Composition having an ethylene / alpha-olefin copolymer, an olefin-based polymer, and a crosslinking agent, and an article prepared therefrom

Abstract

The embodiment relates to a composition comprising an ethylene / α-olefin copolymer, an olefin-based polymer, and a crosslinking agent. The ethylene / α-olefin copolymer comprises a density of 0.860 to 0.900 g / cc, a melt index (I2) of 0.5 to 30 dg / min, with I2 measured according to ASTM D1238 (190°C, 2.16 kg), an I10 / I2 of 8 or more, with I10 measured according to ASTM D1238 (190°C, 10 kg), at least 0.05 vinyls per 1,000 carbons, at least 50% of the total unsaturated vinyl, and an oligomer level of less than 5,000 ppm.

Description

Technology Field

[0001] The embodiments of the present disclosure generally relate to thermoplastic vulcanizate compositions, and specifically to compositions comprising an ethylene / α-olefin copolymer, an olefin-based polymer, and a crosslinking agent, which are used to form a crosslinked composition having an improved compression permanent strain while maintaining processability. Background Technology

[0002] Thermoplastic vulcanizates (TPVs) are materials having cross-linked rubber domains within a continuous thermoplastic matrix. While the rubber domains can influence softness and elasticity properties, the thermoplastic matrix can influence the TPV's oil barrier resistance, flow characteristics, and temperature limits. TPVs are manufactured through dynamic vulcanization of immiscible blends of rubber and thermoplastic materials, that is, by selectively cross-linking the rubber while melt-mixing it with the thermoplastic material. Typically, TPVs are manufactured using polypropylene (PP) as the thermoplastic matrix and ethylene-propylene-diene rubber (EPDM) or polyolefin elastomers as the rubber phase. The rubber phase can be cross-linked using peroxides to maintain good color and reduce toxicity, in contrast to phenolic curing.

[0003] Compared to their non-crosslinked thermoplastic elastomer (TPE) counterparts, TPVs have superior properties in terms of heat resistance, permanent compression strain, chemical resistance, and tensile strength. However, conventional TPVs may lack the desired mechanical properties, particularly permanent compression strain.

[0004] Therefore, a TPV composition having improved compressive permanent strain while maintaining processability is required.

[0005] The embodiments of the present disclosure satisfy this need by using a polyolefin elastomer having a high vinyl level, a low oligomer level, and a high level of long-chain branching (LCB) on the polymer chain-terminals. This provides processability (e.g., 0.1 rad / s) and viscosity (V) as measured at 230°C. 0.1 ) is greater than 105,000 Pa·s, and viscosity (V) as measured at 1,000 rad / s and 230℃ 1k This results in a composition that can be crosslinked to form a crosslinked composition having an improved compressive permanent strain (e.g., 60% or less at 70 hr and 120°C) while maintaining a compressive strain of less than 130 Pa·s.

[0006] In one embodiment, the polyolefin elastomer comprises a composition including an ethylene / α-olefin copolymer, an olefin-based polymer, and a crosslinking agent, wherein the ethylene / α-olefin copolymer has a density of 0.860 to 0.900 g / cc, a melt index (I2) of 0.5 to 30 dg / min, I2 measured according to ASTM D1238 (190°C, 2.16 kg), and I 10 I of 8 or more, measured according to ASTM D1238 (190℃, 10 kg). 10 / I2; contains more than 0.2 vinyls per 1,000 carbons, more than 50% of the total unsaturated vinyl, and less than 5,000 ppm of oligomer levels.

[0007] Additional features and benefits will be described in the following detailed description, and will be partly apparent to those skilled in the art from such description or recognized by practicing the embodiments described herein, including the following detailed description and claims.

[0008] It should be understood that both the foregoing general description and the following detailed description are intended to describe various embodiments and to provide an overview or framework for understanding the nature and features of the claimed subject matter. Specific details for implementing the invention

[0009] Specific embodiments of the present application will now be described. The disclosure may be implemented in different forms and should not be construed as being limited to the embodiments presented in this disclosure. Rather, these embodiments are provided to ensure that the disclosure is complete and sufficiently conveys the scope of the essence of the technology to those skilled in the art.

[0010] definition

[0011] Unless otherwise noted, all test methods are in common use as of the filing date of this disclosure, either implicitly from the context or as is customary in the art.

[0012] In this document, ranges may be expressed as "about" from one specific value and / or "about" from another specific value. When such ranges are expressed, other embodiments include 'greater than' that specific value and / or 'less than' that specific value. Similarly, where a value is expressed as an approximation by the use of the antecedent "about," that specific value will be understood to constitute another embodiment. Furthermore, each endpoint of a range will be understood to be significant in relation to and independently of other endpoints.

[0013] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing the same or different types of monomers. The general term polymer includes homopolymers (used to refer to polymers prepared from only a single type of monomer, and it should be understood that trace amounts of impurities may be incorporated into the polymer structure), and the term interpolymer as defined below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, the polymer is stabilized by one or more stabilizers in very small amounts ("ppm" amounts).

[0014] As used herein, the term "solution polymerization" refers to a polymerization process occurring in a solution of monomers and polymers in a solvent. Polymerization may occur in a single reactor or multiple reactors. Various reactors, for example, loop reactors or continuous stirred tank reactors (CSTRs), are considered suitable. The solution polymerization process may occur at temperatures exceeding 150°C, 170°C, or 180°C. Furthermore, the solution polymerization process may occur at pressures exceeding 30 bar (3 MPa) or 40 bar (4 MPa). Various hydrocarbon solvents are considered suitable for solution polymerization.

[0015] As used herein, the term "copolymer" refers to a polymer produced by the polymerization of at least two different types of monomers. Accordingly, the term copolymer includes the term copolymer (used to refer to a polymer produced from two different types of monomers) and a polymer produced from more than two different types of monomers.

[0016] The term “olefinic polymer” as used herein refers to a polymer that, in a polymerized form, comprises a majority of olefin monomers, e.g., ethylene or propylene (based on the weight of the polymer) and may optionally comprise one or more comonomers.

[0017] The term “polyolefin” as used herein refers to a polymer comprising 50% by weight or most by weight of an olefin, such as ethylene or propylene, in a polymerized form (based on the weight of the polymer), and optionally may comprise one or more comonomers.

[0018] The terms “ethylene-based polymer” or “polyethylene” as used herein refer to a polymer comprising 50% by weight or most by weight of ethylene in a polymerized form (based on the weight of the polymer) and optionally comprising one or more comonomers.

[0019] The term "ethylene / α-olefin copolymer" as used herein means a copolymer comprising a majority amount of polymerized ethylene monomer (based on the weight of the copolymer) and at least one α-olefin.

[0020] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer comprising, in a polymerized form, 50 weight percent or most weight percent of ethylene and α-olefin as only two monomer types (based on the weight of the copolymer). Preferably, the ethylene / α-olefin copolymer is a random copolymer (i.e., having a random distribution of its monomeric components).

[0021] As used herein, the term "propylene-based polymer" refers to a polymer comprising a majority amount of polymerized propylene monomers (based on the weight of the polymer) and optionally comprising one or more comonomers.

[0022] The term "propylene / α-olefin copolymer" as used herein refers to a copolymer comprising, in a polymerized form, a majority amount of propylene monomer and at least one α-olefin (based on the weight of the copolymer).

[0023] The term “propylene / α-olefin copolymer” as used herein refers to a copolymer comprising, in a polymerized form with only two monomer types, a majority amount of propylene monomer and α-olefin (based on the weight of the copolymer).

[0024] The term "propylene / ethylene copolymer" as used herein refers to a copolymer comprising, in a polymerized form, a majority amount of propylene monomer and ethylene (based on the weight of the copolymer).

[0025] The term “propylene / ethylene copolymer” as used herein refers to a copolymer comprising, in a polymerized form as only two monomer types, a majority amount of propylene monomer and ethylene (based on the weight of the copolymer).

[0026] As used herein, the terms "crosslinked composition" or "crosslinked polyolefin elastomer" refer to a composition having a network structure due to the formation of chemical bonds between polymer chains.

[0027] As used herein, the term "composition" includes not only a mixture of materials comprising the composition, but also reaction products and decomposition products formed from the materials of the composition.

[0028] Terms used at this institution "V 0.1 "It serves as the viscosity at a specified temperature and under measurement conditions of 0.1 rad / s (DMS measurement). Unless otherwise noted, complex viscosity is measured by the DMS rheology method.

[0029] Terms used at this institution "V 100 "It serves as the viscosity under measurement conditions of 100 rad / s (DMS measurement) and at a specified temperature. Unless otherwise noted, complex viscosity is measured by the DMS rheology method.

[0030] Terms used at this institution "V 1k 1,000 s by the capillary rheology method -1 It serves as the viscosity under measurement conditions and at a specified temperature.

