ethylene-co-vinyl acetate rubber

Abstract

A composition comprising an ethylene copolymer, the ethylene copolymer comprising units derived from ethylene, 5 at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from the at least one C3-C 20 units derived from

Description

TECHNICAL FIELD

[0001] The present disclosure relates to ethylene-copolymer rubbers and rubber compositions, and to a process for manufacturing such rubbers and rubber compositions and to articles made with such rubbers. BACKGROUND

[0002] Ethylene-a-olefin-elastomers and in particular ethylene-propylene-diene copolymers (EPDM) are used in many applications. In one major application, EPDM-type polymers are used as seals or as components of a seal or sealing system. EPDM rubbers can be found in sealing systems in motor vehicles, watercraft and aircraft, for example as sealing material for doors or windows - also known in the art as "weather stripping" applications. In many transportation applications, the material is required to have a low density and is typically provided as a foamed material (so-called sponge). EPDM rubbers are also used to seal windows in buildings, or as seals to make electrical appliances airtight or watertight - for example as O-rings in water taps or as seals or flanges for openings of washing machines and other equipment. Other applications of such rubbers include their use as belts, for example as conveyor belts, escalator belts, engine belts. Further applications include for example engine mounts, roofing materials and hoses.

[0003] Rubbers suitable for these applications need to have good mechanical properties, such as for example tensile strength, tear strength, and good flexibility, elasticity and shape retention under static as well as dynamic stress. When used in outdoor applications, these properties have to be maintained over a wide temperature range. In many applications, in particular in sealing applications, the rubbers also need to have good damping or sound reducing properties, for example for reducing the sound of an engine.

[0004] In most applications, EPDM rubbers are blended with at least one other ingredient to produce so-called rubber 'compounds'. Such ingredients can be fillers, curing agents or blowing agents. It is known that the mechanical properties of EPDM rubbers, such as tensile strength, increase with the molecular weight of the polymer. This makes it necessary to provide high molecular weight rubbers to achieve improved mechanical properties. However, rubbers with high molecular weight tend to be difficult to process, in particular when manufacturing or processing the compounds. These difficulties can manifest themselves as poor mixing, difficult kneading and the creation of lumps in the compound, as well as the formation of rough surfaces during the extrusion, molding or cutting of the curable or cured rubber compound.

[0005] Several methods are known in the art to reduce these problems. One method is to create a specific polymer architecture and microstructure, for example by controlling the molecular weight distribution or the structure of branched polymers. Another well-known method is to add ingredients to the rubber composition that lower its overall viscosity, for example by diluting the rubber composition by blending with other rubbers having a lower viscosity. Alternatively or additionally, oil can be added to the rubber to create so-called “oil-extended polymers”. Oil-extended polymers are created by blending the polymer during its production or during its post-treatment, i.e. before the polymer is isolated and dried, with one or more extender oils. The extender oil is then homogeneously mixed with the polymer. Such oil-extended polymers can be more easily processed to produce rubber compounds compared to the same polymer that is provided without oil but with oil added only during the process of manufacturing the rubber compound.

[0006] In US patent application No. 2017 / 0313868 A1, oil-extended EPDM polymers having a molecular weight of at least 300,000 g / mol are described. The content of extender oil is from 30 to 70 phr. The rubber composition has good mechanical properties and also good damping properties as determined by a low delta minimum in a phase angle measurement. However, the high oil content leads to increased production costs. The high oil content can also reduce the dynamic properties of the rubber composition, especially if other ingredients are added to the rubber composition. This can limit the amount of these ingredients, such as fillers or rubber additives, that can be added to the rubber composition and reduce the operable window of the oil-extended EPDM polymer. At least some of these problems can be solved by providing ethylene-copolymers having a specific monomer composition and a polymer architecture determined by the branching level, as described in US patent application No. 2019 / 0153206 A1. The oil-extended rubber composition contains ethylene copolymers having a molecular weight of at least 400,000 g / mol and has good mechanical properties and shape retention at a rather low oil content of from 10 to 40 phr. However, US 2019 / 0153206 A1 does not mention damping and noise reduction and dynamic properties, which are useful for sealing applications, and in particular for foamed seals or sponge materials. SUMMARY

[0007] It has now been found that compositions containing ethylene-copolymers having a specific composition and structure, compositions containing the same, can be processed into rubber compounds that have even improved dynamic and mechanical properties.

[0008] In one aspect, an ethylene copolymer is provided, containing

[0009] (i) from 35 up to and including 58 wt%, preferably from 35 to 56 wt%, and more preferably from 38 to 52 wt% of units derived from ethylene;

[0010] (ii) from 17 up to and including 57 wt% of units derived from at least one C3-C 20 α-olefin, and wherein the at least one C3-C 20 α-olefin comprises propylene;

[0011] (iii) from 5 to 20 wt% of units derived from 5-ethylidene-2-norbornene (ENB),

[0012] wherein the wt% in (i) to (iii) are based on the total weight of 100 wt% of the copolymer

[0013] and wherein the copolymer has more than 80 units derived from ENB per polymer chain determined according to formula (I):

[0014] Units derived from ENB = ([ENB] x 10 x Polymer Mn) / 120 g / mol (I)

[0015] wherein‘[ENB]’ is the content of ENB units in the polymer in wt% (based on the total weight of 100 wt% of the polymer), and‘Polymer Mn’ means the number average molecular weight (Mn) of the polymer in kg / mol.

[0016] In another aspect, there is provided a method of manufacturing a rubber compound, the method comprising mixing a composition comprising the ethylene copolymer with at least one curing agent, optionally at least one filler, or a combination thereof.

[0017] In another aspect, there is provided a rubber compound obtained by the method.

[0018] In yet another aspect, there is provided a method of manufacturing an article, the method comprising subjecting a rubber compound to shaping and curing, wherein shaping can be performed after, before or simultaneously with curing.

[0019] In another aspect, there is provided an article obtained by the method.

[0020] In another aspect, there is provided a method of manufacturing an oil-extended polymer composition, the method comprising (i) polymerizing ethylene, at least one C3-C 20 α-olefin and at least one non-conjugated diene in a reaction medium to provide an ethylene-copolymer,

[0021] (ii) mixing the ethylene copolymer with one or more oils in the reaction medium,

[0022] (iii) removing the reaction medium to isolate a composition comprising the copolymer and the oil,

[0023] (iv) optionally, subjecting the composition to at least one of the steps selected from the group consisting of drying, shaping, compressing, washing, and combinations thereof. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a van Gurp-Palmen plot obtained from DMTA measurements with the polymer of Example 1 as described in the experimental section. The dotted lines show the minimum phase angle and the corresponding absolute modulus, G min and G * min .

[0025] Figure 2 is a plot of the loss factor (tan d) versus frequency obtained from dynamic-mechanical analysis as described in the experimental section. DETAILED DESCRIPTION

[0026] In the following description, specifications can be used. If not otherwise indicated, the specifications are used in the version in force on March 1, 2020. If there is no version in force on that date, for example because the standard has been superseded, reference is made to the version in force on the date closest to March 1, 2020.

