the tanδ peak. As shown in Table 5, IEx14 reaches a maximum tanδ peak value of 1.2. Compared to the EPDM-based thermoplastic vulcanizate composition of Example 1, the BIMS-based thermoplastic vulcanizate composition of Example 2 exhibits a similar tanδ peak value and temperature window. Furthermore, the EPDM-based thermoplastic vulcanizate composition of Example 1 and the BIMS-based thermoplastic vulcanizate composition of Example 2 exhibit similar damping, tensile, and elastic properties.

[0210] Example 3 Glass transition temperature

[0211] This embodiment shows that the rigidity of the thermoplastic vulcanized rubber composition can be adjusted by the norbornene content of the cyclic olefin copolymer. The Tg of the thermoplastic vulcanized rubber composition containing the cyclic olefin copolymer is in the range of about 0°C to about 120°C, and in the pure state, the Tg of the cyclic olefin copolymer is in the range of about 30°C to about 180°C and is always higher than the Tg of the thermoplastic vulcanized rubber composition.

[0212] Using ExxonMobil TM VISTALON TM 3666 (MFR 0.8g / 10min, 230℃) is used as an EPDM crosslinked rubber and is derived from ExxonMobil. TM PP5341E1 was used as a polypropylene homopolymer to prepare thermoplastic vulcanizate compositions in a Brabender mixer. PP5341E1 from TOPAS was selected. TM Various cyclic olefin copolymers with different glass transition temperatures (Tg). The cyclic olefin copolymer is TOPAS. TM Models 6017, 6013, 5013, 8007, 9506, 9903, and E140. Vistalon TM 3666 is a high Mooney EPDM with an oil increment of 75 phr. The curing system is a phenolic resin co-catalyzed by SnCl2 / ZnO. The weight ratio of plastic (polypropylene and cyclic olefin copolymer) to EPDM is fixed at 30 / 70.

[0213] Thermoplastic vulcanizates were prepared by dynamically vulcanizing elastic copolymers in a Brabender mixer using a conventional procedure that involves vulcanization with phenolic resin (e.g., phenolic resin in an oil curing agent containing approximately 30 wt% phenolic resin and 70 wt% oil) in the presence of stannous chloride (SnCl2·2H2O) and zinc oxide (ZnO). Specifically, the thermoplastic vulcanizates were prepared in a laboratory Brabender plasticizer (model EPL-V5502). The mixing bowl had a capacity of 85 ml and used a cam-type rotor. First, the rubber was added to the mixing bowl, which was heated to 180°C and rotated at 100 rpm. Then, plastic (typically granulated polypropylene), clay, black MB, and zinc oxide were added to the mixer and melt-mixed for 2 minutes. Paraffin oil (pre-cured oil) was then added dropwise over 1 minute, and mixing continued for 1 to 5 minutes before adding the phenolic resin (at which point a stable torque was obtained). The phenolic resin was then added to the mixing bowl, followed by stannous chloride MB, resulting in an increase in motor torque due to the curing reaction.

[0214] Continue mixing for an additional 4 minutes, then remove the molten TPV from the mixer and run it over a Teflon container. TMThe plates are hot-pressed together to form a thin sheet, which is then cooled, cut, and compressed into shape at approximately 400°F (204.4°C). Wabash is used. TM Compression molding was performed using a press (model 12-1212-2TMB) with a four-cavity Teflon-coated mold measuring 4.5” x 4.5” x 0.06”. The material in the mold was first preheated on a 4” punch at approximately 400°F (204.4°C) under 2 tons of pressure for approximately 2 to 2.5 minutes. The pressure was then increased to 10 tons, and heating continued for an additional 2 to 2.5 minutes. The molding press was then cooled with water to approximately 70°C, after which the mold pressure was released.

[0215] like Figure 3A As shown, with TOPAS TM The thermoplastic vulcanizate compositions of 6017 / 6013 / 5013 show no significant change or a slight increase in hardness with increasing cyclic olefin copolymer content. This can be explained by the fact that the Tg of these pure cyclic olefin copolymers is much higher than room temperature. For TOPAS TM For 8007 / 9506 / 9903 / E140, the hardness of the corresponding thermoplastic vulcanizate compositions decreases significantly with increasing cycloolefin copolymer content, making the thermoplastic vulcanizate compositions feel softer.

