Ethylene-copolymer rubber

Abstract

Units derived from ethylene, at least one C3-C 20 1. A composition comprising an ethylene copolymer comprising an α-olefin and at least one non-conjugated diene, the copolymer comprising: (i) up to 58 wt. %, preferably 35 to 56 wt. %, more preferably 38 to 52 wt. %, of units derived from ethylene, based on the total weight of the copolymer; and (ii) up to 57 wt. %, preferably 17 to 55 wt. %, of at least one C3 to C6 olefin, based on the total weight of the copolymer. 20 -units derived from an α-olefin, preferably propylene; wherein the ethylene copolymer has from about 80 to about 125 units derived from one or more dienes per polymer chain, and the ethylene copolymer is mixed with oil, the total amount of oil in the composition being 29 phr or less, and the composition containing 60 to 100 wt. % ethylene copolymer and oil, based on the total weight of the composition (=100%). Also provided are rubber compositions and rubber compounds and articles comprising the copolymer, as well as methods for making such articles, compositions, and compounds.

Description

[Technical Field]

[0001] This disclosure relates to ethylene copolymer rubber and rubber compositions, as well as processes for producing such rubber and rubber compositions, and articles produced using such rubber. [Background technology]

[0002] Ethylene-α-olefin elastomers and ethylene-propylene-diene copolymers (EPDM) are used in a wide range of applications. In one primary application, EPDM-type polymers are used as seals or as components of seal or sealing systems. EPDM rubber is found in sealing systems in automobiles, ships, and aircraft, for example, as sealing material for doors or windows (also known in the industry as "weatherstrip" applications). In many transportation applications, these materials are required to be low-density and are typically supplied as foamed materials (so-called "sponges"). EPDM rubber is also used in buildings to seal windows, or as seals to provide airtight or watertightness to fixtures (for example, as O-rings in faucets), or as seals or flanges for openings in washing machines and other equipment. Other applications of such rubber include belts, such as conveyor belts, escalator belts, and engine belts. Further applications include engine mounts, roofing materials, and hoses.

[0003] Rubber suitable for these applications is required to possess good mechanical properties, such as tensile strength, tear strength, good flexibility, elasticity, and shape retention under static and dynamic stress. When used in outdoor applications, these properties must be maintained over a wide temperature range. In many applications, particularly sealing applications, the rubber also needs to have good vibration or sound dampening properties (for example, to dampen engine noise).

[0004] In most applications, EPDM rubber is blended with at least one other component to produce so-called rubber "compounds" (hereinafter also referred to as "compounds"). Such components include fillers, curing agents, or foaming agents. It is well known that the mechanical properties of EPDM rubber, such as tensile strength, increase with the molecular weight of its polymer. This necessitates providing high molecular weight rubber to achieve improved mechanical properties. However, rubbers with high molecular weight tend to be difficult to process, particularly when manufacturing or processing compounds. Such difficulties manifest as insufficient mixing, difficulty in kneading, the formation of aggregated lumps in the compound, and surface roughness when curable or cured rubber compounds are extruded, cast, or cut.

[0005] Several methods for mitigating these problems are known in the industry. One approach is to create specific polymer designs and microstructures by controlling, for example, the molecular weight distribution or branching structure of the polymer. Another known approach is to reduce the overall viscosity of the rubber composition by adding several components, for example, blending it with other rubbers of lower viscosity, thereby diluting the rubber composition. Alternatively, or in addition to the above, oil can be added to the rubber to produce so-called "oil-extended polymers." Oil-extended polymers are produced by blending with one or more extender oils either during the polymer preparation process or during the finishing steps (i.e., before the polymer is isolated and dried). The extender oils are then uniformly mixed into the polymer. Such oil-extended polymers can be processed more easily to produce rubber compounds than the same polymer processed without oil, however, the addition of oil is only permitted during the process of producing the rubber compound.

[0006] (Patent Document 1) describes an oil-expanded EPDM polymer having a molecular weight of at least 300,000 g / mol. The extender oil content is 30-70 phr. The rubber composition has good mechanical properties and, furthermore, good vibration damping, expressed as a low delta min value in phase angle measurements. However, the high oil content increases manufacturing costs. The high oil content can also lead to a decrease in the dynamic performance of the rubber composition, especially when other components are added to it. This limits the amount of such components that can be added to the rubber composition, such as fillers or rubber additives, and narrows the operational scope of the oil-expanded EPDM polymer. (Patent Document 2) describes that at least some of these problems can be overcome by providing an ethylene copolymer of a polymer design defined by specific monomer composition and branching levels. The oil-spread rubber composition contains an ethylene copolymer having a molecular weight of at least 400,000 g / mol, and exhibits good mechanical performance and shape retention even with a relatively low oil content of 10 to 40 phr. However, (Patent Document 2) does not describe vibration and noise suppression or dynamic properties, which are useful for sealing applications, particularly for foamed seals, i.e., sponge materials.

[0007] It has now been discovered that compositions containing ethylene copolymers of specific compositions and structures, and compositions containing the same, can be processed to obtain rubber compounds having further improved dynamic and mechanical properties. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] U.S. Patent Application Publication No. 2017 / 0313868A1 [Patent Document 2] U.S. Patent Application Publication No. 2019 / 0153206A1

SUMMARY OF THE INVENTION

MEANS FOR SOLVING THE PROBLEM

[0009] In one aspect, an ethylene copolymer is provided that includes the following: (i) units derived from ethylene of 35% to 58% by weight or less, preferably 35% to 56% by weight, more preferably 38% to 52% by weight; (ii) units derived from at least one C3 - C 20 -α-olefin of 17% to 57% by weight or less (where at least one of the C3 - C 20 -α-olefins includes propylene); (iii) units derived from 5 - ethylidene - 2 - norbornene (ENB) of 5% to 20% by weight; where the weight percentages in (i) to (iii) are based on the total weight of the copolymer (100% by weight), and where the copolymer has more than 80 units derived from ENB per polymer chain, determined according to the following formula (I): Units derived from ENB = ([ENB]×10×Mn of the polymer) / 120 g / mol (I) [where, "[ENB]" is the content of ENB units in the polymer (unit, % by weight) (based on the total weight of the polymer (=100% by weight)), and "Mn of the polymer" means the number average molecular weight (Mn) of the polymer (unit, kg / mol)].

[0010] In another aspect, a method for producing a rubber compound is provided that includes mixing a composition containing an ethylene copolymer with at least one curing agent, optionally at least one filler, or a combination thereof.

[0011] In a further aspect, a rubber compound obtained by the method is provided.

[0012] In yet another embodiment, a method is provided for producing an article, comprising molding and curing the rubber compound, wherein the molding can be performed after, before, or simultaneously with the curing.

[0013] In a further embodiment, articles obtained by the method are provided.

[0014] In another embodiment, a method for preparing an oil-fed polymer composition is provided, which includes the following steps: (i) In the reaction medium, ethylene, at least one C3-C 20 A step of polymerizing an α-olefin and at least one non-conjugated diene to obtain an ethylene copolymer, (ii) A step of mixing the ethylene copolymer with one or more oils in the reaction medium, (iii) a step of removing the reaction medium and isolating the composition containing the copolymer and the oil, (iv) In some cases, the composition is subjected to at least one step selected from drying, molding, compression, washing, and a combination thereof. [Brief explanation of the drawing]

[0015] [Figure 1] This is a van Gurp-Palmen plot obtained from DMTA measurements of the polymer in Example 1 (explained in the Experiment section). The dashed lines represent the minimum phase angle and the corresponding absolute modulus, [δ]min and G*min, respectively. [Figure 2] This is a plot of the loss coefficient (tan delta) versus frequency, obtained from dynamic-mechanical analysis (explained in the experimental section). [Modes for carrying out the invention]

[0016] Standards may be used in the following descriptions. Unless otherwise specified, the standard used is the version in effect as of March 1, 2020. For example, if no version of the standard is in effect due to its expiration or other reasons, the version that was in effect on the date closest to March 1, 2020, will be referred to.