[0027] In the following description, the amount of a component of a composition or a polymer can be interchangeably expressed by “percent by weight”, “wt. %” or “weight %”. The terms “percent by weight”, “wt. %” or “weight %” are used interchangeably and are based on the total weight of the composition or the polymer being 100%, respectively, unless otherwise indicated. When the amount of units of a polymer derived from a monomer or the amount of other components is expressed in weight % based on the weight of the copolymer and the copolymer is oil-extended, the total mass of the copolymer also refers to the total weight of the copolymer. In other words, the total weight of the copolymer of the oil-extended copolymer is the weight of the copolymer and the extender oil minus the weight of the extender oil.

[0028] The term “phr” means parts per hundred of rubber, i.e. a weight percentage based on a total amount of rubber set to 100% by weight. The ethylene-copolymers according to the present disclosure are rubbers. If the composition contains one or more ethylene-copolymers or one ethylene-copolymer and one or more other rubbers, “phr” refers to the total amount of these rubbers.

[0029] Unless otherwise indicated, ranges determined in the present disclosure include and disclose all values and also the endpoints between the values of the range.

[0030] The expressions "comprising" and "containing" are used interchangeably. They are intended to include the components or constituents mentioned, but not to exclude the presence of other components or constituents. The expression "consisting of is used in a limiting sense and is intended to limit the composition to only those components mentioned in the expression consisting of.

[0031] Ethylene-a-olefin-copolymers

[0032] The ethylene-a-olefin copolymers provided herein can be used to provide compounds having good properties, in particular good dynamic properties, particularly useful for sealing applications, such as represented by low tan delta values, high rebound values, low compression set, low dynamic stiffness, and good mechanical properties like tensile strength and elastic properties like elongation at break. These copolymers can be processed into rubber compounds without or with only a small amount of extender oil, despite having a high molecular weight.

[0033] The ethylene-a-olefin copolymers according to the present disclosure are copolymers of ethylene and at least two further comonomers. This means that the copolymer comprises repeating units derived from ethylene and at least two further comonomers. Preferably, the copolymer comprises up to 58 weight percent (wt. %) of units derived from ethylene. More preferably, the copolymers according to the present disclosure comprise up to 56 wt. % and more preferably up to 52 wt. % of units derived from ethylene. In one embodiment, the ethylene-a-olefin copolymers of the present disclosure comprise from 35 to 56 wt. %, preferably from 38 to 52 wt. % of units derived from ethylene. The weight percent is based on the total weight of the copolymer.

[0034] In addition to units derived from ethylene, the copolymers according to the present disclosure have repeating units derived from (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 di- polymerizable diene.

[0035] C3-C 20 - alpha-olefins

[0036] C3-C 20 -α-olefins (also referred to herein as "C3-C 20α-Alkenes are alkenes containing three to twenty carbon atoms and having a single aliphatic carbon-carbon double bond. The double bond is located at the terminal end (α-position) of the alkene. α-Alkenes can be aromatic or aliphatic, and can be straight-chain, branched, or cyclic. Examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecadecene, 1-hexadecene, 1-heptadecene, and 1-octadecene. Alkenes, including 1-nonadecane, 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. α-Alkenes can be used in combination. Preferred α-alkenes are aliphatic C3-C... 12 α-olefins, more preferably aliphatic linear C3-C4 α-olefins, most preferably propylene (C3 α-olefins) and 1-butene (C4 α-olefins). Preferably, the ethylene-α-olefin copolymer disclosed herein contains propylene and one or more other C3-C... 20 -α-olefin. In one embodiment of this disclosure, the ethylene-α-olefin copolymer contains only propylene as a C3-C. 20 -α-olefin. Preferably, the ethylene copolymer contains up to 57 wt.%, more preferably up to 55 wt.%, of C3-C derived olefins. 20 α-olefin units (all weight percentages (wt.%) are based on the total weight of the copolymer). Preferably, the ethylene-α-olefin copolymer contains from 17 to 57 wt.% of total C3-C derived units. 20 α-olefin units. Preferably, the ethylene-α-olefin copolymer contains up to 57 wt.%, more preferably up to 55 wt.%, of propylene-derived units (all weight percentages (wt.%) are based on the total weight of the copolymer). In one embodiment of this disclosure, the ethylene-α-olefin copolymer contains from 17 to 55 wt.%, of total propylene-derived units.

[0037] Non-conjugated dienes

[0038] Nonconjugated dienes are polyenes containing at least two double bonds, which are nonconjugated in chains, rings, cyclic systems, or combinations thereof. Polyenes may have intracyclic and / or excyclic double bonds and may not have the same or different types of substituents. The double bonds are separated by at least two carbon atoms. To a large extent, only one nonconjugated double bond is converted by a polymerization catalyst. Nonconjugated dienes are preferably aliphatic, more preferably alicyclic and aliphatic.

[0039] Suitable non-conjugated dienes include aromatic polyenes, aliphatic polyenes, and alicyclic polyenes, with polyenes having 6 to 30 carbon atoms (C6-C4). 30 - Polyenes, more preferably C6-C 30 Specific examples 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 1,4-Ethyl-1,5-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-nonadiene, 5-Methyl-1,4-nonadiene, 4-Ethyl-1,4-nonadiene, 5-Ethyl-1,4-nonadiene, 5-Methyl-1,5-nonadiene 6-Methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1 5-Decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 1,5,9-dectriene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, dicyclopentadiene, and mixtures thereof. Dicyclopentadiene can be used both as a dipolymerizable diene and as a non-conjugated diene, in which case dicyclopentadiene is used in combination with at least one dipolymerizable diene or at least one non-conjugated diene.

[0040] Preferred non-conjugated dienes include alicyclic polyenes. Alicyclic dienes have at least one cyclic unit. In preferred embodiments, the non-conjugated diene is selected from polyenes having at least one endocyclic double bond and optionally at least one exocyclic double bond. Preferred examples include dicyclopentadiene, 5-methylene-2-norbornene, and 5-ethylidene (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.

[0041] Examples of aromatic non-conjugated polyenes include vinylbenzene (including isomers thereof) and vinyl-isopropenylbenzene (including isomers thereof).

[0042] In typical embodiments of the present disclosure, the copolymer contains at least 5 wt.% and up to and including 20 wt.% of units derived from one or more non-conjugated dienes. In preferred embodiments, the copolymer contains from 6 to 18 wt.%, more preferably from 7 to 18 wt.%, for example from 8 to 15 wt.% of units derived from one or more non-conjugated dienes. In preferred embodiments, the copolymer contains from 5 wt.% and up to 20% wt.% of units derived from ENB, and more preferably from 6 to 18 wt.% of units derived from ENB, or from 7 to 18 wt.%, for example from 8 to 15 wt.% of units derived from ENB (all wt.% based on the total weight of the ethylene-a-olefin copolymer).