[0031] embodiments

[0032] Polyolefin Elastomer (POE) - Ethylene / α-olefin copolymer

[0033] An embodiment of the present disclosure comprises an ethylene monomer and at least one C4-C 12The invention relates to a polyolefin elastomer comprising a polymerized reaction product of an α-olefin comonomer. The terms "polyolefin elastomer" and "ethylene / α-olefin copolymer" are used interchangeably throughout. The polyolefin elastomer comprises: a density of 0.860 to 0.900 g / cc; a melt index (I2) of 0.5 to 30 dg / min, where I2 is measured according to ASTM D1238 (190°C, 2.16 kg); I 10 I of 8 or more, measured according to ASTM D1238 (190℃, 10 kg). 10 / I2; more than 0.2 vinyls per 1,000 carbons; more than 50% of total unsaturated vinyl; and oligomer levels less than 5,000 ppm.

[0034] As mentioned above, polyolefin elastomers are ethylene and C4-C 12 It may include an ethylene-based polymer comprising a polymerized reaction product of an α-olefin comonomer. In one embodiment, the ethylene-based polymer is an ethylene / α-olefin copolymer. C4-C 12 The α-olefin comonomer may include various α-olefin comonomers, for example, 1-butene, 1-hexene, and 1-octene. In one embodiment, the α-olefin comonomer includes 1-octene.

[0035] In at least one embodiment, the ethylene / α-olefin copolymer is an ethylene / α-olefin copolymer.

[0036] The polyolefin elastomer may have a density of 0.860 to 0.900 g / cc, 0.860 to 0.880 g / cc, or 0.865 to 0.875 g / cc.

[0037] The polyolefin elastomer may have a melt index (I2) of 0.5 to 30 dg / min, where I2 is measured according to ASTM D1238 (190°C, 2.16 kg), and in further embodiments, may have an I2 of 1.0 to 25 dg / min, 2.0 to 20 dg / min, or 3 to 18 dg / min. In another embodiment, I2 may have a range extending from a lower limit of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, or 12.0 dg / min to an upper limit of 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 20.0, 25.0, or 30.0 dg / min.

[0038] Polyolefin elastomers are I 10 I of 8 or more, measured according to ASTM D1238 (190℃, 10 kg). 10 / I2 may be included, and in further embodiments, I of 8 to 20, 8 to 18, 8 to 15, 8 to 13, 8 to 10, 10 to 20, 10 to 18, 10 to 15, 13 to 20, 13 to 18, or 13 to 15 10 It may include / I2. Without being limited to theory, such I 10 The / I2 range correlates with increased long-chain branching, which aids in the processability of the resulting cross-linked composition.

[0039] In the embodiment, the polyolefin elastomer has a viscosity V of 600 Pa·s or higher as measured by DMS at 190°C. 0.1It may include. For example, the polyolefin elastomer, as measured by DMS at 190°C, is 600 Pa·s to 15000 Pa·s, 600 Pa·s to 10000 Pa·s, 600 Pa·s to 5000 Pa·s, 600 Pa·s to 2500 Pa·s, 600 Pa·s to 1000 Pa·s, 800 Pa·s to 15000 Pa·s, 800 Pa·s to 10000 Pa·s, 800 Pa·s to 5000 Pa·s, 800 Pa·s to 2500 Pa·s, 800 Pa·s to 1000 Pa·s, 1000 Pa·s to 15000 Pa·s, 1000 Pa·s to 10000 Pa·s, 1000 Pa·s to 5000 Pa·s, or V of 1000 Pa·s to 2500 Pa·s 0.1 It may include.

[0040] In the embodiment, the polyolefin elastomer has a viscosity V of 200 Pa·s to 1200 Pa·s as measured by DMS at 190°C. 100 It may include. For example, the polyolefin elastomer has V of 200 Pa·s to 1200 Pa·s, 200 Pa·s to 1000 Pa·s, 200 Pa·s to 800 Pa·s, 200 Pa·s to 600 Pa·s, 200 Pa·s to 400 Pa·s, 400 Pa·s to 1200 Pa·s, 400 Pa·s to 1000 Pa·s, 400 Pa·s to 800 Pa·s, 400 Pa·s to 500 Pa·s, 500 Pa·s to 1200 Pa·s, 500 Pa·s to 1000 Pa·s, or 500 Pa·s to 800 Pa·s, as measured by DMS at 190°C. 100 It may include. V of the polyolefin elastomer 100 If this is too low, the desired processability of the resulting cross-linked composition may not be achieved.

[0041] The polyolefin elastomer may have a rheology ratio of 2 to 20, and the rheology ratio is V measured by DMS at 190°C 0.1 vs V 100 The ratio is a rheology ratio of 2 to 16 in additional embodiments. For example, the viscosity ratio may be 2 to 16, 2 to 13, 2 to 10, 2 to 8, 2 to 5, 5 to 16, 5 to 13, 5 to 10, 5 to 8, 8 to 16, 8 to 13, 8 to 10, 10 to 16, 10 to 13, or 13 to 16.

[0042] Polyolefin elastomers can have high vinyl unsaturation, as demonstrated by having more than 0.2 vinyls per 1,000 carbons. For example, the polyolefin elastomer comprises 0.2 to 1 vinyl per 1,000 carbons, 0.2 to 0.8 vinyl per 1,000 carbons, 0.2 to 0.7 vinyl per 1,000 carbons, 0.2 to 0.5 vinyl per 1,000 carbons, 0.2 to 0.4 vinyl per 1,000 carbons, 0.4 to 1 vinyl per 1,000 carbons, 0.4 to 0.8 vinyl per 1,000 carbons, 0.4 to 0.7 vinyl per 1,000 carbons, 0.4 to 0.5 vinyl per 1,000 carbons, 0.5 to 1 vinyl per 1,000 carbons, 0.5 to 0.8 vinyl per 1,000 carbons, and 0.5 to 0.7 vinyl per 1,000 carbons. It may include 0.7 to 1 vinyl per 1,000 carbons, 0.7 to 0.8 vinyl per 1,000 carbons, or 0.8 to 1 vinyl per 1,000 carbons.

[0043] The polyolefin elastomer may include more than 0.2 unsaturation per 1,000 carbons, and in further embodiments may include 0.3 to 2 unsaturation per 1,000 carbons, 0.3 to 1 unsaturation per 1,000 carbons, or 0.3 to 0.6 unsaturation per 1,000 carbons.

[0044] Furthermore, the percentage of vinyl in the total unsaturation of the polyolefin elastomer is at least 50%, at least 55%, at least 60%, at least 65%, or at least 70%.

[0045] Additionally, the polyolefin elastomer may have an oligomer level of less than 5000 ppm, and in further embodiments may have an oligomer level of less than 4500 ppm, less than 4000 ppm, less than 3500 ppm, less than 3000 ppm, less than 2500 ppm, less than 2000 ppm, less than 1500 ppm, less than 1000 ppm, less than 500 ppm, less than 250 ppm, or less than 200 ppm. Without being bound by theory, the polyolefin elastomer may have high vinyl levels and low oligomer levels at the chain ends due to the selection of catalyst and process conditions. In polymers having high vinyl levels and high oligomer levels, high levels of oligomers (low Mw components) having vinyl chain ends may be present, which results in low crosslinking efficiency.

[0046] In the embodiment, the polyolefin elastomer has a number average molecular weight (M) of 20 to 35 kg / mol. n It may have ), and in some embodiments M n The amount can be 23 to 33 kg / mol, and Mn is measured by gel permeation chromatography (GPC). For example, M nIt may be 20 kg / mol to 35 kg / mol, 20 kg / mol to 33 kg / mol, 20 kg / mol to 30 kg / mol, 20 kg / mol to 28 kg / mol, 20 kg / mol to 25 kg / mol, 20 kg / mol to 23 kg / mol, 23 kg / mol to 35 kg / mol, 23 kg / mol to 33 kg / mol, 23 kg / mol to 30 kg / mol, 23 kg / mol to 28 kg / mol, 23 kg / mol to 25 kg / mol, 25 kg / mol to 35 kg / mol, or 25 kg / mol to 33 kg / mol.

[0047] In the embodiment, the polyolefin elastomer has a weight-average molecular weight M of 40 kg / mol to 90 kg / mol. w It may include, and M w is measured according to a standard GPC. For example, M w It may be 40 kg / mol to 90 kg / mol, 40 kg / mol to 78 kg / mol, 40 kg / mol to 65 kg / mol, 53 kg / mol to 90 kg / mol, 53 kg / mol to 78 kg / mol, 53 kg / mol to 65 kg / mol, or 65 kg / mol to 90 kg / mol.

[0048] In some embodiments, the polyolefin elastomer has an M of 2.0 to 3.0, 2.4 to 3.0, or 2.5 to 2.6. w / M n It can have, and M w (Weight-average molecular weight) is measured according to conventional GPC.