[0017] In the following description, the amounts of components in a composition or polymer can be expressed interchangeably as "weight percent" or "wt.% (or % by weight)." The terms "weight percent" or "wt.% (or % by weight)" are used interchangeably and are based on the total weight of each component of the composition or polymer (100% unless otherwise specified). The amounts of units derived from the monomer or other components of a polymer are expressed as wt% based on the weight of the copolymer, and even when the copolymer is oil-fed, the total weight of the copolymer still refers to the total weight of the copolymer. In other words, the total weight of an oil-fed copolymer is the weight of the copolymer plus the extender oil minus the weight of the extender oil.

[0018] The term "phr" means parts per 100 parts of rubber, i.e., weight percentage based on the total amount of rubber set at 100% by weight. In this disclosure, ethylene copolymer is rubber. If the composition contains one or more ethylene copolymers, or an ethylene copolymer and one or more other rubbers, "phr" refers to the total amount of those rubbers.

[0019] The ranges indicated in this disclosure include all values ​​between the endpoints of those ranges, and are disclosed, but unless otherwise specified, they also include those endpoints.

[0020] The terms "comprising" and "containing" are interchangeable. They mean that the ingredients or components they suggest are present, but do not exclude the presence of other ingredients or components. The term "consisting," on the other hand, is used in a more limited sense, meaning that the composition is limited to only the components that "consist of it."

[0021] Ethylene-α-olefin copolymer The ethylene-α-olefin copolymers provided herein can be used to obtain compounds having good properties, particularly useful in sealing applications, such as good dynamic properties, such as low tan delta value, high rebound elasticity, low compression set, and low dynamic stiffness, as well as good mechanical properties, such as tensile strength, and elastic properties, such as elongation at break. Despite having high molecular weights, they can be processed into rubber compounds with little to no extender oil.

[0022] The ethylene-α-olefin copolymers in this disclosure are copolymers of ethylene and at least two further comonomers. This means that the copolymer contains repeating units derived from ethylene and those at least two further comonomers. Preferably, the copolymer contains up to 58 weight percent (wt%) of ethylene-derived units. More preferably, the copolymers in this disclosure contain up to 56 weight percent, more preferably up to 52 weight percent, of ethylene-derived units. In one embodiment, the ethylene-α-olefin copolymers in this disclosure contain 35 to 56 weight percent, preferably 38 to 52 weight percent, of ethylene-derived units. The weight percentage is based on the total weight of the copolymer.

[0023] In addition to units derived from ethylene, the copolymers in the present disclosure include repeating units derived from the following: (i) one or more C3 - C 20 -α-olefins, preferably C3 - C 12 -α-olefins, (ii) at least one non-conjugated diene, and (iii) at least one dual polymerizable diene.

[0024] C 3 ~C 20 -α-olefin C3 - C 20 -α-olefins (also referred to herein as "C3 - C 20 -alpha-olefins") contain 3 to 20 carbon atoms and are olefins having a single aliphatic carbon-carbon double bond. That double bond is located at the terminal front end of the olefin. The α-olefin may be aromatic or aliphatic, linear, branched or cyclic. Examples include the following: propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. A combination of multiple alpha-olefins may be used. Preferred alpha-olefins are aliphatic C3 - C 12-α-olefins, more preferably aliphatic linear C3-C4-α-olefins, most preferably propylene (C3-α-olefin) and 1-butene (C4-α-olefin). The ethylene-α-olefin copolymer of the present disclosure is propylene and one or more other C3-C4-olefins. 20 It is preferable that it contains -α-olefin. In one embodiment of the present disclosure, the ethylene-α-olefin copolymer is C3-C 20 -The α-olefin contains only propylene. The ethylene copolymer preferably contains up to 57% by weight, more preferably up to 55% by weight, of C3-C3. 20 - Contains units derived from α-olefins (all weight percentages (W%) are based on the total weight of the copolymer). The ethylene-α-olefin copolymer is present in 17-57 Wt%, C3-C 20 Preferably, the ethylene-α-olefin copolymer contains total units derived from propylene, preferably up to 57% by weight, more preferably up to 55% by weight (all weight percentages are based on the total weight of the copolymer). In one embodiment of the present disclosure, the ethylene-α-olefin copolymer contains 17 to 55% by weight of total units derived from propylene.

[0025] Non-conjugated dienes A non-conjugated diene is a polyene containing at least two double bonds, the double bonds being non-conjugated in the chain, ring, ring structure, or in combination thereof. These polyenes may have intra-ring and / or extra-ring double bonds and may be unsubstituted or have multiple substituents of the same or different types. The double bonds are separated by at least two carbon atoms. Often, only one of the multiple non-conjugated double bonds is converted by the polymerization catalyst. The non-conjugated diene is preferably aliphatic, more preferably alicyclic and aliphatic.

[0026] Suitable non-conjugated dienes include aromatic polyenes, aliphatic polyenes, and alicyclic polyenes, preferably polyenes having 6 to 30 carbon atoms (C6-C6). 30 -Polyene, fufar C6~C 30Examples of non-conjugated dienes include: 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1,6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1, 4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadien, 5-methyl-1,4-nonadien, 4-ethyl-1 ,4-nonadien, 5-ethyl-1,4-nonadien, 5-methyl-1,5-nonadien, 6-methyl-1,5-nonadien, 5-ethyl-1,5-nonadien, 6-ethyl-1,5-nonadien, 6-methyl-1,6-nonadien, 7-methyl-1,6-nonadien, 6-ethyl-1,6-nonadien, 7-ethyl-1,6-nonadien, 7-methyl-1,7-nonadien, 8-methyl-1,7-nonadien, 7-ethyl-1,7-nonadien, 5-methyl-1,4-decadien, 5-ethyl-1,4-decadien, 5-methyl-1,5-decadien N, 6-methyl-1,5-decadien, 5-ethyl-1,5-decadien, 6-ethyl-1,5-decadien, 6-methyl-1,6-decadien, 6-ethyl-1,6-decadien, 7-methyl-1,6-decadien, 7-ethyl-1,6-decadien, 7-methyl-1,7-decadien, 8-methyl-1,7-decadien, 7-ethyl-1,7-decadien, 8-ethyl-1,7-decadien, 8-methyl-1,8-decadien, 9-methyl-1,8-decadien, 8-ethyl-1,8-decadien, 1,5,9-decatriene, 6-methyl-1,6-Undecadien, 9-methyl-1,8-Undecadien, dicyclopentadiene, and mixtures thereof. Dicyclopentadiene can be used both as a dual polymerizable diene or as a non-conjugated diene, in which case dicyclopentadiene is used in combination with at least one dual polymerizable diene or at least one non-conjugated diene.

[0027] Preferred non-conjugated dienes include alicyclic polyenes, which have at least one cyclic unit. In preferred embodiments, the non-conjugated diene is selected from polyenes having at least one intraring double bond and optionally at least one extraring double bond. Preferred examples include dicyclopentadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene (ENB), with ENB being particularly preferred. In one embodiment, the copolymer of the present disclosure contains only ENB as the non-conjugated diene.

[0028] Examples of aromatic non-conjugated polyenes include vinylbenzene (including its isomers) and vinyl-isopropenylbenzene (including its isomers).

[0029] In typical embodiments of the present disclosure, the copolymer contains at least 5% by weight and up to 20% by weight of units derived from one or more non-conjugated dienes. In preferred embodiments, the copolymer contains 6 to 18% by weight, more preferably 7 to 18% by weight, for example 8 to 15% by weight of units derived from one or more non-conjugated dienes. In preferred embodiments, the copolymer contains 5% by weight to a maximum of 20% by weight of units derived from ENBs, more preferably 6 to 18% by weight of units derived from ENBs, or 7 to 18% by weight, for example 8 to 15% by weight of units derived from ENBs (all weight percentages are based on the total weight of the ethylene-α-olefin copolymer).