[0043] Dipolymerizable dienes

[0044] Bipolymerizable dienes are selected from vinyl-substituted aliphatic monocyclic and non-conjugated dienes, vinyl-substituted bicyclic and non-conjugated aliphatic dienes, alpha-omega linear dienes and non-conjugated dienes, wherein both unsaturation sites are polymerizable by a coordination catalyst (e.g., a Ziegler-Natta vanadium catalyst or a metallocene-type catalyst). Examples of bipolymerizable 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-isopropenyl-cyclohexane, 1-isopropenyl-4-vinylcyclohexane, and 1-isopropenyl-3-vinylcyclopentane, dicyclopentadiene, and 1,4-cyclohexadiene. Preferred are non-conjugated vinyl norbornenes and C8-C 12Alpha omega straight-chain dienes. (e.g., 1,7-octadiene, 1,8-nonadiene, 1,9- decadiene, 1,10-undecadiene, 1,11-dodecadiene). The dienes that can be dimerized can be further substituted with at least one group comprising a Group 13-17 heteroatom (e.g., O, S, N, P, Cl, F, I, Br, or combinations thereof). The dienes that can be dimerized can enable or facilitate the formation of polymer branches.

[0045] In preferred embodiments of the disclosure, the dienes that can be dimerized are selected from 2,5-norbornadiene, 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 copolymers of the disclosure contain only VNB as the diene that can be dimerized.

[0046] Preferably, the copolymers of the disclosure contain from 0.05 wt. % to 5 wt. %, more preferably from 0.10 wt. % to 3 wt. %, or from 0.2 wt. % to 1.2 wt. % of units derived from one or more dienes that can be dimerized, more preferably derived from VNB (all weight percents are based on the total weight of the ethylene-alpha-olefin copolymer).

[0047] In preferred embodiments, the copolymers of the disclosure contain units derived from 5-ethylidene-2-norbornene and 5-vinyl norbornene. In more preferred embodiments of the disclosure, the copolymers contain units derived from ethylene, propylene, 5- ethylidene-2-norbornene, and 5-vinyl-2-norbornene. For example, the ethylene-alpha-olefin- copolymer can contain from 5 to 20 wt. % of units derived from ENB and from 0.05 to 5 wt. % of units derived from VNB.

[0048] The ethylene-alpha-olefin-copolymers according to the disclosure can or can not contain units derived from other comonomers. The sum of units derived from ethylene, one or more non-conjugated dienes, one or more dienes that can be dimerized, and one or more alpha-olefins is greater than 99 wt. % and preferably 100 wt. % based on the total weight of the ethylene-alpha-olefin-copolymer. In one embodiment of the disclosure, the sum of units derived from ethylene, propylene, ENB is greater than 75 wt. %, preferably greater than 90 wt. %, and more preferably at least 95 wt. % based on the total weight of the ethylene-alpha-olefin-copolymer polymer.

[0049] The ethylene-alpha-olefin-copolymers according to the disclosure preferably have a high Mooney viscosity, for example a Mooney viscosity ML 1+8 at 150 °C of at least 80, or at least 90, or at least 100, and can in fact have a Mooney viscosity even greater than 150. For example, the copolymer can have a Mooney viscosity ML 1+8 at 150 °C of 80 to 120 or 80 to 150.

[0050] The ethylene-a-olefin copolymer according to the present disclosure preferably 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 can have a Mw between 400,000 g / mol and 700,000 g / mol. The ethylene-copolymer of the present disclosure can have a molecular weight distribution or polydispersity of at least 2.5, for example from 3.0 to 30, or from 3.5 to 25, or from 3.7 to 10. In one embodiment of the present disclosure, the number average molecular weight (Mn) of the ethylene-copolymer of the present disclosure can be from about 40 to 230 kg / mol. The Mw and Mn can be determined by gel permeation chromatography.

[0051] The ethylene-a-olefin copolymer according to the present disclosure can have, for example, a delta delta branching level between 2 and 50, more preferably between 5 and 35, or between 8 and 30, or between 10 and 25. Delta delta (in degrees) is the difference between the phase angle delta at a frequency of 0.1 rad / s and the phase angle delta at a frequency of 100 rad / s, as determined by dynamic mechanical spectroscopy (DMS) at 125 °C.

[0052] Preferably, the ethylene-a-olefin-copolymer according to the present disclosure has at least 80, preferably at least 95, and more preferably at least 100 diene content per polymer chain, and preferably the diene content is ENB. The ethylene-a-olefin-copolymer according to the present disclosure can have from about 80 up to about 125 diene content per polymer chain.

[0053] In a preferred embodiment, the ethylene-a-olefin-copolymer according to the present disclosure has at least 80, preferably at least 95, and more preferably at least 100 ENB content per polymer chain. In one embodiment of the present disclosure, the ethylene-a-olefin-copolymer can have from about 80 up to about 125 ENB content per polymer chain.

[0054] In one embodiment of the disclosure, the ethylene copolymer has a content of units derived from ENB of between 5 and 20 wt.%, based on the total weight of the copolymer, and a branching level expressed as delta delta of between 10 and 25. Such a copolymer preferably has from 5 to 20 wt.% of units derived from 5-ethylidene-2-norbornene (ENB) and from 0.05 to 5 wt.% of units derived from 5-vinyl-2-norbornene (VNB). Preferably, such a copolymer has a high Mooney viscosity, for example a Mooney viscosity ML 1+8 of at least 90, or at least 100, at 150°C, and indeed can have a Mooney viscosity even greater than 150. Preferably, the copolymer of this embodiment has a Mw of between 400,000 and 700,000 g / mol and / or a polydispersity of at least 2.5, for example from 3.0 to 30. The copolymer according to this embodiment can have a number average molecular weight (Mn) of from about 40 to 230 kg / mol.

[0055] The ethylene-a-olefin-copolymers according to the disclosure, preferably when mixed with a small amount of oil, for example as oil-extended copolymers, can be processed into compounds having good or even improved dynamic and mechanical properties. The oil-extended ethylene-a-olefin-copolymers have the same properties as the ethylene-a-olefin-copolymers described above, except that the Mooney viscosity of the oil-extended copolymer is lower than the Mooney viscosity of the non-oil-extended copolymer. Therefore, also provided in the disclosure are compositions comprising one or more of the 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 visible by the naked eye. The solid and homogeneous mixture of oil and polymer preferably comprises the ethylene-copolymer in oil-extended form, i.e. the ethylene-copolymer is oil-extended. The oil-extended copolymer is obtained, for example, by mixing the copolymer with the oil during or after the polymerization process carried out in the reaction medium and before the removal of the reaction medium. The amount of oil can range from more than 0 and up to 29 phr. Therefore, provided are compositions comprising the copolymers of the disclosure mixed with oil and having a total amount of oil of from 5 to 25 phr, preferably from 10 to 20 phr. Preferably, the oil comprises one or more hydrocarbon-based oils. Preferably, the copolymer mixed with the oil is an oil-extended copolymer. Preferably, the oil in the composition is the extender oil in the oil-extended copolymer. Preferably, at least a majority of the oil, i.e. the oil based on the total amount of oil of more than 50 wt.%, is the extender oil, i.e. the oil in the oil-extended copolymer.