[0216] Figure 3B The results show that the Tg of the cyclic olefin copolymer in the thermoplastic vulcanizate composition is lower than that of the pure cyclic olefin copolymer because the amorphous cyclic olefin copolymer is plasticized by the oil in the EPDM rubber. These results indicate that the softness of the thermoplastic vulcanizate composition based on the cyclic olefin copolymer can be altered by different combinations of the cyclic olefin copolymer and the polypropylene homopolymer. Furthermore, the Tg of the cyclic olefin copolymer can be changed by altering the molecular structure of the cyclic olefin copolymer (selecting different cyclic olefin copolymers) or by plasticizing the cyclic olefin copolymer (adding a plasticizer to the formulation).

[0217] Figure 3B It is also shown that the glass transition temperature of the cyclic olefin copolymer increases as norbornene is included in the backbone. The Tg range of thermoplastic vulcanized rubber compositions including cyclic olefin copolymers is from about 0°C to about 120°C, while the Tg range of cyclic olefin copolymers in their pure state is from about 30°C to about 180°C, and is always higher than the Tg of thermoplastic vulcanized compositions.

[0218] One or more specific embodiments of the TPV composition have been described. To provide a concise description of these embodiments, it is impossible to describe all features of an actual implementation in this specification. It should be understood that during the development of any such actual implementation, as in any engineering or design project, numerous decisions must be made regarding specific implementations to achieve the developer's specific objectives, such as compliance with system-related and business-related constraints, which may vary depending on the implementation method. Furthermore, it should be understood that such development efforts can be complex and time-consuming, but will be routine tasks for those skilled in the art who understand the benefits of this invention in design, manufacture, and production.

[0219] Certain terms are used throughout the specification and claims to refer to specific features or components. Those skilled in the art will understand that different people may refer to the same feature or component using different names. This document is not intended to distinguish between components or features that are different in name rather than function.

[0220] The figures disclosed herein are approximate, regardless of whether the words “about” or “approximately” are used in connection with them. When a range of lower and upper limits for numerical values ​​is disclosed, any number within that range is specifically disclosed. When the term “includes” is used, it encompasses “including, but not limited to”. All documents mentioned herein are incorporated herein by reference to apply to all jurisdictions, provided that such reference does not conflict with this document.

[0221] Throughout this specification, references to "an embodiment," "an embodiment," "a particular embodiment," "some embodiments," "some examples," "a specific embodiment," etc., indicate that a particular feature, structure, or characteristic described in connection with that embodiment may be included in at least one embodiment of this disclosure. Therefore, these phrases or similar language throughout this specification may, but not necessarily, refer to the same embodiment.

[0222] The disclosed embodiments should not be construed as limiting the scope of this disclosure (including the claims). It should be fully appreciated that the different teachings of the discussed embodiments can be used alone or in any suitable combination to produce the desired results. Furthermore, those skilled in the art will understand that the description has broad application, and that any discussion of any embodiment is intended only as an example of that embodiment and not to limit the scope of this disclosure (including the claims) to that embodiment.

Claims

1. A thermoplastic vulcanized rubber composition comprising: Thermoplastic matrix and oil containing cyclic olefin copolymers; and Particles dispersed in the thermoplastic matrix and comprising at least partially cross-linked rubber; The cyclic olefin copolymer has a glass transition temperature (Tg) of 30°C to 100°C in its pure state. The cyclic olefin copolymer is selected to influence the vibration damping properties of the thermoplastic vulcanizate composition.

2. The thermoplastic vulcanized rubber composition according to claim 1, wherein, The thermoplastic vulcanizate composition exhibits a tanδ curve including peaks appearing between -20°C and 90°C with peak values ​​ranging from 0.1 to 2.

0.

3. The thermoplastic vulcanized rubber composition according to claim 1, wherein, The thermoplastic vulcanized rubber composition has a compression set of 15% to 50% after being compressed at 70°C for 22 hours.

4. The thermoplastic vulcanized rubber composition according to claim 1, wherein, The thermoplastic vulcanized rubber composition has a hardness of 15 to 95 as measured on a Shore A hardness scale 15 seconds after imprinting.