[0030] Dual polymerizable diene Dual polymerizable dienes are selected from vinyl-substituted aliphatic monocyclic unconjugated dienes, vinyl-substituted bicyclic unconjugated aliphatic dienes, alpha-omega linear dienes, and unconjugated dienes, where both unsaturated moieties can be polymerized by a coordination catalyst (e.g., a Ziegler-Natta vanadium catalyst or a metallocene-type catalyst). Examples of dual polymerizable dienes include: 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane, dicyclopentadiene, and 1,4-cyclohexadiene. Preferably, non-conjugated vinylnorbornene and C8~C 12 These are alpha-omega linear dienes (e.g., 1,7-octadiene, 1,8-nonadien, 1,9-decadien, 1,10-undecadien, 1,11-dodecadien). The dual polymerizable dienes may be further substituted with at least one group containing heteroatoms from groups 13-17, such as O, S, N, P, Cl, F, I, Br, or combinations thereof. The dual polymerizable dienes can cause or contribute to the formation of branching in the polymer.

[0031] In preferred embodiments of the present disclosure, the dual polymerizable diene is selected from 2,5-norbornene, 5-vinyl-2-norbornene (VNB), 1,7-octadiene, and 1,9-decadiene, with 5-vinyl-2-norbornene (VNB) being the most preferred. In one embodiment, the copolymer of the present disclosure contains only VNB as the dual polymerizable diene.

[0032] The copolymers of this disclosure preferably contain 0.05% to 5% by weight, more preferably 0.10% to 3% by weight, or 0.2% to 1.2% by weight, units derived from one or more dual polymerizable dienes, more preferably from VNB (all weight percentages are based on the total weight of the ethylene-α-olefin copolymer).

[0033] In preferred embodiments, the copolymers of the present disclosure include units derived from 5-ethylidene-2-norbornene and 5-vinylnorbornene. In more preferred embodiments of the present disclosure, the copolymers include units derived from ethylene, propylene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene. For example, the ethylene-α-olefin copolymer may contain 5 to 20% by weight of units derived from ENB and 0.05 to 5% by weight of units derived from VNB.

[0034] The ethylene-α-olefin copolymer in this disclosure may or may not contain units derived from other comonomers. The total amount of units derived from ethylene, non-conjugated dienes, dual polymerizable dienes, and α-olefins is greater than 99% by weight, preferably 100% by weight, based on the total weight of the ethylene-α-olefin copolymer. In one embodiment of this disclosure, the total amount of units derived from ethylene, propylene, and ENB is greater than 75% by weight, preferably 90% by weight, and more preferably at least 95% by weight, based on the total weight of the polymer of the ethylene-α-olefin copolymer.

[0035] The ethylene-α-olefin copolymers in this disclosure preferably have a high Mooney viscosity, for example, a Mooney viscosity ML1+8 (150°C) of at least 80, or at least 90, or at least 100, and in fact may have a Mooney viscosity higher than 150. For example, the copolymer may have a Mooney viscosity ML1+8 (150°C) of 80 to 120, or 80 to 150.

[0036] Preferably, the ethylene-α-olefin copolymer in this disclosure has a weight-average molecular weight (Mw) of at least 400,000 g / mol, preferably at least 500,000 g / mol, and more preferably at least 600,000 g / mol. For example, the polymer may have an Mw between 400,000 g / mol and 700,000 g / mol. The ethylene copolymer in this disclosure may have a polydispersity (molecular weight distribution) of at least 2.5, for example, 3.0 to 30, or 3.5 to 25, or 3.7 to 10. In one embodiment of this disclosure, the number-average molecular weight (Mn) of the ethylene copolymer in this disclosure may be about 40 to 230 kg / mol. Mw and Mn can be measured by gel permeation chromatography.

[0037] The ethylene-α-olefin copolymer in this disclosure may be branched, having a degree of branching of, for example, Δδ between 2 and 50, more preferably between 5 and 35, or between 8 and 30, or between 10 and 25. Δδ (in degrees) is the difference between the phase angle δ at a frequency of 0.1 rad / s and the phase angle δ at a frequency of 100 rad / s, and is measured by dynamic mechanical spectroscopy (DMS) at 125°C.

[0038] Preferably, the ethylene-α-olefin copolymer in this disclosure has a diene content per polymer chain of at least 80, preferably at least 95, and more preferably at least 100, and the diene contains ENB. The ethylene-α-olefin copolymer in this disclosure may have a diene content per polymer chain ranging from about 80 to a maximum of about 125.

[0039] In a preferred embodiment, the ethylene-α-olefin copolymer in this disclosure has an ENB content of at least 80, preferably at least 95, and more preferably at least 100 per polymer chain. In one embodiment of this disclosure, the ethylene-α-olefin copolymer may have an ENB content of about 80 to a maximum of about 125 per polymer chain.

[0040] In one embodiment of the present disclosure, the ethylene copolymer has a content of ENB-derived units between 5 and 20% by weight, and a branching degree (expressed as Δδ) between 10 and 25, based on the total weight of the copolymer. Such copolymers preferably have 5 to 20% by weight of 5-ethylidene-2-norbornene (ENB)-derived units and 0.05 to 5% by weight of 5-vinyl-2-norbornene (VNB)-derived units. Preferably, such copolymers have a high Mooney viscosity, for example, a Mooney viscosity ML1+8 (150°C) of at least 90 or at least 100, and may actually have a Mooney viscosity greater than 150. Preferably, the copolymers of this embodiment have a Mw between 400,000 g / mol and 700,000 g / mol, and / or a polydispersity of at least 2.5, for example, 3.0 to 30. The copolymer in this embodiment may have a number-average molecular weight (Mn) of approximately 40 to 230 kg / mol.

[0041] The ethylene-α-olefin copolymers in this disclosure can be processed, preferably mixed with a small amount of oil, to form compounds having good, i.e., further improved, dynamic and mechanical properties, for example, as oil-fed copolymers. The oil-fed ethylene-α-olefin copolymer has properties equivalent to those of the ethylene-α-olefin copolymer described above, except that the Mooney viscosity of the oil-fed copolymer is lower than that of the unoil-fed copolymer. Accordingly, the disclosure also provides compositions comprising one or more ethylene copolymers of the disclosure mixed with oil. Preferably, the oil is incorporated into the polymer. Preferably, the mixture is a solid mixture. Preferably, the mixture is homogeneous. The terms “solid” and “homogeneous” refer to the appearance as seen with the naked eye. Preferably, the solid, homogeneous mixture of oil and polymer contains the ethylene copolymer in an oil-fed form, i.e., the ethylene copolymer is oil-fed. For example, the oil-expanded copolymer is preferably obtained by mixing the copolymer and oil in a reaction medium during or after the polymerization process, after which the reaction medium is removed. The amount of oil is preferably greater than 0 and up to 29 phr. Thus, a composition is provided comprising the copolymer of the Disclosure, which is mixed with oil and contains a total amount of oil of 5 to 25 phr, preferably 10 to 20 phr. The oil preferably contains a hydrocarbon-based oil. The copolymer mixed with oil is preferably an oil-expanded copolymer. The oil in the composition is preferably an extender oil for the oil-expanded copolymer. At least the main portion of the oil, i.e., more than 50% by weight of the oil based on the total amount of oil, is preferably an extender oil, i.e., an oil for the oil-expanded copolymer.

[0042] In one embodiment of the present disclosure, a composition is provided comprising an ethylene-α-olefin copolymer mixed with an oil, wherein the total oil content of the composition is 5 to 25% by weight, preferably 8% to a maximum of 20% by weight, or 8% to a maximum of 18% by weight, based on the total weight of the composition. Preferably, the oil contains a hydrocarbon-based oil. Preferably, the copolymer mixed with the oil is an oil-expanded copolymer. Preferably, the oil in the composition is an extender oil for the oil-expanded copolymer. Preferably, at least the major portion of the oil, i.e., more than 50% by weight of the oil based on the total amount of the oil, is an extender oil, i.e., an oil for the oil-expanded copolymer.

[0043] Typically, compositions comprising ethylene-α-olefin copolymer in this disclosure contain 60% by weight, preferably 90% by weight, more preferably 95% by weight, and even more preferably at least 97% by weight of ethylene copolymer and oil (the weight percentages are based on the total weight (=100%) of the composition). The oil preferably contains one or more hydrocarbon-based oils. The ethylene-α-olefin copolymer is preferably oil-fed. The oil in the composition is preferably an extender oil for the oil-fed copolymer. At least the major portion of the oil, i.e., more than 50% by weight of the oil based on the total amount of oil, is preferably an extender oil, i.e., an oil for the oil-fed copolymer.