[0056] In one embodiment according to this disclosure, a composition comprising an ethylene-α-olefin copolymer mixed with oil is provided, wherein the total oil content of the composition is from 5 to 25 wt.%, preferably from 8 and up to 20 wt.%, or from 8 and up to 18 wt.% based on the total weight of the composition. Preferably, the oil comprises one or more hydrocarbon-based oils. Preferably, the copolymer mixed with the oil is an oil-extended copolymer. Preferably, the oil in the composition is a filler oil in an oil-extended copolymer. Preferably, at least a majority of the oil, i.e., more than 50% by weight of the total oil content, is a filler oil, i.e., oil in an oil-extended copolymer.

[0057] Typically, compositions comprising the ethylene-α-olefin copolymer according to this disclosure contain 60% by weight, preferably 90% by weight, more preferably 95% by weight, or even at least 97% by weight of the ethylene copolymer and oil (weight percentages are based on 100% of the total weight of the composition). Preferably, the oil comprises one or more hydrocarbon-based oils. Preferably, the ethylene-α-olefin copolymer is oil-extended. Preferably, the oil in the composition is a filler oil in an oil-extended copolymer. Preferably, at least a majority of the oil, i.e., more than 50% by weight of the total oil-based oil, is a filler oil, i.e., oil in an oil-extended copolymer.

[0058] Mixtures of oils and copolymers (e.g., oil-extended ethylene-α-olefin copolymers according to this disclosure) are typically solid compositions and homogeneous mixtures of oils and polymers. They can be prepared to provide oil-extended copolymers by preferably blending the ethylene copolymer with at least a portion, preferably all, of the oil in a liquid phase during polymer preparation. The oils that can be used can be any conventional oil or softener known in the field of rubber production as 'filler oils'. The oil preferably comprises one or more hydrocarbon-based oils, or hydrocarbon-based oils or mixtures thereof. "Hydrocarbon-based" means that the oil contains at least 50% by weight of hydrogen and carbon based on the total composition of the oil. Hydrocarbon-based oils may contain preferably at least 90% by weight, more preferably at least 95% by weight of carbon and hydrogen. Preferably, the oil is liquid at 25°C and atmospheric pressure (1 atm). Examples of 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 paraffin oils, naphthenic oils, and mineral oils. Suitable oils also include aromatic oils, such as those obtained from the boiling point fractions of petroleum. These oils typically exhibit a viscosity of 5 to 35 mm at 100°C. 2The dynamic viscosity of the oil at 25°C. Preferred oils include paraffinic oils. Suitable oils are commercially available, for example, under the trade name PLI PROCESS OIL P 460 SUNPAR 2280 from Sunoco, CONOPURE 12P from ConocoPhillips, and PARALUX 6001 from Chevron Texaco. Other examples include oils made by gas to liquid (GTL) processes, such as, for example, RISSELLA X 430 from Shell. The oil can contain olefin oligomers, such as homo- 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:

[0059] a. a viscosity (Brookfield viscosity) of 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 at a temperature of 190°C; and / or

[0060] b. a viscosity of from 200 mPa.sec to 20.000 mPa.sec, from 400 to 20.000 mPa.sec, or from 500 to 20.000 mPa.sec, or from 1,000 to 10.000 mPa.sec at a temperature of 60°C, determined according to ASTM D3236. In one embodiment, the olefin oligomers are reactive with the polymer during polymerization and can be incorporated into the polymer chain during the polymerization process.

[0061] In another preferred embodiment according to the present disclosure, there is provided a composition comprising the ethylene-alpha-olefin-copolymer of the present disclosure and greater than 0 and up to 29 phr, preferably from 5 to 25 phr, more preferably from 10 to 20 phr of an oil, wherein the composition has a Mooney viscosity ML 1+8 at 150°C of from about 80 to about 120, preferably, for example, from about 85 to about 110. Preferably, the oil comprises one or more hydrocarbon-based oils. Advantageously, the composition can have a delta minimum (delta min) of greater than 1 and less than 4.0, preferably less than 3.70, and more preferably less than 3.20. min). For example, the ethylene-a-olefin-copolymers according to the present disclosure can have a delta minimum (delta min ) of greater than 2.0 and lower than 3.5.

[0062] Preferably, the ethylene-a-olefin-copolymers are oil-extended. Preferably, the oil in the composition is the extender oil in the oil-extended copolymer. Preferably, at least a majority of the oil, i.e. more than 50 wt.% of the oil based on the total amount of oil, is extender oil, i.e. the oil in the oil-extended copolymer.

[0063] In one embodiment of the present disclosure, a composition comprising an ethylene copolymer having a content of units derived from ENB of between 5 and 20 wt.% based on the total weight of the copolymer and a branching level expressed as delta delta of between 10 and 25 is provided. Such a copolymer preferably has from 5 to 20 wt.% of units derived from 5-ethylidene-2-norbornene (ENB) and from 0.05 to 5 wt.% of units derived from 5-vinyl-2-norbornene (VNB). Preferably, such a copolymer has a high Mooney viscosity, for example a Mooney viscosity ML 1+8 at 150°C of at least 90, or at least 100, and can in fact have a Mooney viscosity of even greater than 150. Preferably, the copolymer of this embodiment has a Mw of between 400,000 g / mol and 700,000 g / mol and / or a polydispersity of at least 2.5, for example from 3.0 to 30. The copolymer according to this embodiment can have a number average molecular weight (Mn) of from about 40 to 230 kg / mol. The total oil content of the composition of this embodiment is up to 29 phr of oil. Preferably, the ethylene-copolymers are oil-extended. Preferably, the oil in the composition is the extender oil in the oil-extended copolymer. Preferably, at least a majority of the oil, i.e. more than 50 wt.% of the oil based on the total amount of oil, is extender oil, i.e. the oil in the oil-extended copolymer.

[0064] Polymer production

[0065] The copolymers according to the present disclosure can be produced by a process comprising polymerizing ethylene, at least one C 3- C 20- copolymerization of an alpha-olefin, at least one non-conjugated diene, and optionally at least one di- polymerizable diene monomer, as known in the art of producing ethylene- copolymers. The polymer can be produced by using a conventional catalyst such as, for example, a Ziegler-Natta vanadium catalyst, or a metallocene-type catalyst, or a post-metallocene catalyst, or by a combination of catalysts. Ziegler-Natta vanadium catalysts are non-metallocene-type catalysts based on transition metal, in particular titanium or vanadium, halides. A “metallocene-type catalyst” is an organometallic catalyst in which 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 vanadium catalyst is used. In another embodiment, a metallocene-type catalyst is preferably used. In another embodiment, a combination of two or more metallocene-type catalysts is used.

[0066] The polymerization can be carried out in the gas phase, in slurry, or in solution in an inert solvent, preferably a hydrocarbon solvent.

[0067] The polymerization can occur in different polymerization zones. A polymerization zone is a vessel in which polymerization occurs, and can be a batch reactor or a continuous reactor. When multiple reactors are used, for example multiple reactors connected in series or in parallel, each reactor is considered to be a separate polymerization zone.