5. The thermoplastic vulcanized rubber composition according to claim 1, wherein, The thermoplastic vulcanized rubber composition has a hardness of 15 to 50 as measured on a Shore D hardness scale 15 seconds after imprinting.

6. The thermoplastic vulcanized rubber composition of claim 1, wherein, The cyclic olefin copolymer has a glass transition temperature (Tg) of 30°C to 90°C in its pure state.

7. The thermoplastic vulcanized rubber composition of claim 1, wherein, The thermoplastic matrix comprises blends of cyclic olefin copolymers with different glass transition temperatures.

8. The thermoplastic vulcanized rubber composition of claim 1, wherein, The cyclic olefin copolymer includes an ethylene-norbornene copolymer containing 10 wt% to 90 wt% norbornene.

9. The thermoplastic vulcanized rubber composition of claim 1, wherein, The at least partially crosslinked rubber includes brominated isobutyl p-methylstyrene (BIMSM) polymers, ethylene α-olefin non-conjugated diene copolymers, ethylene propylene diene copolymers, or combinations thereof.

10. The thermoplastic vulcanized rubber composition of claim 9, wherein, The ethylene-propylene diene copolymer includes a diene, which includes ethylidene norbornene, vinyl norbornene, or a combination thereof.

11. The thermoplastic vulcanized rubber composition of claim 1, wherein, The at least partially crosslinked rubber is ethylene propylene rubber, butyl rubber, halogenated butyl rubber, C4 to C7 isomonoolefins and p-alkylstyrene halogenated copolymers or combinations thereof.

12. The thermoplastic vulcanized rubber composition of claim 11, wherein, The butyl rubber is isobutylene-p-methylstyrene rubber, which contains 0.5 wt% to 25 wt% p-methylstyrene based on the weight of the isobutylene-p-methylstyrene rubber.

13. The thermoplastic vulcanized rubber composition of claim 11, wherein, The butyl rubber is an isobutylene-isoprene rubber, which contains 0.5 wt% to 30 wt% isoprene based on the weight of the isobutylene-isoprene rubber.

14. The thermoplastic vulcanized rubber composition of claim 11, wherein, The butyl rubber is brominated isobutylene-isoprene rubber, chlorinated isobutylene-isoprene rubber, or a combination thereof, and contains 0.3 wt% to 7 wt% of halogen based on the weight of the butyl rubber.

15. The thermoplastic vulcanized rubber composition of claim 11, wherein the thermoplastic vulcanized rubber composition comprises, by weight, 50 to 450 parts (50 phr to 450 phr) of the oil per 100 parts of rubber.

16. The thermoplastic vulcanized rubber composition of claim 15, wherein, The oil is selected from mineral oil, paraffin oil, polyisobutylene, synthetic oil, and combinations thereof.

17. The thermoplastic vulcanized rubber composition of claim 1, wherein, The thermoplastic vulcanized rubber composition comprises, by weight, 20 to 500 parts (20 phr to 500 phr) of the thermoplastic matrix per 100 parts of rubber.

18. The thermoplastic vulcanized rubber composition of claim 1, wherein, The thermoplastic matrix comprises 1 wt% to 100 wt% of the cyclic olefin copolymer and up to 99 wt% of a semi-crystalline acyclic polyolefin.

19. The thermoplastic vulcanized rubber composition of claim 1, wherein, The thermoplastic matrix comprises polypropylene.

20. The thermoplastic vulcanized rubber composition of claim 1, wherein, The thermoplastic vulcanized rubber composition further comprises a heat stabilizer, an ultraviolet stabilizer, or a combination thereof.

21. The thermoplastic vulcanized rubber composition of claim 1, wherein, The thermoplastic vulcanized rubber composition further comprises fillers, slip agents, nucleating agents, or combinations thereof.

22. The thermoplastic vulcanized rubber composition of claim 21, wherein, The filler includes calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, mica, wood flour, or a combination thereof.

23. The thermoplastic vulcanized rubber composition of claim 21, further comprising a curing system.

24. The thermoplastic vulcanized rubber composition of claim 23, wherein, The curing system includes phenolic resin, peroxide, maleimide, hexamethylenediamine carbamate, silicon-based curing agent, silane-based curing agent, metal oxide, sulfur-based curing agent, or a combination thereof.