[0044] A mixture of oil and copolymer, such as the oil-expanded ethylene-α-olefin copolymer in this disclosure, is typically a solid composition and a homogeneous mixture of oil and polymer. They can be prepared by blending the ethylene copolymer with at least a portion, preferably all, of the oil in a liquid phase, preferably while preparing the polymer, to obtain the oil-expanded copolymer. The oils that can be used may be various commonly used oils, or softeners, known in the art as "extender oils" in rubber production. The oil preferably contains one or more hydrocarbon-based oils, or is a mixture thereof. The term "hydrocarbon-based" means that the oil contains at least 50% by weight of hydrogen and carbon based on the total composition of the oil. The hydrocarbon-based oil preferably contains at least 90% by weight, more preferably at least 95% by weight of carbon and hydrogen. The oil is preferably liquid at 25°C and atmospheric pressure (1 atm). Suitable oils include hydrocarbon-based oils, such as those obtained from high-boiling fractions of petroleum. Specific examples include oils primarily based on alkanes and / or cycloalkanes, such as paraffinic oils, naphthenic oils, and mineral oils. Aromatic oils, such as those obtained from petroleum distillates, are also suitable. These oils typically have a boiling point of 5-35 mm at 100°C. 2It exhibits a dynamic viscosity of / s. Preferred oils include paraffinic oils. Suitable oils are commercially available under trade names such as: PLI PROCESS OIL P 460SUNPAR 2280 (available from Sunoco), CONOPURE 12P (available from ConocoPhillips), and PARALUX 6001 (available from Chevron Texaco). Other examples include oils produced by gas-to-liquidation (GTL) processes, such as RISELLA X 430 (made by Shell). These oils may contain olefin oligomers, such as homo-oligomers or co-oligomers of olefins, preferably alpha-olefin oligomers. In one embodiment, the oil contains one or more alpha-olefin oligomers or polymers and exhibits one or more of the following properties: a. Viscosity at 190°C (Brookfield viscosity): 90,000 mPa·sec or less, or 80,000 or less, or 70,000 or less, or 60,000 or less, or 50,000 or less, or 40,000 or less, or 30,000 or less, or 20,000 or less, or 10,000 or less, or 8,000 or less, or 5,000 or less, or 4,000 or less, or 3,000 or less, or 1,500 or less, or between 250 and 15,000 mPa·sec, or between 500 and 5,500 mPa·sec, or between 500 and 3,000 mPa·sec; and / or b. Viscosity at 60°C (measured according to ASTM D3236): 200 mPa·sec to 20,000 mPa·sec, 400 to 20,000 mPa·sec, or 500 to 20,000 mPa·sec, or 1,000 to 10,000 mPa·sec. In one embodiment, the olefin oligomer may be reactive with the polymer during polymerization and incorporated into the polymer chain during the polymerization process.

[0045] Another preferred embodiment of the present disclosure provides a composition comprising the ethylene-α-olefin copolymer of the present disclosure and an oil ranging from 0 to a maximum of 29 phr, preferably 5 to 25 phr, more preferably 10 to 20 phr, wherein the composition has a Mooney viscosity ML1+8 (150°C) of about 80 to about 120, preferably for example, about 85 to about 110. The oil preferably contains a hydrocarbon-based oil. The composition has a delta min(δ) greater than 1 and less than 4.0, preferably less than 3.70, more preferably less than 3.20. min It is advantageous to have a delta min(δ) greater than 2.0 and less than 3.5. For example, the ethylene-α-olefin copolymer in this disclosure has a delta min(δ) greater than 2.0 and less than 3.5. min It is preferable to have ).

[0046] It is preferable that the ethylene-α-olefin copolymer is oil-distributed. It is preferable that the oil in the composition is an extender oil for the oil-distributed copolymer. It is preferable that at least the main portion of the oil, i.e., more than 50% by weight of the oil based on the total amount of oil, is an extender oil, i.e., an oil for the oil-distributed copolymer.

[0047] One embodiment of the present disclosure provides a composition comprising an ethylene copolymer having a content of ENB-derived units between 5 and 20% by weight, and a branching degree (expressed as Δδ) between 10 and 25, based on the total weight of the copolymer. Such a copolymer preferably has 5 to 20% by weight of 5-ethylidene-2-norbornene (ENB)-derived units and 0.05 to 5% by weight of 5-vinyl-2-norbornene (VNB)-derived units. Preferably, such a copolymer has a high Mooney viscosity, for example, a Mooney viscosity ML1+8 (150°C) of at least 90 or at least 100, and may actually have a Mooney viscosity greater than 150. Preferably, the copolymer of this embodiment has a Mw between 400,000 g / mol and 700,000 g / mol, and / or a polydispersity of at least 2.5, for example, 3.0 to 30. The copolymer in this embodiment may have a number-average molecular weight (Mn) of about 40 to 230 kg / mol. The composition in this embodiment has a total oil content of up to 29 phr of oil. It is preferable that the ethylene copolymer is oil-fed. It is preferable that the oil in the composition is an extender oil for the oil-fed copolymer. It is preferable that at least the major portion of the oil, i.e., more than 50% by weight of the oil based on the total amount of oil, is an extender oil, i.e., an oil for the oil-fed copolymer.

[0048] <Preparation of polymers> The copolymers in this disclosure are ethylene, at least one C3-C copolymer, as is known in the art with respect to the survival of ethylene copolymers. 20These polymers can be prepared by a process comprising copolymerizing an α-olefin, at least one non-conjugated diene, and optionally at least one dual-polymerizable diene monomer. These polymers may be produced using conventional catalysts, such as Ziegler-Natta catalysts, or metallocene-type catalysts, or post-metallocene catalysts, or combinations of multiple catalysts. Ziegler-Natta catalysts are non-metallocene-type catalysts based on transition metal halides, particularly titanium or vanadium. Metallocene-type catalysts are organometallic catalysts, where the metal is bonded to at least one cyclic organic ligand, preferably at least one cyclopentadienyl ligand or at least one indenyl ligand. In one embodiment, a Ziegler-Natta catalyst is used. In another embodiment, a metallocene-type catalyst is preferably used. In yet another embodiment, a combination of two or more metallocene-type catalysts is used.

[0049] The polymerization can be carried out in the gas phase, in a slurry, or in a solution in an inert solvent, preferably a hydrocarbon solvent.

[0050] Polymerization can also occur in different polymerization zones. One polymerization zone may be a container where polymerization takes place, whether it is a batch reactor or a continuous reactor. When using multiple reactors (for example, reactors connected in series or in parallel), each reactor is considered an independent polymerization zone.

[0051] Preferred solvents include one or more hydrocarbon solvents. 5~12Examples of hydrocarbons include pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, pentamethylheptane, naphtha hydrogenates, and their isomers and mixtures. Polymerization can be carried out at temperatures of 10 to 250°C, depending on the product to be produced. When polymerization is carried out in solution, it is most preferable to carry it out at a temperature higher than 50°C.

[0052] In preferred embodiments, the polymerization involves the use of one or more chain transfer agents for the purpose of controlling the molecular weight of the polymer. A preferred chain transfer agent is hydrogen (H2). The diene content per polymer chain can be controlled, for example, by controlling the amount and molecular weight (chain length) of the diene in the reaction, as is known in the art. Branching can be introduced, as is known in the art, for example, by using a specific catalyst, such as a catalyst that creates branching in the polymer, such as a catalyst that creates vinyl groups, or by using a monomer that creates branching in the polymer, such as a dual polymerizable diene, or by using a combination of both. The degree of branching can be controlled, for example, by adjusting the amount of branching during polymerization, i.e., the feedstream, as is known in the art. The minimum phase angle can be controlled by the level of long-chain branching.

[0053] Oil-fed ethylene copolymers are preferably obtained by blending one or more extender oils with the ethylene copolymer during the preparation of the polymer and before finishing the polymer, more specifically before removing the solvent. It is preferable to add one or more oils to the reaction solution after the reaction solution has been removed from the reaction vessel and / or after the polymerization reaction for producing the oil-fed polymer has been stopped and before the solvent of the reaction solution has been removed. For example, the addition may be carried out after the polymerization reactor and before the removal of volatile components, for example, before the steam stripper or dry-finish extruder. It is preferable to blend the extender oils with the ethylene-α-olefin copolymer when the ethylene-α-olefin copolymer is dissolved or suspended in the reaction medium, preferably when it has been withdrawn from the polymerization reactor.