[0068] Preferred solvents include one or more hydrocarbon solvents. Suitable solvents include C 5-12 hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, pentamethylheptane, hydrogenated naphtha, isomers and mixtures thereof. The polymerization can be carried out at a temperature from 10 °C to 250 °C, depending on the product manufactured. Most preferably, if carried out in solution, the polymerization is carried out at a temperature greater than 50 °C.

[0069] In preferred embodiments, the polymerization includes the use of one or more chain transfer agents to control the molecular weight of the polymer. Preferred chain transfer agents include hydrogen (H2). The diene content in each polymer chain can be controlled, for example, by controlling the amount of diene in the reaction and the molecular weight (chain length), as known in the art. Branching can be introduced, as known in the art, for example, by using a specific catalyst, for example, a catalyst that produces branches in the polymer (such as, for example, a catalyst that produces vinyl groups); or by using a monomer that produces branching of the polymer, for example, a di- polymerizable diene; or by using a combination of both. The degree of branching can be controlled, for example, by adjusting their amounts or feed streams during polymerization, as known in the art. The minimum phase angle can be controlled by the long chain branching degree.

[0070] The oil-extended ethylene copolymer is preferably obtained by blending one or more extender oils with the ethylene-copolymer during polymer production and prior to post-treatment of the polymer, more specifically prior to removal of the solvent. Preferably, the one or more oils are added to the reaction solution to produce the oil-extended polymer after the reaction solution has left the reaction vessel and / or after the polymerization reaction has terminated and prior to removal of the solvent from the reaction solution. For example, the addition can occur after the polymerization reactor but prior to removal of volatiles (e.g. prior to a stripping column or dry finish extruder). Preferably, the extender oil is blended with the ethylene-a-olefin copolymer when the extender oil is dissolved or suspended in the reaction medium (preferably from the polymerization reactor).

[0071] Ethylene-copolymer compounds

[0072] The ethylene-copolymer according to the present disclosure, preferably the composition comprising the copolymer according to the present disclosure mixed with oil, more preferably the oil-extended copolymer can be combined with one or more additional ingredients. Such additional ingredients include, but are not limited to (a) one or more than one curing agent, (b) one or more than one filler, (c) one or more than one rubber aid. The ethylene-copolymer and oil-extended composition can be mixed with such ingredients to provide a rubber compound, to produce rubber compounds, which are typically homogeneous solid mixtures of rubber and additional ingredients. In the rubber compound, typically, the content of ingredients other than the ethylene-copolymer and oil is at least or more than 10 wt.% based on the total weight of the composition. The rubber compound is curable and can be cured to provide a vulcanized compound or “vulcanized product”.

[0073] Curing agents

[0074] Suitable curing (vulcanizing) agents include, but are not limited to, sulfur, sulfur chlorides, sulfur dichloride, 4,4'-dithiodimorpholine, morpholine disulfide; alkyl phenol disulfide, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), selenium dimethyl dithiocarbamate, and organic peroxides. Organic peroxides include, but are not limited to, dicumyl peroxide (DCP), 2,5-di(tert-butylperoxy)-2,5-dimethyl-hexane (DTBPH), di(tert-butylperoxy isopropyl)benzene (DTBPIB), 2,5-di(benzoylperoxy)-2,5-dimethylhexane, 2,5-(tert-butylperoxy)-2,5-dimethyl-3-hexyne (DTBPHY), di-tert-butyl peroxide, and di-tert-butyl peroxide-3,3,5-trimethylcyclohexane (DTBTCH), or mixtures of these peroxides. Of these, preferred are sulfur, TMTD, TETD, DCP, DTBPH, DTBPIB, DTBPHY, and DTBTCH.

[0075] In the case of sulfur vulcanization, sulfur or sulfur-containing curatives are preferably used in an amount of 0.1 to 10 phr, preferably from 0.5 to 5 phr, or even more preferably 0.5 to 2 phr.

[0076] In the case of peroxide vulcanization, curatives based on organic peroxides can be used in an amount of from 0.1 to 15 phr, preferably from 0.5 to 5 phr.

[0077] Sulfur as a vulcanizing agent can 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, 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-thiomorpholinyl)benzothiazole, dibenzothiazyl disulfide, diphenyl guanidine, triphenyl guanidine, di-o-tolyl guanidine, o-tolyl di-guanidine, diphenyl guanidine phthalate, acetaldehyde-aniline reaction product, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde amine, 2-mercaptoimidazoline, diphenyl thiourea, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, di-o-tolyl thiourea, tetramethyl thiuram monosulfide, TMTD, TETD, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, zinc dimethyl dithiocarbamate, zinc diethyl-dithiocarbamate, zinc di-n-butyl dithiocarbamate, zinc ethyl phenyl dithiocarbamate, zinc butyl phenyl dithiocarbamate, sodium dimethyl dithiocarbamate, selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, zinc dibutyl xanthate, and ethylene thiourea. The vulcanization accelerator, if used, is preferably used in an amount of from 0.1 to 10 parts by weight per 100 parts by weight of ethylene-copolymer, and more preferably from 0.2 to 5 parts by weight, and most preferably between 0.25 and 2 phr.

[0078] Examples of vulcanization activators include, but are not limited to, metal oxides such as magnesium oxide and zinc oxide, stearic acid or its metal stearate salts, or combinations thereof, for example, like zinc oxide in combination with stearic acid. The vulcanization activator is typically used in an amount of from 0.5 to 10 phr based on the ethylene copolymer, preferably in an amount of from 0.5 to 5 phr.

[0079] When a peroxide or a mixture of peroxides is used as a vulcanizing agent, a peroxide crosslinking coagent can be used. Examples of such peroxide crosslinking coagents are 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. Preferably, from 0.1 to 5 phr of a peroxide crosslinking coagent can be used. More preferably, from 0.25 to 2.5 phr of a peroxide crosslinking coagent can be used. Furthermore, when a peroxide is used as a vulcanizing agent, sulfur (elemental or as part of a sulfur accelerator or sulfur donor) can preferably be used to obtain so-called hybrid cure systems. These cure systems combine the high heat resistance properties (typically for peroxide cure) with very high ultimate properties (such as tensile and tear) and excellent dynamic and fatigue properties (typically associated with sulfur cure systems). The dosage level of applied sulfur is preferably from 0.05 to 1.0 phr, preferably from 0.2 to 0.5 phr.

[0080] Fillers

[0081] Preferably, fillers can be used in an amount of from 20 to 500 phr. Preferred fillers include carbon black and / or inorganic fillers such as silica, calcium carbonate, talc, and clay, which are conventionally used in rubber. The type of carbon black is classified according to ASTM D-1765 as a function of the particle size (BET, in m 2 / g) and structure (DBP adsorption, in cm 3 / 100 g) of the carbon black. Preferably, carbon black fillers having a BET value from 5 to 150 and a DBP value from 30 to 140 are used. In the industry, these types of carbon black are commonly referred to by acronyms such as MT, SRF, GPF, FEF, HAF, ISAF, SAF. The inorganic fillers can be surface treated with suitable silanes. A combination of two or more of such fillers can be used. Most preferably, the filler comprises carbon black and / or silanized silica.