[0049] In an embodiment, the polyolefin elastomer may comprise 20% to 80% by weight based on the combined weight of the polyolefin elastomer, the olefin-based polymer, and the crosslinking agent. For example, the weight percentage of the polyolefin elastomer based on the combined weight of the polyolefin elastomer, the olefin-based polymer, and the crosslinking agent is 20 wt% to 80 wt%, 20 wt% to 73 wt%, 20 wt% to 65 wt%, 20 wt% to 58 wt%, 20 wt% to 50 wt%, 20 wt% to 43 wt%, 20 wt% to 35 wt%, 20 wt% to 28 wt%, 28 wt% to 80 wt%, 28 wt% to 73 wt%, 28 wt% to 65 wt%, 28 wt% to 58 wt%, 28 wt% to 50 wt%, 28 wt% to 43 wt%, 28 wt% to 35 wt%, 35 wt% to 80 wt%, 35 wt% to 73 wt%, It may be 35 wt% to 65 wt%, 35 wt% to 58 wt%, 35 wt% to 50 wt%, 35 wt% to 43 wt%, 43 wt% to 80 wt%, 43 wt% to 73 wt%, 43 wt% to 65 wt%, 43 wt% to 58 wt%, 43 wt% to 50 wt%, 50 wt% to 80 wt%, 50 wt% to 73 wt%, 50 wt% to 65 wt%, 50 wt% to 58 wt%, 58 wt% to 80 wt%, 58 wt% to 73 wt%, 58 wt% to 65 wt%, 65 wt% to 80 wt%, 65 wt% to 73 wt%, or 73 wt% to 80 wt%. If the weight percentage of the polyolefin elastomer based on the combined weight of the polyolefin elastomer, the olefin-based polymer, and the crosslinking agent is too low, the processability or mechanical properties of the crosslinked composition may be degraded.

[0050] In an embodiment, the combined weight of the polyolefin elastomer and the olefin-based polymer may include more than 60 weight% based on the combined weight of the polyolefin elastomer, the olefin-based polymer, and the crosslinking agent. For example, the combined weight of the polyolefin elastomer and the olefin polymer based on the combined weight of the polyolefin elastomer, the olefin polymer, and the crosslinking agent is 60 wt% to 100 wt%, 60 wt% to 95 wt%, 60 wt% to 90 wt%, 60 wt% to 85 wt%, 60 wt% to 80 wt%, 60 wt% to 75 wt%, 60 wt% to 70 wt%, 60 wt% to 65 wt%, 65 wt% to 100 wt%, 65 wt% to 95 wt%, 65 wt% to 90 wt%, 65 wt% to 85 wt%, 65 wt% to 80 wt%, 65 wt% to 75 wt%, 65 wt% to 70 wt%, 70 wt% to 100 wt%, 70 It may be 95 wt% to 70 wt% to 90 wt%, 70 wt% to 85 wt%, 70 wt% to 80 wt%, 70 wt% to 75 wt%, 75 wt% to 100 wt%, 75 wt% to 95 wt%, 75 wt% to 90 wt%, 75 wt% to 85 wt%, 75 wt% to 80 wt%, 80 wt% to 100 wt%, 80 wt% to 95 wt%, 80 wt% to 90 wt%, 80 wt% to 85 wt%, 85 wt% to 100 wt%, 85 wt% to 95 wt%, 85 wt% to 90 wt%, 90 wt% to 100 wt%, 90 wt% to 95 wt%, or 95 wt% to 100 wt%. If the combined weight of the polyolefin elastomer and the olefin-based polymer based on the total weight of the cross-linked composition is too low, the processability or mechanical properties of the cross-linked composition may be reduced.

[0051] In an embodiment, the polyolefin elastomer may comprise more than 30 weight percent based on the total weight of the cross-linked composition. For example, the weight percentage of the polyolefin elastomer based on the total weight of the cross-linked composition is 30 wt% to 100 wt%, 30 wt% to 90 wt%, 30 wt% to 80 wt%, 30 wt% to 70 wt%, 30 wt% to 60 wt%, 30 wt% to 50 wt%, 30 wt% to 40 wt%, 40 wt% to 100 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 40 wt% to 60 wt%, 40 wt% to 50 wt%, 50 wt% to 100 wt%, 50 wt% to 90 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, 50 wt% to 60 wt%, It may be 60 wt% to 100 wt%, 60 wt% to 90 wt%, 60 wt% to 80 wt%, 60 wt% to 70 wt%, 70 wt% to 100 wt%, 70 wt% to 90 wt%, 70 wt% to 80 wt%, 80 wt% to 100 wt%, 80 wt% to 90 wt%, or 90 wt% to 100 wt%. If the weight percentage of the polyolefin elastomer based on the total weight of the cross-linked composition is too low, the processability or mechanical properties of the cross-linked composition may be reduced.

[0052] Olefin polymers

[0053] The embodiments of the present disclosure relate to olefinic polymers.

[0054] In at least one embodiment, the olefin-based polymer is selected from the group consisting of: polypropylene homopolymer, propylene / ethylene copolymer, propylene / α-olefin copolymer, low-density polyethylene (LDPE), high-density polyethylene (HDPE), and heterogeneous branched ethylene / α-olefin copolymer and additional copolymer. The heterogeneous branched ethylene-based copolymer and additional copolymer are typically prepared using a Ziegler / Natta catalyst system. These linear copolymers and copolymers lack long-chain branching, or a measurable amount of long-chain branching. In additional embodiments, the α-olefin is selected from propylene, 1-butene, 1-hexene, or 1-octene.

[0055] In at least one embodiment, the olefinic polymer may have a melting point (Tm) of 140°C or higher, or 150°C or higher.

[0056] In at least one embodiment, the olefinic polymer may have a melting point (Tm) of 165°C or lower, or 160°C or lower.

[0057] In at least one embodiment, the olefinic polymer has a density of 0.855 g / cc or more, or 0.860 g / cc or more, or 0.870 g / cc or more.

[0058] In at least one embodiment, the olefinic polymer has a density of 0.915 g / cc or less, or 0.910 g / cc or less, or 0.905 g / cc or less.

[0059] In at least one embodiment, the olefin polymer is a propylene polymer.

[0060] In at least one embodiment, the propylene-based polymer is selected from polypropylene homopolymer, propylene / α-olefin copolymer, or propylene / ethylene copolymer.

[0061] In at least one embodiment, the propylene-based polymer has a melt flow rate (MFR at 2.16 kg / 230°C) of 0.1 to 50, or 0.1 to 20, or 0.1 to 5 g / 10 min.

[0062] In at least one embodiment, the polypropylene polymer has a heat of fusion (ΔH) of 85 J / g or more as determined by DSC. f has ).

[0063] In at least one embodiment, the propylene-based polymer has an M of 2.5 or more, or 3.0 or more, or 4.0 or more. w / M n Have rain.

[0064] In at least one embodiment, the propylene-based polymer is 20 or less, or 15 or less, or 10 or less M w / M n Have rain.

[0065] In some embodiments, the propylene-based polymer is a propylene / α-olefin copolymer. Some α-olefins are C4-C 20 It can be selected from the group of α-olefins. Examples of suitable α-olefins include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

[0066] In at least one embodiment, the propylene-based polymer is a propylene / ethylene copolymer, and preferably a copolymer. In a further embodiment, the propylene / ethylene copolymer contains 3 weight percent or less of ethylene based on the weight of the composition.

[0067] In at least one embodiment, the propylene-based polymer is a propylene homopolymer.

[0068] Polypropylene homopolymers may include a combination of two or more embodiments as described herein.

[0069] The propylene / α-olefin copolymer or copolymer may include a combination of two or more embodiments as described herein.

[0070] In an embodiment, the olefin-based polymer may comprise 20% to 80% by weight based on the combined weight of the polyolefin elastomer, the olefin-based polymer, and the crosslinking agent. For example, the weight percentage of the olefin polymer based on the combined weight of the polyolefin elastomer, the olefin polymer, and the crosslinking agent is 20 wt% to 80 wt%, 20 wt% to 73 wt%, 20 wt% to 65 wt%, 20 wt% to 58 wt%, 20 wt% to 50 wt%, 20 wt% to 43 wt%, 20 wt% to 35 wt%, 20 wt% to 28 wt%, 28 wt% to 80 wt%, 28 wt% to 73 wt%, 28 wt% to 65 wt%, 28 wt% to 58 wt%, 28 wt% to 50 wt%, 28 wt% to 43 wt%, 28 wt% to 35 wt%, 35 wt% to 80 wt%, 35 wt% to 73 wt%, 35 It may be 65 wt% to 35 wt% to 58 wt%, 35 wt% to 50 wt%, 35 wt% to 43 wt%, 43 wt% to 80 wt%, 43 wt% to 73 wt%, 43 wt% to 65 wt%, 43 wt% to 58 wt%, 43 wt% to 50 wt%, 50 wt% to 80 wt%, 50 wt% to 73 wt%, 50 wt% to 65 wt%, 50 wt% to 58 wt%, 58 wt% to 80 wt%, 58 wt% to 73 wt%, 58 wt% to 65 wt%, 65 wt% to 80 wt%, 65 wt% to 73 wt%, or 73 wt% to 80 wt%. If the weight percentage of the olefin polymer based on the combined weight of the polyolefin elastomer, the olefin polymer, and the crosslinking agent is too low, the processability or mechanical properties of the crosslinked composition may be reduced.