[0054] Ethylene copolymer compound The ethylene copolymer in this disclosure, preferably a composition containing the copolymer in this disclosure mixed with oil, more preferably an oil-fed copolymer, may also be combined with one or more additional components. Such additional components include, but are not limited to, (a) one or more curing agents, (b) one or more fillers, and (c) one or more rubber additives. By mixing the ethylene copolymer and the oil-fed composition with such components, a rubber compound can be obtained for producing a rubber compound, which is typically a homogeneous, solid mixture of rubber and these further components. In the rubber compound, typically, the content of components other than the ethylene copolymer and oil is at least 10% by weight, or more than 10% by weight, based on the total weight of the composition. These rubber compounds are curable and can be cured to give a vulcanized compound, i.e., a "vulcanized product".

[0055] hardening agent Suitable curing agents (vulcanizing agents) include, but are not limited to, the following: sulfur, sulfur chloride, sulfur dichloride, 4,4'-dithiodimorpholine, morpholine disulfide; alkylphenol disulfide, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), seleniumdimethyldithiocarbamate, and organic peroxides. Examples of organic peroxides include, but are not limited to, dicumyl peroxide (DCP), 2,5-di(t-butylperoxy)-2,5-dimethylhexane (DTBPH), di(t-butylperoxyisopropyl)benzene (DTBPIB), 2,5-di(benzoylperoxy)-2,5-dimethylhexane, 2,5-(t-butylperoxy)-2,5-dimethyl-3-hexine (DTBPHY), di-t-butyl peroxide, and di-t-butylperoxide-3,3,5-trimethylcyclohexane (DTBTCH), or mixtures thereof. Of these, sulfur, TMTD, TETD, DCP, DTBPH, DTBPIB, DTBPHY, and DTBTCH are preferred.

[0056] In the case of sulfur vulcanization, it is preferable to use sulfur or a sulfur-containing curing agent in an amount of 0.1 to 10 phr, preferably 0.5 to 5 phr, and more preferably 0.5 to 2 phr.

[0057] In the case of peroxide vulcanization, it is preferable to use an organic peroxide-based curing agent in an amount of 0.1 to 15 phr, preferably 0.5 to 5 phr.

[0058] Sulfur as a vulcanizing agent may be used in combination with one or more vulcanization accelerators and one or more vulcanization activators. Examples of vulcanization accelerators include, but are not limited to, the following: N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, dibenzothiazyl disulfide, diphenylguanidine, triphenylguanidine, di-o-tolylguanidine, o-tolyl-biguanide, diphenylguanidine phthalate, acetaldehyde-aniline reaction product, butyraldehyde-aniline Condensates, hexamethylenetetramine, acetaldehyde ammonia, 2-mercaptoimidazoline, thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, di-o-tolylthiourea, tetramethylthiuram monosulfide, TMTD, TETD, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethyl-thiocarbamate, zinc di-n-butylthiocarbamate, zinc ethylphenyldithiocarbamates, zinc butylphenyldithiocarbamates, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, telluride diethyldithiocarbamate, zinc dibutylxanthate, and ethylenethiourea. If a vulcanization accelerator is used, it is preferably used in an amount between 0.1 and 10 parts by weight, more preferably 0.2 and 5 parts by weight, and most preferably between 0.25 and 2 phr, per 100 parts by weight of the ethylene copolymer.

[0059] Examples of vulcanization activators include, but are not limited to, the following: metal oxides, such as magnesium oxide and zinc oxide; stearic acid or its metal salts; stearic acid or combinations thereof, such as a combination of zinc oxide and stearic acid. The vulcanization activator is usually used in an amount of 0.5 to 10 phr, preferably 0.5 to 5 phr, relative to the ethylene copolymer.

[0060] When using a peroxide or a mixture of peroxides as a vulcanizing agent, a peroxide crosslinking aid may be used. Examples of such peroxide crosslinking aids include: cyanurate compounds, such as triallyl cyanurate and triallyl isocyanurate; (meth)acrylate compounds, such as trimethylolpropane-trimethacrylate and ethylene glycol-dimethacrylate; zinc-dimethacrylate and zinc diacrylate; divinylbenzene; p-quinone dioxime; m-phenylenedimaleimide; (high vinyl) polybutadiene; and combinations thereof. A peroxide crosslinking aid with a value of 0.1 to 5 phr is preferred, and a peroxide crosslinking aid with a value of 0.25 to 2.5 phr is more preferred. When a peroxide is used in addition as a vulcanizing agent, it is preferable to use sulfur (elementally or as part of a sulfur vulcanization accelerator or donor) to obtain a so-called hybrid curing system. These curing systems combine the high heat resistance typical of peroxide curing with the extremely good extreme properties typically associated with sulfur vulcanization systems, such as tensile and tear properties, as well as excellent dynamic and fatigue performance. The amount of sulfur used is preferably 0.05 to 1.0 phr, and more preferably 0.2 to 0.5 phr.

[0061] Filler The filler is preferably used in an amount of 20 to 500 phr. Preferred fillers include carbon black and / or inorganic fillers such as silica, calcium carbonate, talcum, and clay, which are commonly used with rubber. The type of carbon black is specified by ASTM D-1765, based on its particle size (BET, in units of m). 2 ( / g) and structure (DBP adsorption amount, unit cm) 3 They are classified according to (100g). It is preferable to use carbon black fillers having a BET number of 5 to 150 and a DBP number of 30 to 140. In the industry, these types of carbon black are often represented by abbreviations such as MT, SRF, GPF, FEF, HAF, ISAF, and SAF. These inorganic fillers may be surface-treated with a suitable silane. Two or more such fillers can also be used in combination. It is most preferable that the filler contains carbon black and / or silica silane.

[0062] Further fillers include other rubbers, including one or more types of EPDM rubber, and rubber blends.

[0063] Other rubber additives (rubber enhancers) Other rubber additives include those commonly used in the rubber compounding industry. Examples include, but are not limited to, the following: antioxidants (e.g., hindered phenol compounds, such as those marketed by BASF under trade names IRGANOX 1010 or IRGANOX 1076); phosphates (e.g., under the trade name IRGAFOS (as marketed as 168), desiccants (e.g., calcium oxide), tackifiers (e.g., polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal stearate and glycerol stearate, and rosin hydrogenate, etc.), binders, heat stabilizers; anti-tacks; release agents; antistatic agents; pigments; colorants; dyes, processing aids (e.g., vulcanizing oils, fatty acids, stearates, poly- or di-ethylene glycol), antioxidants, heat stabilizers (e.g., poly-2,2,4-trimethyl-1,2-dihydroquinoline, or zinc 2-mercaptobenzimidazole), UV stabilizers, anti-ozone agents, foaming agents and release agents, dispersing agents, or processing aids such as talc or metal salts, such as zinc stearate, magnesium stearate, or calcium stearate, and plasticizers (plasticizer lubricating oil, e.g., trade name PLI PROCESS OIL) (P460, commercially available materials, paraffin, liquid paraffin, petroleum asphalt, petrolatum, low molecular weight polyisobutylene or polybutylene, liquid EPDM or EPM, coal tar pitch, castor oil, linseed oil, beeswax, atactic polypropylene, and coumarone indene resin). The plasticizer is preferably used in an amount of 20 to 250 phr. The rubber additive may contain a plasticizer which may contain one or more oils, and the total oil content in the rubber compound should be higher than that of the composition used to produce the compound. Further additives known in the industry may be used.

[0064] Process for manufacturing rubber compounds Rubber compounds containing ethylene copolymers in this disclosure can be produced by mixing a composition containing ethylene copolymer, preferably ethylene copolymer mixed with oil, with one or more components, such as a) one or more of the curing agents described above, b) one or more of the fillers described above, and / or c) one or more of the rubber additives described above. A typical process for forming a vulcanizable rubber compound involves mixing the following to form a vulcanizable rubber composition: (i) A composition comprising an ethylene copolymer mixed with oil, preferably as an oil-spread ethylene copolymer, (ii) One or more curing agents, (iii) One or more fillers, (iv) One or more other rubber additives (preferably including at least one plasticizer).