[0082] Furthermore, the filler can comprise one or more than one other rubber, including EPDM rubber and rubber blends.

[0083] Other rubber additives

[0084] Other rubber additives include those commonly used in the rubber compounding art. Examples include, but are not limited to, antioxidants (e.g., hindered phenols such as those commercially available from BASF under the trade designation IRGANOX 1010 or IRGANOX 1076); phosphites (e.g., those commercially available under the trade designation IRGAFOS 168); drying agents (e.g., calcium oxide); tackifiers (e.g., polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal stearates and glycerol stearate, and hydrogenated rosins and the like); bonding agents; heat stabilizers; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; processing aids (e.g., petrolatums, fatty acids, stearates, poly- or di-ethylene glycol); antioxidants; heat stabilizers (e.g., poly-2,2,4-trimethyl-l,2-dihydroquinoline or 2-mercaptobenzimidazole zinc); UV stabilizers; antiozonants; blowing agents and release agents; partitioning agents or processing aids like talc or metal salts (e.g., like zinc stearate, magnesium stearate or calcium stearate); and plasticizers ( Plasticizers lubricating oils such as those commercially available under the trade designation PLI PROCESS OIL P460, paraffin, liquid paraffin, petroleum pitch, vaseline, low molecular weight polyisobutylene or polybutene, liquid EPDM or EPM, coal tar pitch, castor oil, linseed oil, beeswax, atactic polypropylene and coumarone indene resin). The plasticizer can be used in an amount from 20 to 250 phr. Rubber aids include plasticizers which can comprise one or more oils, and the overall oil content in the rubber compound can be higher than the oil content in the composition used to make the compound. Furthermore, additives as known in the art can also be used.

[0085] Method of manufacturing a rubber compound

[0086] The ethylene-copolymer containing rubber compound according to the present disclosure can be manufactured by mixing the ethylene-copolymer, preferably a composition containing the ethylene-copolymer mixed with oil, with one or more components (e.g., a) one or more curing agents as described above, b) one or more fillers as described above, and / or c) one or more rubber aids as described above). Typical methods for forming a vulcanizable rubber compound include mixing the following to form a vulcanizable rubber composition:

[0087] (i) a composition comprising an ethylene copolymer mixed with oil, preferably as an oil-extended ethylene-copolymer,

[0088] (ii) one or more curing agents,

[0089] (iii) one or more fillers,

[0090] (iv) one or more other rubber additives, preferably including at least one plasticizer.

[0091] Mixing preferably includes kneading, for example using conventional rubber mixing equipment, including, for example, a kneader, an open roller mill, an internal mixer, or an extruder. As is known to those skilled in the art, mixing can be performed in one or more steps.

[0092] Ethylene copolymers, and especially compositions containing copolymers blended with oil (preferably as oil-extended copolymers), can be used to prepare vulcanized rubber blends or articles having at least two, preferably at least three, and more preferably at least four or all of the following properties:

[0093] (a) Shore A hardness of at least 40.

[0094] (b) A tensile strength at break of at least 10 MPa.

[0095] (c) At least 400% elongation at break,

[0096] (d) tanδ less than 0.16, preferably less than 0.15.

[0097] (e) Dynamic stiffness less than 1.35, preferably less than 1.25.

[0098] (f) Rebound of at least 63% at 23°C and 60°C.

[0099] Typically, blends with low compression set can be prepared, for example, with a compression set of less than 9 at 72 hours and 23°C.

[0100] Articles and applications

[0101] To produce an article, a curable (vulcanizable) rubber compound is subjected to at least one forming step and shaped, for example, by extrusion and / or molding, and at least one vulcanization step. Vulcanization may be performed before, during, or after forming, such as during or after extrusion or molding. Articles made by using ethylene-polymers according to this disclosure contain a polymer in a cured form, i.e., the polymer is crosslinked with itself or with other crosslinkable components (e.g., other curable rubbers) in the compound or composition used to manufacture the article.

[0102] Therefore, a method for manufacturing an article is provided, the method comprising subjecting a rubber compound according to the present disclosure to molding and curing, wherein molding may be performed after, before, or simultaneously with curing. Therefore, an article obtained by this method is also provided.

[0103] The ethylene copolymers according to the present disclosure, as well as compositions and compounds containing them, can be used for a variety of end-use applications, including any application suitable for EPDM copolymers. Examples include, but are not limited to, hoses, belts, seals, motor mounts, roofing materials, or gaskets.

[0104] The ethylene-copolymers according to the present disclosure, including compounds made therefrom, can be particularly suitable as sealing materials or for the manufacture of seals. Seals include solid seals. By solid seal is meant that the material is not foamed and, in contrast to foamed materials, does not contain a honeycomb or sponge-like structure. The ethylene-copolymers and compositions according to the present disclosure, including compounds made therefrom, can be particularly suitable for the manufacture of foamed articles, including sponge-like seals or foamed seals. In one embodiment of the present disclosure, the article is a foamed article, more preferably a foamed seal, and more preferably an article having a density of less than 1.0 g / cm3, for example a density between 0.4 and 0.8. In another embodiment of the present disclosure, there is provided an article comprising the ethylene-copolymers according to the present disclosure in cured form, wherein the article is preferably a solid seal, i.e. a non-foamed seal. 3

[0105] List of specific embodiments

[0106] The present disclosure will now be further described by way of a list of illustrative embodiments of the present disclosure, but is not intended to be limited to these illustrative embodiments listed below.

[0107] First illustrative embodiment: A composition comprising an ethylene copolymer, the ethylene copolymer comprising units derived from ethylene, at least one C3-C 20 α-olefin, and at least one non-conjugated diene, wherein the copolymer contains

[0108] (i) up to and including 58 wt%, preferably from 35 to 56 wt%, and more preferably from 38 to 52 wt%, based on the total weight of the copolymer, of units derived from ethylene;

[0109] (ii) up to and including 57 wt%, preferably from 17 to 55 wt%, based on the total weight of the copolymer, of units derived from the at least one C3-C 20 α-olefin, preferably propylene;

[0110] wherein the ethylene copolymer has from about 80 up to about 125 units derived from the one or more dienes per polymer chain, and wherein the ethylene copolymer is mixed with oil and the total amount of oil in the composition is 29 phr or less, and wherein the composition contains from 60 wt% to 100 wt% of the ethylene copolymer and oil, based on 100% of the composition.

[0111] ​A second illustrative embodiment: The composition as recited in the first specific embodiment, wherein the copolymer comprises 5-ethylidene-2-norbornene (ENB) as the non-conjugated diene.

[0112] A third illustrative embodiment: The composition as recited in the first or second illustrative embodiment, wherein the copolymer comprises 5-ethylidene-2-norbornene (ENB) as the non-conjugated diene and wherein the ethylene copolymer has from 80 up to 125 units derived from ENB per polymer chain.