[0071] In an embodiment, the olefin-based polymer may be included in an amount of more than 15% by weight based on the total weight of the cross-linked composition. For example, the weight percentage of the olefinic polymer based on the total weight of the cross-linked composition is 15 wt% to 70 wt%, 15 wt% to 61 wt%, 15 wt% to 52 wt%, 15 wt% to 43 wt%, 15 wt% to 33 wt%, 15 wt% to 24 wt%, 24 wt% to 70 wt%, 24 wt% to 61 wt%, 24 wt% to 52 wt%, 24 wt% to 43 wt%, 24 wt% to 33 wt%, 33 wt% to 70 wt%, 33 wt% to 61 wt%, 33 wt% to 52 wt%, 33 wt% to 43 wt%, 43 wt% to 70 wt%, 43 wt% to 61 wt%, 43 wt% to 52 wt%, 52 wt% to It may be 70 wt%, 52 wt% to 61 wt%, or 61 wt% to 70 wt%. If the weight percentage of the olefin-based polymer based on the total weight of the cross-linked composition is too low, the processability or mechanical properties of the cross-linked composition may be reduced.

[0072] crosslinking agent

[0073] An embodiment of the present disclosure comprises an ethylene monomer and at least one C4-C 12 The present invention relates to a composition comprising an ethylene / α-olefin copolymer produced from the polymerization reaction product of an α-olefin comonomer, an olefin-based polymer, and a crosslinking agent.

[0074] In at least one embodiment, the cross-linked composition includes a cross-linking agent.

[0075] In at least one embodiment, the crosslinking agent may comprise one or more inert carriers. For example, the inert carrier may comprise calcium carbonate.

[0076] In at least one embodiment, the crosslinking agent comprises an organic peroxide. The organic peroxide may comprise 0.2% to 5% by weight based on the combined weight of the ethylene / α-olefin copolymer, the olefin polymer, and the organic peroxide. For example, the organic peroxide may be 0.2 wt% to 5 wt%, 0.2 wt% to 4 wt%, 0.2 wt% to 3 wt%, 0.2 wt% to 2 wt%, 0.2 wt% to 1 wt%, 1.2 wt% to 5 wt%, 1.2 wt% to 4 wt%, 1.2 wt% to 3 wt%, 1.2 wt% to 2 wt%, 2.1 wt% to 5 wt%, 2.1 wt% to 4 wt%, 2.1 wt% to 3 wt%, 3.1 wt% to 5 wt%, 3.1 wt% to 4 wt%, or 4 wt% to 5 wt%.

[0077] In an embodiment, the organic peroxide may include di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, di-(tert-butylperoxyisopropyl)benzene, tert-butyl peroxybenzoate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, or a combination thereof.

[0078] In at least one embodiment, the crosslinked composition further comprises a crosslinking aid. The crosslinking aid may comprise 0% to 5% by weight based on the combined weight of the ethylene / α-olefin copolymer, the olefin polymer, the crosslinking agent, and the crosslinking aid. For example, the crosslinking aid may comprise 0% to 5% by weight, 0% to 4% by weight, 0% to 3% by weight, 0% to 2% by weight, 1% to 5% by weight, 1% to 4% by weight, 1% to 2% by weight, 1% to 3% by weight, 1% to 1.5% by weight, 2% to 5% by weight, 2% to 4% by weight, or 2% to 3% by weight based on the combined weight of the ethylene / α-olefin copolymer, the olefin polymer, the crosslinking agent, and the crosslinking aid.

[0079] In an embodiment, the crosslinking agent may include trialyl cyanurate, trialyl isocyanurate, trifunctional acrylate, or a combination thereof.

[0080] In an embodiment, the weight ratio of the crosslinking agent to the auxiliary agent may be 0.2:1 to 2:1. For example, the weight ratio of crosslinking agent to auxiliary agent is 0.2:1 to 2:1, 0.2:1 to 2:1, 0.2:1 to 1:1, 0.2:1 to 1:1, 0.2:1 to 1:1, 0.2:1 to 1:1, 0.5:1 to 2:1, 0.5:1 to 2:1, 0.5:1 to 1:1, 0.5:1 to 1:1, 0.5:1 to 1:1, 0.8:1 to 2:1, 0.8:1 to 2:1, 0.8:1 to 1:1, 0.8:1 to 1:1, 1.1:1 to 2:1, 1.1:1 to 2:1, 1.1:1 to 1:1, 1.4:1 to 2:1, 1.4:1 It may be up to 2:1, or 1.7:1 to 2:1.

[0081] additives

[0082] In at least one embodiment, the cross-linked composition further comprises an antioxidant. In an embodiment, the antioxidant may be included in an amount of 0.05 wt% to 0.5 wt% based on the weight of the cross-linked composition. For example, the weight percentage of the antioxidant may be 0.05 wt% to 0.5 wt%, 0.05 wt% to 0.4 wt%, 0.05 wt% to 0.3 wt%, 0.05 wt% to 0.2 wt%, 0.1 wt% to 0.5 wt%, 0.1 wt% to 0.4 wt%, 0.1 wt% to 0.3 wt%, 0.2 wt% to 0.5 wt%, 0.2 wt% to 0.4 wt%, or 0.2 wt% to 0.3 wt%.

[0083] In at least one embodiment, the cross-linked composition further comprises oil. In an embodiment, the oil is a hydrocarbon oil or a hydrocarbon process oil. In an embodiment, the oil may comprise 10% to 60% by weight based on the weight of the cross-linked composition. For example, the weight percentage of the oil may be 10% to 60% by weight, 10% to 50% by weight, 10% to 40% by weight, 20% to 60% by weight, 30% to 60% by weight, or 30% to 40% by weight.

[0084] Cross-linked composition

[0085] When using a composition as described herein, processability (e.g., 0.1 rad / s and viscosity (V) as measured at 230°C) 0.1 ) is greater than 105,000 Pa·s, and viscosity (V) as measured at 1,000 rad / s and 230℃ 1k It can result in a cross-linked composition having an improved compressive permanent strain (e.g., 60% or less at 70 hr and 120°C) while maintaining a compressive strain of less than 130 Pa·s.

[0086] In an embodiment, the cross-linked composition may have a compressive permanent strain of less than 60% at 70 hr and 120°C. For example, the compressive permanent strain may be 0% to 60%, 0% to 58%, 0% to 56%, 0% to 54%, 10% to 60%, 10% to 58%, 10% to 56%, 10% to 54%, 25% to 60%, 25% to 58%, 25% to 56%, 25% to 54%, 50% to 60%, 50% to 58%, 50% to 56%, or 50% to 54%.

[0087] In the embodiment, the cross-linked composition has a viscosity V of 105,000 Pa·s or higher at 230°C. 0.1 It may include. For example, the polyolefin elastomer has V at 230°C of 105,000 Pa·s to 300,000 Pa·s, 105,000 Pa·s to 250,000 Pa·s, 105,000 Pa·s to 200,000 Pa·s, 115,000 Pa·s to 300,000 Pa·s, 115,000 Pa·s to 250,000 Pa·s, 115,000 Pa·s to 200,000 Pa·s, 125,000 Pa·s to 300,000 Pa·s, 125,000 Pa·s to 250,000 Pa·s, or 125,000 Pa·s to 200,000 Pa·s. 0.1 It may include. V at 230℃ 0.1 If this is too low, the resulting cross-linked composition may have low sag resistance, low dimensional stability during melt extrusion, or both.

[0088] In an embodiment, the cross-linked composition has a viscosity V of 130 Pa·s to 1000 Pa·s at 230°C. 100It may include. For example, the cross-linked composition has V of 130 Pa·s to 1000 Pa·s, 130 Pa·s to 750 Pa·s, 130 Pa·s to 500 Pa·s, 150 Pa·s to 1000 Pa·s, 150 Pa·s to 750 Pa·s, 150 Pa·s to 500 Pa·s, 250 Pa·s to 1000 Pa·s, 250 Pa·s to 750 Pa·s, 250 Pa·s to 500 Pa·s, 350 Pa·s to 1000 Pa·s, 350 Pa·s to 750 Pa·s, or 350 Pa·s to 500 Pa·s at 230°C. 100 It may include.

[0089] In the embodiment, the cross-linked composition has a viscosity V of 130 Pa·s or less at 230°C. 1k It may include. For example, the cross-linked composition has V of 50 Pa·s to 130 Pa·s, 50 Pa·s to 120 Pa·s, 50 Pa·s to 110 Pa·s, 50 Pa·s to 100 Pa·s, 75 Pa·s to 130 Pa·s, 75 Pa·s to 120 Pa·s, 75 Pa·s to 110 Pa·s, or 75 Pa·s to 100 Pa·s at 230°C. 1k It may include. V at 230℃ 1k If it is too high, the desired processability may not be achieved.

[0090] The cross-linked composition may include a rheology ratio of 300 to 500, and the rheology ratio is viscosity V at 230°C. 0.1 Viscosity V 100 The ratio is and may include a rheology ratio of 325 to 400 in additional embodiments. For example, the viscosity ratio of the cross-linked composition may be 300 to 500, 300 to 400, 325 to 500, 325 to 400, 350 to 500, or 350 to 400.