[0065] The mixing preferably involves kneading using conventional rubber mixing equipment, such as a kneader, open roll mill, internal mixer, or extruder. The mixing can be carried out in one or more steps known to those skilled in the art.

[0066] A composition comprising an ethylene copolymer, preferably an oil-fed copolymer mixed with oil, is used to prepare a vulcanized rubber compound or article having at least two, preferably at least three, more preferably at least four, or all of the following properties: (a) Shore A hardness: at least 40, (b) Tensile strength at break: at least 10 MPa, (c) Elongation at break: at least 400%, (d) tan delta: less than 0.16, preferably less than 0.15. (e) Dynamic stiffness: less than 1.35, preferably less than 1.25. (f) Rebound elasticity: at least 63% (at 23°C and 60°C).

[0067] Generally, compounds with low compression set, for example, less than 9 at 72 hours and 23°C, can be prepared.

[0068] Articles and Applications To manufacture an article, a curable (vulcanizable) rubber compound is subjected to at least one molding step, such as extrusion and / or die molding, and then subjected to at least one vulcanization step. The vulcanization can be carried out before, during, or after molding, for example, during or after extrusion and / or die molding. Articles made using the ethylene copolymer in this disclosure include a cured form of the polymer, i.e., the polymer is crosslinked by itself or with other crosslinkable components in an article, such as a compound or composition used to make other curable rubbers.

[0069] Therefore, a method for producing an article is also provided, which includes molding and curing the rubber compound of this disclosure, although the molding may be carried out after, before, or simultaneously with curing. Thus, an article obtained by this method is also provided.

[0070] The ethylene copolymers and compositions and compounds containing them as disclosed herein can be used in a variety of end-use applications, including various applications suitable for EPDM polymers. Examples include, but are not limited to, hoses, belts, seals, engine mounts, roofing materials, or gaskets.

[0071] The ethylene copolymers in this disclosure, including compounds made therefrom, may be particularly suitable as sealing materials or for making seals. Examples of seals include solid seals. A solid seal means that the material is not foamed, and unlike foamed materials, it is not porous or has a spongy structure. The ethylene copolymers and compositions in this disclosure, including compounds made therefrom, may be particularly suitable for making foamed articles, including spongy seals or foamed seals. In one embodiment of this disclosure, the article is a foamed article, more preferably a foamed seal, more preferably 1.0 g / cm³ 3 The article has a density of less than 0.8, for example, between 0.4 and 0.8. In yet another embodiment of the present disclosure, the article comprising the ethylene copolymer of the present disclosure is provided in a cured form, where the article is preferably a solid seal, i.e., a non-foaming seal.

[0072] <List of specific embodiments> The Disclosure is described in more detail here by a list of exemplary embodiments, but the Disclosure is not limited to these exemplary embodiments shown in the following list.

[0073] First exemplary embodiment: Units derived from ethylene, at least one type of C3-C 20 A composition comprising an ethylene copolymer containing an α-olefin and at least one non-conjugated diene, wherein the copolymer includes the following: (i) up to 58% by weight, preferably 35-56% by weight, more preferably 38-52% by weight, of the total weight of the copolymer, units derived from ethylene; (ii) Based on the total weight of the copolymer, up to 57% by weight, preferably 17-55% by weight, of at least one C3-C 20 Units derived from -α-olefins, preferably from propylene; Here, the ethylene copolymer has approximately 80 to 125 units per polymer chain, derived from one or more dienes, and here the ethylene copolymer is mixed with oil, the total amount of oil in the composition being 29 phr or less, and here the composition contains 60% to 100% by weight of ethylene copolymer and oil, based on the total weight (=100%) of the composition.

[0074] A second exemplary embodiment: A composition of the first specific embodiment, wherein the copolymer comprises 5-ethylidene-2-norbornene (ENB) as a non-conjugated diene.

[0075] A third exemplary embodiment: A composition according to the first and second exemplary embodiments, wherein the copolymer comprises 5-ethylidene-2-norbornene (ENB) as a non-conjugated diene, and wherein the ethylene copolymer has 80 to a maximum of 125 units derived from ENB per polymer chain.

[0076] Fourth exemplary embodiment: A composition according to any one of the preceding exemplary embodiments, wherein the minimum phase angle δ is greater than 1 and less than 4.00, preferably less than 3.70, and more preferably less than 3.20. min It has.

[0077] Fifth exemplary embodiment: A composition according to any one of the preceding exemplary embodiments, wherein the composition has a Mooney viscosity of 80 to 120 ML1+8 (150°C).

[0078] Sixth exemplary embodiment: A composition according to any one of the preceding exemplary embodiments, wherein the ethylene copolymer has a branching degree (expressed as Δδ) between 2 and 50.

[0079] Seventh exemplary embodiment: A composition according to any one of the preceding exemplary embodiments, wherein the ethylene copolymer has a content of units derived from ENB between 5 and 20% by weight, based on the total weight of the copolymer, and a branching degree (expressed as Δδ) between 10 and 25.

[0080] Eighth exemplary embodiment: A composition according to any one of the preceding exemplary embodiments, wherein the ethylene copolymer comprises 5 to 20% by weight of units derived from 5-ethylidene-2-norbornene (ENB), 0.05 to 5% by weight of units derived from 5-vinyl-2-norbornene (VNB), 35 to 56% by weight of units derived from ethylene, and 17 to 55% by weight of units derived from propylene, where by weight % is based on the total weight of the copolymer, wherein the ethylene copolymer has about 80 to a maximum of about 125 units derived from ENB and VNB per polymer chain, and wherein the total amount of oil in the composition is 5 to 25 phr.

[0081] Ninth exemplary embodiment: A composition according to any one of the preceding exemplary embodiments, comprising at least 90% by weight, preferably at least 95% by weight, of ethylene copolymer and oil, based on the total weight (=100%) of the composition, wherein the total oil content in the composition is up to 29 phr, preferably 5 to 25 phr, more preferably 10 to 20 phr, and the oil comprises one or more hydrocarbon-based oils.

[0082] Tenth exemplary embodiment: A method for producing a rubber compound, comprising mixing the composition described in any one of the preceding exemplary embodiments with at least one curing agent, optionally at least one filler, or a combination thereof.

[0083] Eleventh exemplary embodiment: A rubber compound obtained by the method of exemplary embodiment 10.

[0084] Twelfth exemplary embodiment: A method for producing an article, comprising molding and curing a rubber compound described in the exemplary embodiment, wherein molding may be performed after, before, or simultaneously with curing.

[0085] Thirteenth exemplary embodiment: An article obtained by the method of exemplary embodiment twelfth.

[0086] Fourteenth exemplary embodiment: The article described in exemplary embodiment thirteen, which is a foamed article.

[0087] Fifteenth exemplary embodiment: An article as described in exemplary embodiment thirteen, having at least two of the following properties (i) to (iv): (i) Dynamic stiffness: less than 1.30, (ii) tan delta: less than 0.15, (iii) Elongation at break: at least 500%, (iv) Compression set (72 hours, 23°C): less than 20, preferably less than 9.

[0088] Sixteenth Exemplary Embodiment: A method for preparing the composition described in any one of Exemplary Embodiments 1 to 9, (i) In the reaction medium, ethylene, at least one C3-C 20 A step of polymerizing an α-olefin and at least one non-conjugated diene to obtain an ethylene copolymer, (ii) A step of mixing the ethylene copolymer with one or more oils in the reaction medium, (iii) The step of removing the reaction medium and isolating the composition containing the copolymer and the oil, (iv) In some cases, the composition is subjected to at least one step selected from drying, molding, compression, washing, and a combination thereof. A method that includes this.

[0089] The present disclosure will be further illustrated with examples, but the present disclosure is not intended to be limited to these examples or the embodiments used within them.

[0090] <Testing Method> Polymer testing methods Polymer composition The copolymer composition (C2 / C3 ratio according to ASTM D 3900 and diene content according to D 6047) of compression-molded polymer films was measured using Fourier transform infrared spectroscopy (FT-IR).