[0113] A fourth illustrative embodiment: The composition as recited in any of the preceding illustrative embodiments, having a phase angle minimum δ min .

[0114] A fifth illustrative embodiment: The composition as recited in any of the preceding illustrative embodiments, wherein the composition has a Mooney viscosity ML 1+8 at 150 °C from 80 to 120.

[0115] A sixth illustrative embodiment: The composition as recited in any of the preceding illustrative embodiments, wherein the ethylene copolymer has a branching level, expressed as Δδ, between 2 and 50.

[0116] A seventh illustrative embodiment: The composition as recited in any of the preceding illustrative embodiments, wherein the ethylene copolymer has a content of units derived from ENB between 5 and 20 wt.-% and a branching level, expressed as Δδ, between 10 and 25, based on the total weight of the copolymer.

[0117] An eighth illustrative embodiment: The composition as recited in any of the preceding illustrative embodiments, wherein the ethylene copolymer comprises from 5 to 20 wt.-% units derived from 5-ethylidene-2-norbornene (ENB), from 0.05 to 5 wt.-% units derived from 5-vinyl-2-norbornene (VNB), from 35 to 56 wt.-% units derived from ethylene, and from 17 to 55 wt.-% units derived from propylene, wherein all wt.-% are based on the total weight of the copolymer, and wherein the ethylene copolymer has from about 80 up to 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.

[0118] Ninth illustrative example: A composition as described in any of the foregoing illustrative examples, comprising at least 90% by weight, preferably at least 95% by weight, of an ethylene copolymer and an oil, based on 100% of the total weight of the composition, wherein the total oil content in the composition is up to 29 phr, preferably from 5 to 25 phr, and more preferably from 10 to 20 phr, and wherein the oil comprises one or more hydrocarbon-based oils.

[0119] Tenth illustrative embodiment: A method for manufacturing a rubber compound, the method comprising mixing a composition according to any one of the foregoing illustrative embodiments with at least one curing agent, optionally at least one filler, or a combination thereof.

[0120] Eleventh illustrative example: A rubber compound obtained by the method described in illustrative example 10.

[0121] Twelfth illustrative embodiment: A method of manufacturing an article of articles, the method comprising subjecting a rubber compound as described in the illustrative embodiment to molding and curing, wherein molding may be performed after, before, or simultaneously with curing.

[0122] Thirteenth illustrative embodiment: An article of manufacture obtained by the method described in illustrative embodiment 12.

[0123] Fourteenth illustrative example: The article as described in illustrative example 13 is a foamed article.

[0124] Fifteenth illustrative embodiment: The article as described in illustrative embodiment 13 has at least two of the following characteristics (i) to (iv): (i) a dynamic stiffness of less than 1.30, (ii) a tanδ of less than 0.15, (iii) an elongation at break of at least 500%, and (iv) a compressive deformation of less than 20, preferably less than 9, at 72 h and 23 °C.

[0125] Sixteenth Illustrative Example: A method of manufacturing a composition as described in any one of Illustrative Examples 1 to 9, the method comprising...

[0126] (i) Ethylene, at least one C3-C 20 α-olefins and at least one non-conjugated diene are polymerized in a reaction medium to provide ethylene copolymers.

[0127] (ii) The ethylene copolymer is mixed with one or more oils in the reaction medium.

[0128] (iii) Remove the reaction medium to separate the composition containing the copolymer and the oil.

[0129] (iv) optionally, subjecting the composition to at least one of the steps selected from the group consisting of drying, shaping, compressing, washing, and combinations thereof.

[0130] The present disclosure will now be further described by way of example, but is not intended to be limited to these examples and the embodiments used in the examples.

[0131] Test methods

[0132] Polymer testing

[0133] Polymer composition:

[0134] The composition of the copolymer was determined using Fourier transform infrared spectroscopy (FT-IR) according to ASTM D 3900 for C2 / C3 ratio and D 6047 for diene content on pressed polymer films.

[0135] Δδ:

[0136] The polymer branching level is 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, as determined by dynamic mechanical spectroscopy (DMS) at 125 °C and 10% strain. This quantity Δδ is a measure of the amount of long-chain branched structures present in the polymer and has been introduced in H.C. Booij, Kautschuk + Gummi Kunststoffe, Vol. 44, No. 2, pp. 128-130, which is incorporated herein by reference.

[0137] Molecular weight and molecular weight distribution:

[0138] 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) of the polymer were determined by gel permeation chromatography (GPC / SEC-DV) using a Polymer Char GPC from Polymer Characterization S.A, Valencia, Spain. The size exclusion chromatograph was equipped with an online viscometer (Polymer char V-400 viscometer), an online infrared detector (IR % MCT), and 3 AGILENT PL OLEXIS columns (7.5 x 300 mm) and a Polymer Char autosampler. The system was universally calibrated with polyethylene (PE) standards.

[0139] Polymer samples were weighed (concentration range 0.3 to 1.3 mg / ml) into vials of a PolymerChar autosampler. The vials were automatically filled with 1 g / l di-tert-butyl-p- cresol (DBPC) stabilized solvent (1,2,4-tri-chlorobenzene, TCB) in the autosampler. The samples were kept in a high temperature oven (160 °C) for 4 hours. After this dissolution time the samples were automatically filtered through an in-line filter before injection into the column. The chromatograph system was operated at 160 °C. The flow rate of the TCB eluent was 1.0 mL / min. The chromatograph included a built-in concentration with on-line infrared detector (IR5MCT) and a built-in PolymerChar on-line viscosimeter. The system was universally calibrated with polyethylene (PE) standards.

[0140] diene units in each chain:

[0141] The number of diene units in each polymer chain (also referred to herein as ‘diene content’ or ‘units derived from dienes’) corresponds to:

[0142]

[0143] wherein ‘[diene]i’ means the content of diene i units in the polymer in wt.% (= content of units derived from dienes); ‘polymer Mn’ means the number average molecular weight of the polymer, expressed in kg / mol; ‘Mw diene i’ means the molecular weight of a diene i molecule, expressed in g / mol.

[0144] In case the polymer contains units derived from several different dienes, the total diene content in each polymer chain is the sum of the content of the different dienes in each chain. For example, the diene content in each polymer chain, i.e. the number of dienes in each polymer chain, of a polymer containing diene units derived from diene A and diene B is calculated according to:

[0145] Number of dienes in each chain = {([diene A] x 10 x polymer Mn) / Mw diene A} + {([diene B] x 10 x polymer Mn) / Mw diene B)}.

[0146] The number of ENB units in each polymer chain corresponds to: ([ENB] x 10 x polymer Mn) / 120 g / mol, wherein ‘[ENB]’ is the content of ENB units in the polymer in wt.% (based on the total weight of the polymer of 100%). 120 g / mol is the molecular weight of ENB. ‘polymer Mn’ means the number average molecular weight of the polymer, expressed in kg / mol.

[0147] Mooney viscosity:

[0148] The Mooney viscosity was measured according to ISO 289.