[0091] In an embodiment, the cross-linked composition can be prepared by heat, irradiation, electron beam irradiation, or ultraviolet (UV) irradiation.

[0092] The cross-linked composition may have a hardness of 50 to 100 Shore A. For example, the hardness may be 50 Shore A to 100 Shore A, 50 Shore A to 90 Shore A, 70 Shore A to 100 Shore A, or 70 Shore A to 90 Shore A.

[0093] The cross-linked composition may have a tear strength of 25 to 75 N / mm. For example, the tear strength may be 25 N / mm to 75 N / mm, 25 N / mm to 50 N / mm, 30 N / mm to 75 N / mm, or 30 N / mm to 50 N / mm.

[0094] The cross-linked composition may have a tensile stress at fracture of 1 to 20 MPa. For example, the tensile stress at fracture may be 1 MPa to 20 MPa, 1 MPa to 10 MPa, 5 MPa to 20 MPa, or 5 MPa to 10 MPa.

[0095] The cross-linked composition may contain a tensile 10% stress of 1 to 10 MPa. For example, the tensile 10% stress may be 1 MPa to 10 MPa or 1 MPa to 5 MPa.

[0096] Article composition

[0097] An embodiment of the present disclosure relates to an article comprising at least one component formed from a cross-linked composition.

[0098] In an embodiment, the article comprises an ethylene monomer and at least one C4-C 12 It may include at least one component formed from a crosslinked composition comprising a polymerization reaction product of an α-olefin comonomer.

[0099] In an embodiment, the article may include at least one component formed from a cross-linked composition.

[0100] In an embodiment, an article comprising at least one component formed from a cross-linked composition may be a door profile, a window profile, a gasket, or a molded part.

[0101] Manufacturing process of polyolefin elastomers

[0102] Embodiments of the present disclosure relate to a process for producing an ethylene / α-olefin copolymer polyolefin elastomer, the process comprising solution polymerizing ethylene and an α-olefin comonomer in the presence of a catalyst. The cross-linked polyolefin elastomer may be produced from a cross-linkable polyolefin elastomer formulation through a curing process known to those skilled in the art. In some embodiments, curing may be initiated by heat, irradiation, electron beam irradiation, or ultraviolet (UV) radiation.

[0103] In an embodiment, a process for producing an ethylene / α-olefin copolymer may include solution polymerizing ethylene and an α-olefin comonomer in the presence of a precatalyst having the following structure (I):

[0104]

[0105] Structure (I)

[0106] In the above structure, M is Zr or Hf, and the metal is in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is an independently selected monodentate ligand; the total catalyst is charge-neutral; and R1 and R 16 At least one of them is selected from structure (II), structure (III), and structure (IV):

[0107]

[0108] In the above structure, R 31-35 , R 41-48 , and R 51-59 is independently -H, C1-C 40 Heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or selected from halogen, where R C C1-C independently 40 Selected from hydrocarbil; R3 and R 14 C1-C independently 40 Hydrocarbyl or hydrogen; R6 and R 11 C1-C independently 40 Hydrocarbyl or hydrogen; R2, R4, R5, R7, R8, R9, R 10 , R 12 , R 13 , and R 15 C1-C independently 40 Hydrocarbyl, C1-C 40 Heterohydrocarbil, -Si(R C )3, selected from the group consisting of halogen atoms, hydrogen atoms, and combinations thereof; R 17 and R 18 is independently a C1-C3 hydrocarbylene; R 19 and R 20 C1-C independently 40 It is hydrocarbyl or hydrogen.

[0109] In the embodiment, R1 and R of the total catalyst structure (I)16 Each can be a structure (III):

[0110]

[0111] In an embodiment, R3 and R of the total catalyst structure (I) 14 are respectively C1-C 12 It can be an alkyl.

[0112] In an embodiment, R6 and R of the total catalyst structure (I) 11 are C1-C respectively 12 It can be an alkyl.

[0113] In the embodiment, R3, R6, and R of the total catalyst structure (I) 11 , and R 14 are C6-C respectively 11 It can be an alkyl.

[0114] In an embodiment, R of the total catalyst structure (I) 17 and R 18 It can be -CH2-.

[0115] In an embodiment, R of the total catalyst structure (I) 19 is C2-C 10 It can be an alkyl.

[0116] In an embodiment, R of the total catalyst structure (I) 20 C2-C 10 It can be an alkyl.

[0117] In another embodiment, R2, R4, R5, R7, R8, R9, R of the total catalyst structure (I) 10 , R 12 , R 13 and R 15 It can be a hydrogen atom.

[0118] In an embodiment, the structure (I) may not contain a halogen.

[0119] In an embodiment, M of the total catalyst structure (I) may be Zr.

[0120] In an embodiment, a process for producing an ethylene / α-olefin copolymer may include solution polymerizing ethylene and α-olefin comonomers in the presence of a precatalyst in a single reactor at a temperature greater than 150°C.

[0121] In an embodiment, a process for producing an ethylene / α-olefin copolymer may include solution polymerizing ethylene and α-olefin comonomers in the presence of a co-catalyst comprising alumoxic acid.

[0122] In an embodiment, the process for preparing a cross-linked composition may include solution polymerizing ethylene and α-olefin comonomers in the presence of a co-catalyst comprising ammonium borate.

[0123] Test method

[0124] density

[0125] Density is measured according to ASTM D792 and is gram / cm³ 3 (g / cc or g / cm²) 3 It is displayed as ).

[0126] Tensile stress at fracture and 10% tensile stress

[0127] Tensile stress at fracture and tensile stress at 10% elongation (i.e., stress at 10% elongation) were measured in accordance with ASTM D1708 using an Instron Tester at a speed of 5 inches / min.

[0128] Melt index (I 2 ) and (I 10 )

[0129] The melt index (I2) is measured according to ASTM D-1238 (190°C / 2.16 kg). Melt index (I 10 ) is measured according to ASTM D-1238 (190℃ / 10 kg).

[0130] Tear strength

[0131] Tear strength was measured according to ASTM D624 using Type C specimens.

[0132] Compressive permanent strain

[0133] Compressive permanent strain was measured according to ASTM D395 at 120°C for 70 hours.

[0134] A puck with a diameter of 29 mm (±0.5 mm) was extracted from a compression-molded plaque approximately 3 mm (1 / 8 inch) thick. For each sample, four pucks were inspected for notches, non-uniform thickness, and non-uniformity, and then stacked to achieve a recommended thickness of 12.5 mm (±0.5 mm). The stacked pucks were placed in a compression device and secured in place. The device was then set to an appropriate temperature for a specified time (70 hours at 120°C). The stress was released at the test temperature, and the thickness of the sample was measured after a 30-minute equilibrium period at room temperature. Compression permanent strain is a measure of the degree of recovery of the sample after compression and is calculated according to Equation 1 below:

[0135] Equation 1

[0136] H 0 Original thickness

[0137] H 1 Thickness of the spacer bar used

[0138] H 2 Final thickness

[0139] hardness

[0140] The Shore A hardness of the TPV sample is measured according to ASTM D2240 after a 10 s delay.

[0141] Capillary rheology

[0142] Capillary rheology at 230°C V 1kIt was used to measure the viscosity of the cross-linked composition. Capillary tests were performed on either a Rheotester 2000 or a Rheograph 25 capillary rheometer, both of which are It was manufactured by. The die used in the test has a diameter of 1 mm and an entry angle of 180 degrees. The die used in the Rheograph 25 capillary has a length of 30 mm and an active length of 20 mm. The rheotester used a 20 mm long capillary, with an active length of 20 mm. The test was performed isothermally at 230°C.

[0143] Before starting the test, the sample pellet was loaded into the capillary barrel and allowed to reach equilibrium at the test temperature for 10 minutes. After the waiting period, the test began, at which point the piston inside the barrel applied force to the molten sample for approximately 150 s -1 to 10,000 s -1 An apparent shear rate within the specified range is achieved. The pressure drop across the capillary die is measured by a transducer. The pressure drop was used to determine the apparent shear stress near the wall relative to the apparent shear rate. Additional calculations provided by the capillary test include apparent viscosity, corrected shear rate, and corrected viscosity. Apparent viscosity is obtained by dividing the apparent wall shear stress by the corresponding apparent shear rate. The corrected shear rate is obtained by implementing the Rabinowitsch correlation using the apparent shear rate and shear stress datasets. Consequently, the corrected viscosity was calculated by dividing the apparent wall shear stress by the corrected shear rate.

[0144] DMS Frequency Sweep

[0145] DMS is V 0.1 and V 100It was used to measure the viscosity of the polyolefin elastomer at 190°C and the viscosity of the cross-linked composition at 230°C. Samples were prepared by placing them in a 9.75 in. × 10.25 in. rectangular chase with a thickness of 1.85 mm and compression molding them at 190°C for 6.5 minutes at a pressure of 25,000 lbs using a Carver Hydraulic Press. The samples were then cooled to room temperature and processed with a 25 mm diameter die cutter to extract disc-shaped samples for rheological testing.