[0091] Δδ: The degree of branching of the polymer was characterized by the parameter Δδ. Δδ (in degrees) is the difference between the phase angle δ at a frequency of 0.1 rad / s and the phase angle δ at a frequency of 100 rad / s, and is measured by dynamic mechanical spectroscopy (DMS) at 125°C and 10% strain. The magnitude of this Δδ is an indicator of the amount of long-chain, branched structures present in the polymer, as proposed in HCBooij, Kautschuk + Gummi Kunststoffe, Vol.44, No.2, pp.128-130 (cited for reference and incorporated herein).

[0092] Molecular weight and molecular weight distribution: The molecular weight (Mw) of the polymer, the number-average molecular weight (Mn) of the polymer, the z-average molecular weight (Mz) of the ethylene copolymer, and the molecular weight distribution (MWD, defined as the ratio between Mw and Mn) were measured by gel permeation chromatography (GPC / SEC-DV) using a Polymer Char GPC (Polymer Characterisation SA (Valencia, Spain)). The size exclusion chromatograph was equipped with an online viscometer (Polymer charV-400 Viscometer), an online infrared detector (IR% MCT), three AGILENT PL OLEXIS columns (7.5 × 300 mm), and a Polymer Char autosampler. Universal calibration of the system was performed using polyethylene (PE) standards.

[0093] Polymer samples were weighed into vials of a Polymer Char autosampler (concentration range: 0.3–1.3 mg / mL). The autosampler automatically filled the vials with solvent (1,2,4-trichlorobenzene, TCB, stabilized with 1 g / L di-tert-butyl-para-cresol (DBPC)). These samples were held in a high-temperature oven (160°C) for 4 hours. After this dissolution time, the samples were automatically filtered through an in-line filter and then injected into the column. The chromatograph system was operated at 160°C. The TCB eluate flow rate was 1.0 mL / min. The chromatograph incorporated a built-in online infrared detector (IR5 MCT) for concentration and a built-in Polymer Char online viscometer. Universal calibration of the system was performed using polyethylene (PE) standards.

[0094] Diene units per chain: The number of diene units (also referred to herein as “diene content” or “units derived from diene”) per polymer chain corresponds to the following formula:

number

[0095] If the polymer contains units derived from several different dienes, the total diene content per polymer chain is the sum of the per-chain content of each diene. For example, the diene content per polymer chain, i.e., the number of dienes per polymer chain, of a polymer containing diene units derived from diene A and diene B is calculated according to the following formula: The number of dienes per chain = {([Diene A] × 10 × Mn of polymer) / Mw of diene A} + {([Diene B] × 10 × Mn of polymer) / Mw of diene B)}.

[0096] The number of ENB units per polymer chain corresponds to the following formula: [ENB] × 10 × Polymer Mn) / (120g / mol) Here, [ENB] represents the content of ENB units in the polymer (unit: weight %) relative to the total weight of the polymer (=100%). 120 g / mol is the molecular weight of ENB. "Mn of polymer" refers to the number-average molecular weight of the polymer (unit: kg / mol).

[0097] Mooney viscosity Mooney viscosity was measured in accordance with ISO 289.

[0098] minimum phase angle, δ min Ethylene copolymers can be characterized by their curves in van-Gurp-Palmen (vGP) plots. In the vGP plot, the phase angle (δ) is equal to the absolute modulus ([G *It is plotted against ]). Its phase angle and absolute modulus are obtained from rheological measurements, where the temperature-dependent storage modulus and loss modulus, G'(T) and G''(T), are measured. The phase angle δ is calculated from tan(G'' / G'). The absolute modulus [G * ] is (G') 2 +(G) 2 It is calculated from the square root of, that is,

number

[0099] In that plot, the point where the phase angle takes its minimum value is the absolute modulus [G * This is also the point where the value of ] is minimized, and it can be used to characterize ethylene-α-olefin copolymers (see, for example, M. van Gurp, J. Palmen, "Time temperature superposition for polymeric blends", Rheol. Bull, 67 (1998), 5, and S. Trinkle, C. Friedrich, "Van Gurp-Palmen-plot: a way to characterize polydispersity of linear polymers", Rheol. Acta, 40 (2001), 322. Although the paper by S. Trinkle et al. focuses only on linear polymers, it is also possible to characterize branched polymers by measuring delta-min).

[0100] δ min To determine the storage modulus and loss modulus, G'(T) and G''(T), which are temperature-dependent, were determined by dynamic mechanical thermal analysis (DMTA) measurements from -100°C to +100°C at a frequency of 1 Hz and a heating rate of 1 K / min using a Mettler Toledo DMA 861e rheometer equipped with a double sandwich simple shear sample holder. Test specimens with a diameter of 8 mm and a thickness of 1 mm were cut from a slab that was compression-molded at 105°C and 120 bar for 10 minutes.

[0101] Using G'(T) and G''(T), absolute modulus,

number

[0102] oil content The oil content can be determined by extraction methods, for example, methods D: unvulcanized rubber and A: vulcanized rubber according to ISO 1407 (2011).

[0103] Testing of compound materials Mooney viscosity: The Mooney viscosity of curable compounds (measurement conditions: ML(1+4)@100℃) was measured in accordance with DIN 53523-3 using NatureFlex NP / 28μm film (Putz Folien (D-65232, Taunusstein Wehen, Germany)).

[0104] Compression set (CS): The compression set (CS) was determined for the cured compound in accordance with DIN ISO 815.

[0105] Tensile strength at break (TS) and elongation at break (EB): The tensile strength (TS) and elongation at break (EB) were determined in accordance with DIN ISO 37 for the cured compound using an S2 dumbbell at 23°C.

[0106] hardness: Shore A hardness (H) was determined for the cured compound in accordance with DIN ISO 7629-1.

[0107] Rebound elasticity: Rebound elasticity was measured at 23°C in accordance with DIN 53512.

[0108] tan delta and dynamic stiffness: A dynamic-mechanical analyzer from MTS Systems Cooperation was used. Two test specimens (6 mm high, 20 mm in diameter) were placed in a double shear sandwich sample holder and allowed to reach equilibrium at 60°C for at least 30 minutes before measurements began. Subsequently, the linear viscoelastic properties of the rubber material were demonstrated in the simple shear shape by applying a peak-to-peak size of 0.3 mm at frequencies in the range of 0.1 to 200 Hz (logarithmic notation, 8 data points per logarithmic scale division). The results are shown in Figure 2. The tan delta was determined at 200 Hz. Dynamic stiffness, DS, was obtained from the ratio of absolute modulus measured at 180 Hz and 10 Hz: DS = |G * (180Hz)| / |G * (10Hz)|.

[0109] Tear strength: Tear resistance was measured using a Delft specimen at 23°C, following ISO 34-2 standards. [Examples]

[0110] experiment Example 1 and Comparative Examples C1-C5: Polymerization was carried out substantially by a continuous polymerization method, following the description of a general continuous polymerization procedure using compound 19 as a catalyst in International Publication No. 2005 / 090418 (which is incorporated herein by reference). The polymerization was carried out in two liquid-filled solution polymerization reactors connected in series. The volume of both reactors was 3 L. To maintain the entire system in the solution phase, the pressure of the entire system was kept above the degassing pressure. The feeds of ethylene and alpha-olefins, as well as the catalyst, were adjusted to generate the unit contents shown in Table 1. The ENB feed was 988 mmol / h, the VNB feed was 61 mmol / h, and the hydrogen content was adjusted to 0.09 NL / h to obtain the desired chain length, Mooney viscosity, and diene-to-chain ratio. The polymer production rate was approximately 900 g / h. The polymer solution was continuously extracted through a discharge line, where a solution of IRGANOX 1076 in isopropanol was added. A paraffinic oil was added to the polymer solution, and the polymer (and oil) solution was treated by continuous steam stripping. The oil-spread EPDM obtained in this manner was dried in batches on a two-roll mill. The rheological properties of the polymer in Example 1 (Ex1) were compared with those of various EPDM polymers with various compositions and structures (Comparative Examples, C1-C6). The results are summarized in Table 1.