25. A thermoplastic vulcanized rubber composition comprising: A thermoplastic matrix and oil containing partially crystalline cyclic olefin copolymer elastomers; and Particles dispersed in the thermoplastic matrix and comprising at least partially cross-linked rubber; The partially crystalline cyclic olefin copolymer elastomer comprises norbornene and ethylene, and has a glass transition temperature (Tg) of less than 30°C, a crystallization melting temperature of less than 125°C, and a crystallinity of 40 wt% or less.

26. The thermoplastic vulcanized rubber composition of claim 25, wherein, The thermoplastic matrix further comprises a blend of the partially crystalline cyclic olefin copolymer elastomer and the amorphous cyclic olefin copolymer.

27. The thermoplastic vulcanized rubber composition of claim 25, wherein, The thermoplastic matrix further comprises a blend of the partially crystalline cyclic olefin copolymer elastomer and the acyclic polyolefin.

28. The thermoplastic vulcanized rubber composition of claim 27, wherein, The acyclic polyolefin is polypropylene.

29. The thermoplastic vulcanized rubber composition of claim 27, wherein, The acyclic polyolefin is polyethylene.

30. A thermoplastic vulcanizate composition comprising a reaction product of dynamically curing a composition comprising: rubber; Crosslinking agent; Thermoplastic resins containing cyclic olefin copolymers; and Oil; The cyclic olefin copolymer has a glass transition temperature (Tg) of 30°C to 100°C in its pure state. The cyclic olefin copolymer is selected to influence the vibration damping properties of the thermoplastic vulcanizate composition.

31. The thermoplastic vulcanized rubber composition of claim 30, wherein, The thermoplastic vulcanized rubber composition has a vibration damping peak that appears between -20°C and 90°C.

32. The thermoplastic vulcanized rubber composition of claim 30 or 31, wherein, The cyclic olefin copolymer has a glass transition temperature (Tg) of 30°C to 90°C in its pure state.

33. The thermoplastic vulcanized rubber composition of claim 30, wherein, The cyclic olefin copolymer includes an ethylene-norbornene copolymer, wherein the ethylene-norbornene copolymer contains 40 wt% to 90 wt% norbornene.

34. The thermoplastic vulcanized rubber composition of claim 30, wherein, The rubber includes an ethylene propylene diene (EPDM) polymer.

35. The thermoplastic vulcanized rubber composition of claim 30, wherein, The rubber comprises a brominated isobutyl p-methylstyrene (BIMSM) polymer.

36. The thermoplastic vulcanized rubber composition of claim 30, wherein, The composition comprises, by weight, 50 to 450 parts (50 phr to 450 phr) of the oil per 100 parts of rubber.

37. The thermoplastic vulcanized rubber composition of claim 30, wherein, The thermoplastic vulcanized rubber composition comprises, by weight, 20 to 500 parts (20 phr to 500 phr) of the thermoplastic resin per 100 parts of rubber.

38. The thermoplastic vulcanized rubber composition of claim 30, wherein, The thermoplastic resin comprises 1 wt% to 100 wt% of the cyclic olefin copolymer and up to 99 wt% of a semi-crystalline acyclic polyolefin.

39. A thermoplastic vulcanized rubber composition comprising: Dynamically cured rubber containing ethylene propylene diene (EPDM) polymer or brominated isobutyl p-methylstyrene (BIMSM) polymer; A thermoplastic resin comprising, by weight, 20 to 500 parts (20 phr to 500 phr) of thermoplastic resin per 100 parts of rubber, wherein the thermoplastic resin comprises 1 wt% to 100 wt% of a cyclic olefin copolymer and up to 99 wt% of a semi-crystalline acyclic polyolefin, wherein the cyclic olefin copolymer has a glass transition temperature (Tg) of 30°C to 100°C in its pure state; and Oil in amounts of 50 to 450 parts by weight (50 to 450 phr) per 100 parts of rubber; and The tanδ curve of the thermoplastic vulcanized rubber composition includes peaks appearing between -20°C and 90°C with peak values ​​between 0.1 and 2.0; and The thermoplastic vulcanized rubber composition described herein has a compression set of 15% to 50% after compression at 70°C for 22 hours, and a hardness of 15 to 95 as measured on a Shore A hardness scale 15 seconds after indentation.

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