[0146] Dynamic Mechanical Spectroscopy (DMS) frequency sweeps were performed using 25 mm parallel plates at frequencies ranging from 0.1 rad / s to 100 rad / s. The test interval separating the plates was 1.8 mm, and a strain satisfying linear viscoelastic conditions, typically 10% strain, was used. Each test was performed under a nitrogen atmosphere and isothermal conditions of 190°C or 230°C as specified. To initiate the DMS test, the rheometer oven was first allowed to equilibrate at the desired test temperature for at least 30 minutes before loading the sample onto the test geometry. Then, the sample was allowed to equilibrate inside the oven for 1 minute with the oven door closed. Next, the test interval was set to 1.8 mm, and the sample was given 5 minutes to allow the resulting normal forces to relax. Afterward, the oven was opened, and the sample was trimmed to ensure there were no protrusions. Then, the oven was closed again, and DMS measurements were initiated.

[0147] All DMS frequency tests were performed on ARES-G2 or DHR-3 rheometers, both manufactured by TA Instruments. Data analysis was performed using TA Instruments TRIOS software.

[0148] Gel Permeation Chromatography (GPC)

[0149] The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160°C, and the column and detector compartments were set to 150°C. The columns used were four Agilent "Mixed-Type A" 30 cm 20-micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). Nitrogen was used as the solvent source for sparging. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliter / min.

[0150] Calibration of the GPC column set was performed using at least 21 polystyrene standards with a narrow molecular weight distribution and molecular weights ranging from 580 to 8,400,000. The standards were arranged in six "cocktail" mixtures spaced at least 10-fold apart from the individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and at 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes and then cooled; the room-temperature solution was transferred to an autosampler dissolution oven and maintained at 160°C for 30 minutes. The standard peak molecular weight of polystyrene was converted to the molecular weight of polyethylene using Formula 2 (as described in the literature [Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)]):

[0151] M 폴리에틸렌 = A × ( M 폴리스티렌 ) B Equation 2

[0152] In the above formula, M is the molecular weight, A has a value of 0.4163, and B is 1.0.

[0153] Each polyethylene equivalent correction point was fitted using a fifth-order polynomial.

[0154] The total plate count of the GPC column set was performed using decane introduced into the blank sample via a micropump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system must exceed 18,000 for four Agilent "Mixed-Type A" 30 cm 20-micron linear mixed-bed columns.

[0155] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, gravimetrically targeted at 2 mg / ml, and a solvent (containing 200 ppm BHT) was added to pre-nitrogen-sparged and diaphragm-capped via a PolymerChar high-temperature autosampler. Samples were dissolved at 160°C for 2 hours under "low-speed" shaking.

[0156] Mn (GPC) , Mw (GPC), and Mz (GPC) The calculation was based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 3 to 5, using the PolymerChar GPCOne™ software, baseline-subtracted IR chromatogram at each equally spaced data acquisition point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard correction curve for point (i) from Equation 2.

[0157] Equation 3

[0158] Equation 4

[0159] Equation 5

[0160] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. Using this flow marker (FM), the pump flow rate (flow rate (nominal)) of each sample was linearly corrected by aligning the RV of the decane peak within each sample (RV (FM sample)) with the RV of the decane peak in the narrow standard correction (RV (FM corrected)). Subsequently, any change in the decane marker peak over time is assumed to be associated with a linear shift in the flow rate (flow rate (effective)) over the entire run. After calibrating the system based on the flow marker peak, the effective flow rate (for the narrow standard correction) is calculated according to Equation 6. Processing of the flow marker peak was performed using PolymerChar GPC One™ software. An acceptable flow rate correction is that the effective flow rate must be within + / - 0.5% of the nominal flow rate.

[0161] Flow Rate (Effective) = Flow Rate (Nominal) * (RV (FM Correction) / RV (FM Sample)) Equation 6

[0162] 1 H NMR

[0163] The sample was prepared by adding approximately 130 mg of the sample to 3.25 g of 50 / 50 tetrachloroethane-d2 / perchloroethylene by weight, containing 0.001 M Cr(AcAc)3 and 100 ppm antioxidant (Irganox168), in a NORELL 1001-7, 10 mm, NMR tube. The sample was purged to prevent oxidation by bubbling N2 through the solvent for approximately 5 minutes using a pipette inserted into the tube. Next, the tube was capped, sealed with TEFLON tape, and then immersed overnight at room temperature to promote sample dissolution. During storage, before preparation, and after preparation, the sample was kept in an N2 purge box to minimize exposure to O2. The sample was heated and vortexed at 110°C to ensure homogeneity.

[0164] 1 ¹H NMR was performed on a Bruker AVANCE 400 or 600 MHz spectrometer equipped with a Bruker high-temperature cryoprobe at a sample temperature of 120 °C. Two experiments were conducted to obtain a spectrum, a control spectrum for quantifying total polymer protons, and a dual pre-saturation experiment that suppresses high-intensity peaks associated with polymer chains and enables a high-sensitivity spectrum for terminal group quantification. The control was run with a ZG pulse, TD 16384, NS 16, DS 4, SWH 10,000 Hz, AQ 1.64 s, and D114 s. The dual pre-saturation experiment was performed with a modified pulse sequence, lc1prf2.zz, TD 16384, NS 64 scans, DS 4, SWH 10,000 Hz, AQ 1.64 s, D11 s, and D 13The experiment was performed for 13 seconds. Unsaturation measurements were made according to the method described below. The area under resonance of the polymer chains (i.e., CH, CH2, and CH3 within the polymer) was measured from the spectrum obtained during the first experiment described above (control spectrum). The area under the four major types of unsaturation (i.e., vinyl, vinylene, trisubstituted, and vinylidene) was measured from the spectrum obtained during the second (pre-saturation) experiment described above. Both spectra were normalized to the area under resonance in the solvent. The moles of each unsaturation were calculated by dividing the area under the unsaturation resonance by the number of protons contributing to that resonance. The moles of carbon within the polymer were calculated by dividing the area under the peak for the polymer chains (i.e., CH, CH2, and CH3 within the polymer) by 2. Subsequently, the total amount of unsaturation was expressed as the relative ratio of the total moles of unsaturation to the moles of carbon within the polymer, expressed as the number of unsaturations per 1,000 carbons.

[0165] Examples

[0166] The following examples illustrate the features of the present disclosure and are not intended to limit the scope of the present disclosure. The following experiments analyzed the performance of the embodiments of the compositions described herein.

[0167] ENGAGE™ 8150 and ENGAGE™ 8003 are polyolefin elastomers available from The Dow Chemical Company, Midland, Michigan, USA.

[0168] H110-02N is a polypropylene homopolymer available from Braskem with an MFR (2.16 kg / 230℃) of 2.0 g / 10 min.

[0169] ParaLux ® 6001 is a process oil available from Chevron.

[0170] Vul-cup ®40C is an organic peroxide available from Arkema. Vul-cup ® 40C is a 40% organic peroxide (di-(tert-butylperoxyisopropyl)benzene) on a calcium carbonate carrier.

[0171] Triallyl isocyanurate (TAIC) is commercially available from Beijing Kerudite.

[0172] Irganox ® B225 is a commercially available antioxidant from BASF.

[0173] Ethylene / α-olefin copolymer

[0174] The ethylene / α-olefin copolymer used in the examples is provided in Table 1.

[0175] [Table 1]

[0176]

[0177] Preparation of ethylene / α-olefin copolymer

[0178] The polyolefin elastomers (POE A, POE B, and POE C) in Table 1 were prepared in a polymerization reactor filled with a sufficiently mixed liquid, operated under steady-state conditions. All raw materials (ethylene monomer and 1-octene comonomer) and process solvent (high-purity isoparaffinic solvent with a narrow boiling range, Isopar-E supplied by ExxonMobil Chemical Company) were purified by molecular sieve before being introduced into the reaction environment. Hydrogen was supplied pressurized to a high-purity grade and was not further purified. The ethylene flow rate and reactor volume were selected to obtain the residence times specified in Table 2. The catalyst and co-catalyst used are listed in Table 3. The solvent, comonomer, hydrogen, catalyst, and co-catalyst were supplied to the reactor according to the process conditions outlined in Table 2. The catalyst flow rate was adjusted to achieve the desired ethylene conversion rate. The reactor temperature was measured at or near the reactor outlet. The copolymers were separated and pelletized.