[0111] [Table 1]

[0112] These polymers contained propylene as an α-olefin comonomer. Table 1 does not list the content of units derived from propylene, but since the rest of the polymer is listed, it can be calculated by subtracting the sum of units derived from ethylene, ENB, and VNB from 100% (except for polymer C5A). The amount of C2 units was extracted from the datasheet, but corrections for diene content cannot be made. The total amount of C2 units (ethylene) and C3 units (propylene), based on the polymer (100 wt%), can be somewhat less.

[0113] Comparative Examples C1 to C5A are commercially available products, and the data was either taken from publicly available data sheets or obtained experimentally. C1 was an EPDM sample available from Lion Copolymer Geimar, LLC under the trade name ROYALENE 547; C2 was an EPDM sample available from KUMHO POLYCHEM under the trade name KEP2480; C3 was an EPDM sample available from ExxonMobil under the trade name VISTALON 8800; C4 was an EPDM sample available from ExxonMobil under the trade name VISTALON 8700; C5 was an EPDM sample available from Mitsui Chemicals, Inc. under the trade name EPT8120E; and C5A was an EPDM sample available from Sumitomo Chemical under the trade name ESPRENE 5527F.

[0114] As can be seen from Table 1, and as is well known in this industry, generally, the higher the Mooney viscosity, the higher the molecular weight (Mw). The higher the Mw, the higher the number-average molecular weight (Mn). Mn can be reduced by broadening the molecular weight distribution (MWD). The ENB content can be adjusted so that the ENB content per polymer chain is greater than 80. When the molecular weight (Mw) and (Mn) are high, less ENB may be required than for polymers with lower molecular weights.

[0115] The following additional commercially available samples were analyzed for the content of units derived from ENB per polymer chain: EPDM available from ARLANXEO under the product name KELTAN K8340A: ENB=44 per chain; EPDM available from ARLANXEO under the product name KELTAN K7341A: ENB=63 per chain; EPDM available from Exxon under the product name VISTALON 7500: ENB=34 per chain.

[0116] Example 2 and Comparative Examples C6-C10: The polymers of Example 1 and Comparative Examples C1-C5 were compounded with the components shown in Table 2 using an internal mixer (GK1,5 E1 from Harburg-freudenberger Maschinenbau GmbH; ram pressure 8 bar, 50 rpm, filler density 72%, total mixing time 5 minutes). The curing system was added on an open mill (roll diameter 200 mm; 20 rpm, roll and friction temperature 40°C).

[0117] [Table 2]

[0118] The EPDM compounds obtained in this manner were tested for their properties. Example 2 is a compound prepared using the polymer from Example 1. Comparative Examples C6 to C10 are compounds obtained using the polymers from Comparative Examples C1 to C5.

[0119] Test specimens were prepared by curing a 2mm x 6mm thick test plate at 180°C for a time equivalent to 1.10 to 1.25 times t90 (t90 being the time it takes to reach 90% of the maximum torque measured by the rheometer). The test results are shown in Table 3.

[0120] [Table 3]

[0121] As shown in Table 3, the compounds prepared from the polymers of this disclosure possess good mechanical strength, as indicated by the tensile strength at break, and good elastic properties, as indicated by the elongation at break greater than 500%. These compounds also exhibit good shape retention, as indicated by the low compression set values. Their compression set was low over a wide temperature range. The compounds made from the polymers of this disclosure also possessed improved elastic and dynamic properties, as indicated by the high rebound elasticity and low tan delta values. The compounds made from the polymers of this disclosure also exhibited excellent resilience, as indicated by the low dynamic stiffness values ​​in Table 3. Low dynamic stiffness values ​​are particularly desirable for damping vibration and noise and are useful properties for sealing applications, and especially for producing foamed seals, or sponge materials.

Claims

1. A composition containing an ethylene copolymer, The aforementioned ethylene copolymer (i) Units derived from 35–52% by weight of ethylene; (ii) At least one type of C, in an amount of 17% to 55% by weight. ３ ~C ２０ A unit derived from -α-olefin, wherein at least one of the C ３ ~C ２０ -α-olefin containing propylene, unit; (iii) 8–20% by weight of units derived from 5-ethylidene-2-norbornene (ENB); Includes, The weight percentages in (i) to (iii) are based on the total weight (= 100% by weight) of the copolymer. The copolymer has 95 to a maximum of 125 units derived from ENB per polymer chain, determined according to the following formula (I): Unit derived from ENB = ([ENB] × 10 × Mn of polymer) / 120 g / mol (I) [In the formula, "[ENB]" means the content of ENB units in the polymer (unit, weight %) (based on the total weight of the polymer (= 100 weight %)), and "Mn of polymer" means the number average molecular weight (Mn) of the polymer (unit, kg / mol)]; Furthermore, the ethylene copolymer is (iv) Units derived from 5-vinyl-2-norbornene (VNB) in amounts of 0.10% to 3% by weight, based on the total weight of the copolymer which is 100% by weight. including, and, The ethylene copolymer is mixed with oil, and the total amount of oil in the composition is 5 to 25 phr. A composition comprising at least 97% by weight of ethylene copolymer and oil, based on the total weight of the composition (with the total weight being 100% by weight).

2. The composition according to claim 1, wherein the ethylene copolymer has a branching degree (expressed as Δδ) between 5 and 20 [wherein Δδ (unit, degrees) is the difference between the phase angle δ at a frequency of 0.1 rad / s and the phase angle δ at a frequency of 100 rad / s, and is measured by dynamic mechanical spectroscopy (DMS) at 125°C and 10% strain].

3. The composition according to claim 1 or 2, wherein the ethylene copolymer has a weight-average molecular weight (Mw) of at least 400,000 g / mol as measured by gel permeation chromatography.

4. The composition according to any one of claims 1 to 3, wherein the ethylene copolymer has a content of 95 to 120 units derived from ENB per polymer chain.

5. The composition according to any one of claims 1 to 4, wherein the ethylene copolymer further comprises 0.2 to 1.2% by weight of units derived from 5-vinyl-2-norbornene (VNB), based on the total weight (= 100% by weight) of the copolymer.

6. The composition according to any one of claims 1 to 5, wherein the ethylene copolymer contains 38 to 52% by weight of units derived from ethylene, based on the total weight of the polymer, and the ethylene copolymer has a content of units derived from ENB between 7 to 18% or between 8 to 15% by weight, based on the total weight (= 100% by weight) of the ethylene copolymer.

7. A composition according to any one of claims 1 to 6, having a Mooney viscosity of at least 80 ML1 + 8 (150°C) as measured in accordance with ISO 289.

8. Phase angle (δ) vs absolute modulus ([G ＊ The minimum phase angle δ obtained from the plot of ]) is greater than 1 and less than 4.

00. ｍｉｎ A composition according to any one of claims 1 to 7, having the following characteristics.

9. A composition according to any one of claims 1 to 8, having a Mooney viscosity ML1+8 (150°C) ranging from 80 to a maximum of 150.

10. A method for producing a rubber compound, comprising mixing the composition described in any one of claims 1 to 9 with at least one curing agent, optionally at least one filler, and optionally at least one foaming agent, or a combination thereof.

11. A rubber compound obtained by the method described in claim 10.

12. A method for producing an article, comprising molding and curing a rubber compound as described in claim 11, wherein the molding can be performed after, before, or simultaneously with curing.

13. An article obtained by the method described in claim 12.

14. The article according to claim 13, which is a foamed article.

15. The article according to claim 12 or 13 having at least two of the following properties (i) to (iv): (i) Dynamic stiffness: less than 1.30, (ii) tan delta: less than 0.15, (iii) Elongation at break: at least 500%, (iv) Compression set (72 hours, 23°C): Less than 20.

16. A method for preparing an oil-dispersed polymer composition, (i) In the reaction medium, ethylene, at least one C ３ ~C ２０ A step of polymerizing an α-olefin and at least one non-conjugated diene to obtain an ethylene copolymer as defined in claim 1, (ii) A step of mixing the ethylene copolymer with one or more oils in the reaction medium, (iii) A step of removing the reaction medium to isolate the composition containing the copolymer and the oil, (iv) optionally, the composition is subjected to at least one step selected from drying, molding, compression, washing, and a combination thereof. A method that includes this.

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