[0179] [Table 2]

[0180]

[0181] [Table 3]

[0182]

[0183] Formulation of catalyst BPP-A

[0184] The BPP-A catalyst was prepared according to the following 3-step process:

[0185] Step 1: Synthesis of Subfragment 3

[0186]

[0187] This reaction was carried out in a nitrogen-filled glove box. 1 (5.52 g, 19.3 mmol), 2 A slurry of (International Publication WO 2022015369 A1) (1.65 g, 7.74 mmol) and K3PO4 (5.75 g, 27.1 mmol) in DMF (7 mL) was heated to 75°C and maintained at this temperature for 5 hours while stirring. After this time, the temperature was lowered to 70°C and maintained at this temperature for 11 hours while stirring. After cooling to room temperature, the mixture was removed from the glove box. Et2O (10 mL) was added to the reaction vial, and the mixture was filtered through a 1:1 (40 g) basic alumina / SiO2 gel plug. The plug was further extracted with Et2O (3 × 30 mL). The combined Et2O extracts were transferred to a separatory funnel and washed with 4 N NaOH (10 mL), H2O (10 mL), brine (10 mL), 4 N NaOH (10 mL), H2O (10 mL), and brine (10 mL). Subsequently, the Et2O layer was dried over Na2SO4 and filtered into a 250 mL RB flask to remove the Na2SO4. The Et2O was removed by rotary evaporator 3 (5.25 g, 7.39 mmol, yield: 96%) was provided as a colorless oil and used without further purification.1 H NMR (400 MHz, chloroform-d) δ 7.49 (d, J = 2.4 Hz, 2H), 7.24 (dd, J = 8.6, 2.4 Hz, 2H), 6.96 (d, J = 8.7 Hz, 2H), 3.94 (s, 4H), 1.69 (s, 4H), 1.40 - 1.36 (m, 2H), 1.32 (s, 12H), 1.21 (app d, J = 7.4 Hz, 12H), 0.74 (s, 18H).

[0188] Synthesis of 5 (compound 4 (It was manufactured as described in International Publication WO 2018170138)

[0189]

[0190] Degassed THF (5 mL) and degassed water (2 mL) 4 (0.948 g, 1.63 mmol), 3It was added to a 40 mL vial filled with (0.330 g, 0.464 mmol), PdCl(Crotyl)Amphos (0.00861 g, 0.0186 mmol), and NaOH (0.0929 g, 2.32 mmol). The reaction mixture was heated to 50°C and maintained at this temperature for 16 hours. After this time, the reaction mixture was cooled to room temperature. Et2O (20 mL) and saturated aqueous NH4Cl (10 mL) were added to the reaction mixture. After shaking the solution, the layers separated, the organic phase was removed using a pipette, and transferred to a 4 oz bottle containing Na2SO4. The aqueous phase was further extracted with Et2O (20 mL). The combined Et2O extract was filtered through a round-bottom flask to remove Na2SO4 and concentrated until dry. After adding THF (10 mL) and MeOH (10 mL) to the separated material, concentrated HCl (5 drops from a glass pipette) was added. The solution was heated to 85°C (external temperature), stirred for 18 hours, and then the solvent was removed under reduced pressure. The yellow oil was treated with isopropyl alcohol (IPA) (10 mL) via rotary evaporator, the oil was taken in IPA (15 mL), placed in a rotary evaporator bath, and heated to 55°C while rotating. The solution was then removed from the bath and rotated at room temperature, and eventually a solid precipitated. After 1 hour at room temperature, the solid was collected by filtration. The solid was washed with IPA (2 × 3 mL). IPA / MeOH (1:1, 15 mL) was added to the solid (approx. 420 mg) in a 100 mL round-bottom (RB) flask, and the flask was placed in a rotary evaporator bath and heated to 75°C while rotating. The suspension (which was not completely dissolved) was then removed from the bath and rotated at room temperature. After 1 hour at room temperature, the solid was collected by filtration. The solid was washed with IPA (2 × 3 mL).MeOH / Et2O (5:1, 18 mL) was added to the solid (approx. 360 mg) in a 100 mL RB flask, and the flask was placed in a rotary evaporator bath and heated to 45°C while rotating. The (incompletely dissolved) suspension was then removed from the bath and kept at room temperature. After leaving it at room temperature overnight, the solid was collected by filtration. The solid was washed with MeOH (2 × 3 mL). 5 (0.290 g, 0.211 mmol, yield: 45%) was provided as a white solid. 1 H NMR (400 MHz, chloroform-d) δ 8.23 ​​(d, J = 7.6 Hz, 4H), 7.39 - 7.26 (m, 10H), 7.22 - 7.15 (m, 4H), 7.12 (d, J = 2.4 Hz, 4H), 6.66 (s, 2H), 5.76 (br s, J = 21.5 Hz, 2H), 5.53 (s, 2H), 3.42 (br s, 4H), 1.65 (s, 4H), 1.59 - 1.51 (m, 4H), 1.32 - 1.06 (m, 51H), 0.85 (t, J = 6.8 Hz, 6H), 0.79 - 0.65 (m, 32H).

[0191] Step 3: Synthesis of BPP-A

[0192]

[0193] MeMgBr (3 M in diethyl ether, 0.283 mL, 0.849 mmol) in tetrachlorozirconium (0.0475 g, 0.204 mmol) and in Et2O (10 mL) and toluene (2 mL) 5It was added to a room temperature suspension of (0.275 g, 0.200 mmol). After stirring the mixture for 4 hours, additional MeMgBr (50 μL) was added, and the reaction mixture was then stirred overnight at room temperature. After this time, the solvent was removed under reduced pressure. Pentane (10 mL) was added to the dark-colored residue and passed through a CELITE pad. The residue and pad were extracted with additional pentane (10 mL). The combined pentane extract was concentrated until dry to yield BPP A (0.255 g, 0.171 mmol, yield: 85%): 1 H NMR (400 MHz, benzene-d6) δ 8.37 (d, J = 7.7 Hz, 2H), 8.10 (dd, J = 7.2, 1.7 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 2.5 Hz, 2H), 7.55 (d, J = 2.5 Hz, 2H), 7.52 (d, J = 2.5 Hz, 2H), 7.51 - 7.44 (m, 2H), 7.43 - 7.34 (m, 4H), 7.12 (dd, J = 7.8, 1.6 Hz, 3H), 7.05 (dd, J = 5.5, 3.3 Hz, 2H), 5.17 (d, J = 8.7 Hz, 2H), 4.24 (d, J = 14.0 Hz, 2H), 3.24 (d, J = 14.0 Hz, 2H), 1.88 (d, J = 14.6 Hz, 2H), 1.60 (d, J = 14.6 Hz, 3H), 1.45 - 1.21 (m, 50H), 1.19 (s, 6H), 0.80 (s, 18H), 0.57 (t, J = 7.9 Hz, 12H), 0.37 (p, J = 7.4 Hz, 2H), -0.88 (s, 6H).

[0194] Without being limited by theory, BPP-A was found to result in high vinyl levels at the chain-terminals in combination with a low oligomer content in the polymer.

[0195] Haake blending of polymers

[0196] The POE composition of Table 1 was formed into the cross-linked TPV composition of Table 6 using a Haake blender after partial pre-work. The pre-work was performed by impregnating the POE pellets with oil in a glass bottle at 50°C for 24 hours to produce impregnated POE pellets. This was done to minimize slippage and reduce mixing time.

[0197] Mixing of the composition formulation was performed in a Haake mixer, during which the Haake mixer bowl was heated to an initial temperature of 190°C. After reaching this temperature, polypropylene (DOW H110-02N) pellets were added and mixed at 75 rpm for 4 minutes to form a first melt. Impregnated POE pellets were added to the first melt and mixed at 75 rpm for 5 minutes to form a second melt. Triallyl isocyanurate preparation (Beijing Keruidite, TAIC-TLC-72) and Vul-cup ® A peroxide was added and mixed at 75 rpm for 3 minutes to form a third melt. An antioxidant (IRGANOX B225, BASF) was added and mixed at 75 rpm for 3 minutes to form a fourth melt.

[0198] The fourth melt was transferred from the Haake mixer to a 2-roll mill (RELIABLE 2-roll mill mixer) at 190°C for further mixing. The fourth melt was passed through the roll mill to form a sheet, and the resulting sheet was rolled into a cigar-shaped specimen, positioned so that the ends entered the mill first, and the "rolled sheet" was passed through the mill. Roll mill mixing was repeated 6 times to form a sample, and the sample was removed from the mill as a final sheet. The final sheet was transferred to a preheated hydraulic press.

[0199] The hydraulic press was heated to 190°C. A 3.2 mm thick mold chase was mounted on the press, and the sample was filled into the mold chase. In the chase, the final compound mixture was compressed at 2,000 psi for 2 minutes. Subsequently, the final compound mixture was compressed at 55,000 psi for 4 minutes. Sequential compressive loading produces a test plaque without visible cracks. The sample was removed from the chase and transferred to a cooling hydraulic press at room temperature. The final compound mixture was compressed at 55,000 psi for 4 minutes at room temperature.

[0200] POE, H110-02N, ParaLux ® 6001, Vul-cup ® 40C, trialyl isocyanurate (TAIC), and Irganox ® The amounts of B225 are listed in Table 4 as parts (phr) and weight percentage (weight%) per 100 based on the total weight of the composition.

[0201] POE, H110-02N, and Vul-cup ® The amount of 40C is POE, H110-02N, and Vul-cup ® phr and weight% based on the total weight of 40C are listed in Table 5.

[0202] [Table 4]

[0203]

[0204] [Table 5]

[0205]

[0206] Characteristics of the generated TPV cross-linked compositions, Comparative Examples CE-A, CE-B, CE-C, CE-D, and CE-E, and Examples IE-1 and IE-2 (i.e., I2, I 10 / I2, viscosity) is listed in Table 6. Viscosities V listed in Table 6 0.1 and V 100 was measured using DMS rheology, and the viscosity V listed in Table 61k It was measured using capillary rheology.

[0207] [Table 6]

[0208]

[0209] IE-1 and IE-2, which are cross-linked compositions prepared from the compositions described herein, have compressive permanent strains of 53% and 58%, respectively; V of 132,174 Pa·s and 226,461 Pa·s, respectively. 0.1 ; and V of 87 Pa·s and 117 Pa·s, respectively 1k had

[0210] Both CE-C and CE-E had a compressive permanent strain of 58%. CE-C had a V of 79 Pa·s. 1k It had, but V of 100,647 Pa·s 0.1 It had. CE-E is 207,835 Pa·s V 0.1 It had, but V of 135 Pa·s 1k had

[0211] CE-A, CE-B, and CE-D have compressive permanent strains of 79%, 86%, and 85%, respectively; V of 39,354 Pa·s, 71,726 Pa·s, and 179,109 Pa·s, respectively. 0.1 ; and V of 72 Pa·s, 86 Pa·s, and 85 Pa·s, respectively 1k had

[0212] As exemplified by Table 6, the cross-linked composition formed from the composition described herein has improved compressive permanent strain while maintaining processability.

[0213] Although specific embodiments of the present disclosure have been illustrated and described, those skilled in the art will understand that various other changes and modifications are possible without departing from the spirit and scope of the present disclosure. Accordingly, it should be understood that the appended claims include all changes and modifications within the scope of the present disclosure.

Claims

Claim 1 The composition comprises an ethylene / α-olefin copolymer; an olefin-based polymer; and a crosslinking agent. The ethylene / α-olefin copolymer is, Density of 0.860 to 0.900 g / cc; I2 of 0.5 to 30 dg / min, with a melt index (I2) measured according to ASTM D1238 (190℃, 2.16 Kg); I 10 I of 8 or more, measured according to ASTM D1238 (190℃, 10 kg). 10 / I2; More than 0.2 vinyls per 1,000 carbons; 50% or more of the percentage of vinyl in total unsaturation; and A composition containing an oligomer level of less than 5,000 ppm. Claim 2 A composition according to claim 1, wherein the ethylene / α-olefin copolymer is an ethylene / α-olefin copolymer. Claim 3 A composition according to claim 1 or 2, wherein the olefin-based polymer is a propylene-based polymer. Claim 4 A composition according to any one of claims 1 to 3, wherein the ethylene / α-olefin copolymer has a melt index (I2) of 0.5 to 15 dg / min, and I2 is measured according to ASTM D1238 (190°C, 2.16 kg). Claim 5 A composition according to any one of claims 1 to 4, wherein the ethylene / α-olefin copolymer comprises more than 0.2 unsaturation per 1,000 carbons. Claim 6 In any one of claims 1 to 5, I of the ethylene / α-olefin copolymer 10 A composition in which / I2 is 9 to 20. Claim 7 A composition according to any one of claims 1 to 6, wherein the ethylene / α-olefin copolymer comprises 0.2 to 1 vinyl per 1,000 carbons. Claim 8 A composition according to any one of claims 1 to 7, wherein the crosslinking agent comprises an organic peroxide. Claim 9 A composition according to claim 8, comprising 0.2% to 5% by weight of an organic peroxide based on the combined weight of the ethylene / α-olefin copolymer, the olefin-based polymer, and the organic peroxide. Claim 10 A composition according to claim 8 or 9, wherein the organic peroxide comprises di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, di-(tert-butylperoxyisopropyl)benzene, tert-butyl peroxybenzoate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, or a combination thereof. Claim 11 A composition comprising a crosslinking agent in any one of claims 1 to 10. Claim 12 A composition according to claim 11 comprising more than 0 weight% to 5 weight% of a crosslinking aid based on the combined weight of an ethylene / α-olefin copolymer, an olefin-based polymer, a crosslinking agent, and a crosslinking aid. Claim 13 A composition according to claim 11 or 12, wherein the crosslinking agent comprises trialyl cyanurate, trialyl isocyanurate, trifunctional acrylate, or a combination thereof. Claim 14 A composition according to any one of claims 11 to 13, wherein the weight ratio of the crosslinking agent to the auxiliary agent is 0.2:1 to 2:

1. Claim 15 A composition according to any one of claims 1 to 14, comprising 20% ​​to 80% by weight of an ethylene / α-olefin copolymer based on the combined weight of the ethylene / α-olefin copolymer, the olefin-based polymer, and the crosslinking agent. Claim 16 A composition according to any one of claims 1 to 15, comprising 20% ​​to 80% by weight of an olefin polymer based on the combined weight of the ethylene / α-olefin copolymer, the olefin polymer, and the crosslinking agent. Claim 17 A composition according to any one of claims 1 to 16, wherein the combined weight of the ethylene / α-olefin copolymer and the olefin-based polymer is greater than 60% by weight based on the combined weight of the ethylene / α-olefin copolymer, the olefin-based polymer, and the crosslinking agent. Claim 18 A cross-linked composition formed from the composition of any one of claims 1 to 17. Claim 19 A cross-linked composition according to claim 18, comprising a compressive permanent strain of 60% or less as measured at 120°C for 70 hours according to ASTM D395. Claim 20 A cross-linked composition according to claim 18 or 19, comprising a viscosity of greater than 105,000 Pa·s, measured at 0.1 rad / s at 230°C. Claim 21 In any one of paragraphs 18 to 20, 1,000 s at 230℃ -1 A cross-linked composition having a viscosity of less than 130 Pa·s, measured as. Claim 22 A cross-linked composition according to any one of claims 18 to 21, prepared by heat, irradiation, electron beam irradiation, or ultraviolet (UV) irradiation. Claim 23 An article comprising a cross-linked composition according to any one of paragraphs 18 to 22. Claim 24 Articles in paragraph 23 that are door profiles, window profiles, gaskets, or molded parts. Claim 25 A process for producing an ethylene / α-olefin copolymer according to any one of claims 1 to 17, comprising solution polymerizing ethylene and an α-olefin comonomer in the presence of a precatalyst having structure (I): Structure (I) In the above structure, M is Zr or Hf, and the metal is in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is an independently selected monodentate ligand; the total catalyst is charge-neutral; and R1 and R 16 At least one of them is selected from structure (II), structure (III), and structure (IV): In the above structure, R 31-35 , R 41-48 , and R 51-59 is independently -H, C1-C 40 Hydrocarbyl, C1-C 40 Heterohydrocarbil, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or selected from halogen, and R C C1-C independently 40 Selected from hydrocarbil; R3 and R 14 C1-C independently 40 Hydrocarbyl or hydrogen; R6 and R 11 C1-C independently 40 Hydrocarbyl or hydrogen; R2, R4, R5, R7, R8, R9, R 10 , R 12 , R 13 , and R 15 C1-C independently 40 Hydrocarbyl, C1-C 40 Heterohydrocarbil, -Si(R C )3, selected from the group consisting of halogen atoms, hydrogen atoms, and combinations thereof;R 17 and R 18 is independently C1-C3 hydrocarbylene and;R 19 and R 20 C1-C independently 40 It is hydrocarbyl or hydrogen. Claim 26 In paragraph 25, R1 and R 16 Process, which is structure (III) respectively: In the above structure, R 41-48 is independently selected from -H or C1-C6 alkyl. Claim 27 In paragraph 25 or 26, R3 and R 14 are respectively C1-C 12 Alkyl phosphorus, process. Claim 28 In any one of paragraphs 25 through 27, R6 and R 11 are C1-C respectively 12 Alkyl phosphorus, process. Claim 29 In any one of paragraphs 25 through 28, R3, R6, R 11 , and R 14 are C6-C respectively 11 Alkyl phosphorus, process. Claim 30 In any one of paragraphs 25 through 29, R 17 and R 18 It is -CH2-, process. Claim 31 In any one of paragraphs 25 through 30, R 19 and R 20 C2-C independently 10 Alkyl phosphorus, process. Claim 32 In any one of paragraphs 25 through 31, R2, R4, R5, R7, R8, R9, R 10 , R 12 , R 13 and R 15 is a hydrogen atom, process. Claim 33 In any one of paragraphs 25 to 32, the process is one in which the pre-catalyst is halogen-free. Claim 34 A process according to any one of paragraphs 25 to 33, wherein the polymerization occurs in a reactor at a temperature greater than 150°C. Claim 35 A process according to any one of paragraphs 25 to 34, wherein polymerization occurs in the presence of a co-catalyst comprising alumonic acid. Claim 36 A process according to any one of paragraphs 25 to 34, wherein the polymerization occurs in the presence of a co-catalyst comprising ammonium borate. Claim 37 A process in any one of paragraphs 25 through 36, wherein M is Zr.

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