[0149] phase angle minimum, δ min :

[0150] Ethylene-copolymers can be characterized by their curves in a van-Gurp-Palmen (vGP) plot. In a vGP plot, the phase angle (δ) is plotted against the absolute modulus ([G*]). The phase angle and the absolute modulus are obtained from rheological measurements of the temperature dependent storage modulus and loss modulus G'(T) and G"(T). The phase angle δ is calculated by tan G" / G'. The absolute modulus [G*] is calculated by the square root of the sum of (G') 2 +(G") 2 i.e.

[0151]

[0152] The point in the plot where the phase angle has a minimum is also the point where the absolute modulus [G*] has a minimum and this point can be used to characterize the ethylene-a-olefin copolymer (see e.g. 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 article of S. Trinkle et al. only refers to linear polymers, the determination of the δ minimum can also be used to characterize branched polymers).

[0153] To determine δ min , the temperature dependent storage modulus and loss modulus G'(T) and G"(T) are determined by dynamic mechanical thermal analysis (DMTA) measurements with a Mettler Toledo DMA 861 e rheometer equipped with a double sandwich simple shear sample holder at a frequency of 1 Hz and a heating rate of 1 K / min from -100 °C to +100 °C. Test samples with a diameter of 8 mm and a thickness of 1 mm are cut from plaques compression molded at 105 °C and 120 bar for 10 min.

[0154] From G'(T) and G"(T) the absolute modulus, and the phase angle, δ = tan G" / G', are calculated. Figure 1The van Gurp-Palmen (vGP) plot shown is obtained by plotting δ against the measured |G * | of Example 1. Figure 1 The dashed line in the vGP plot indicates the minimum phase angle (δ min ) and the corresponding absolute modulus, which is referred to herein as G * min .

[0155] Oil content:

[0156] The oil content can be determined by extraction, for example according to method D for non-vulcanized rubber and method A for vulcanized rubber in ISO 1407 from 2011.

[0157] Compound testing

[0158] Mooney viscosity:

[0159] The Mooney viscosity (measuring conditions at 100 °C, ML (1+4)) of the curable compound was determined according to DIN 53523-3 using NatureFlex NP / 28 pm film manufactured by Putz Folien, D-65232 Taunusstein Wehen, Germany.

[0160] Compression set (CS):

[0161] The compression set (CS) was determined on the cured compound according to DIN ISO 815.

[0162] Tensile strength at break (TS) and elongation at break (EB):

[0163] The tensile strength at break (TS) and elongation at break (EB) of the cured compound were determined on S2 dumbbells at 23 °C according to DIN ISO 37.

[0164] Hardness:

[0165] The Shore A hardness (H) was determined on the cured compound according to DIN ISO 7629-1.

[0166] Rebound:

[0167] The rebound resilience was measured at 23 °C according to DIN 53512.

[0168] Tan delta and dynamic stiffness:

[0169] A dynamic mechanical analyzer from MTS Systems Cooperation was used. Prior to the start of the measurement, two test specimens (6 mm high and 20 mm in diameter) were placed in the double shear sandwich sample holder and equilibrated at 60 °C for at least 30 min. Thereafter, the linear viscoelastic properties of the rubber material were probed by applying a simple shear geometry of peak-to-peak amplitude of 0.3 mm at frequencies ranging from 0.1 to 200 Hz (logarithmic scale with octaves of 8 data points). The results are shown in Figure 2 Fig. 1. Tan delta was determined at 200 Hz. Dynamic stiffness (DS) was obtained from the ratio of the absolute moduli measured at 180 Hz and 10 Hz: DS = |G * (180 Hz) / |G * (10 Hz).

[0170] Tear strength:

[0171] The tear resistance was measured at 23 °C using Delft test specimens applying ISO 34-2.

[0172] Experiment

[0173] Example 1 and Comparative Examples CI to C5:

[0174] Polymerization was carried out essentially by continuous polymerization as described in the general continuous polymerization procedure in International Patent Application No. WO 2005 / 090418, which is incorporated herein by reference, wherein compound 19 was used as catalyst. Polymerization was carried out in two liquid-filled solution polymerization reactors connected in series. Both reactors had a volume of 3 L. The overall system pressure was maintained above the venting pressure, keeping the entire system in solution phase. The ethylene and alpha-olefin feeds, as well as the catalyst feed, were adjusted to produce the unit content as 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 per chain ratio. The polymer production rate was about 900 g / h. The polymer solution was continuously discharged through a discharge line, where a solution of IRGANOX 1076 in isopropyl alcohol was added. Paraffin oil was added to the polymer solution and the solution of polymer (and oil) was post-treated by continuous stripping. The obtained oil-extended EPDM was batch-dried on a 2-roll mill. The rheological properties of the polymer of Example 1 were compared to the properties of different EPDM polymers (Comparative Examples, CI to C6) having different compositions and structures. The results are summarized in Table 1.

[0175] Table 1: Comparison of the polymer of Example 1 (Ex 1) to comparative polymers CI to C6.

[0176]

[0177]

[0178] n.d. = not detected; detection limit < 0.04%

[0179] ** = ML (1+4) at 150°C according to data sheet;

[0180] *** according to data sheet.

[0181] The polymers contain propylene as the alpha-olefin comonomer. Although the content of units derived from propylene is not shown in Table 1, it constitutes the remainder of the polymer and can be calculated by 100% minus the total content of units derived from ethylene, ENB, and VNB, with the exception of Polymer C5A. The amount of C2 units is taken from the data sheet and can not be corrected for diene content. The total amount of C2 units (ethylene) and C3 units (propylene) based on 100% wt of the polymer can be slightly low.

[0182] Comparative Examples C1 to C5A are commercial products and the data are taken from public data sheets or determined experimentally. C1 is an EPDM sample available from Lion Copolymer Geimar, LLC under the trade designation ROYALENE 547; C2 is an EPDM sample available from KUMHO POLYCHEM under the trade designation KEP 2480; C3 is an EPDM sample available from ExxonMobil under the trade designation VISTALON 8800; C4 is an EPDM sample available from ExxonMobil under the trade designation VISTALON 8700; C5 is an EPDM sample available from Mitsui Chemical Inc under the trade designation EPT8120E; C5A is an EPDM sample available from Sumitomo Chemical under the trade designation ESPRENE 5527F.

[0183] As can be seen from Table 1 and as is known in the art, generally, the higher the Mooney viscosity, the higher the molecular weight (Mw). The higher the Mw, the higher the number average molecular weight Mn. The Mn can be reduced by increasing the molecular weight distribution (MWD). The ENB content can be adjusted accordingly to achieve more than 80 ENB per polymer chain. For high molecular weight (Mw) and (Mn), lower amounts of ENB can be required than for low molecular weight polymers.

[0184] The content of units derived from ENB per polymer chain was analyzed in the following additional commercial samples:

[0185] EPDM available from ARLANXEO under the trade name KELTAN K8340A: ENB / polymer chain = 44;

[0186] EPDM available from ARLANXEO under the trade name KELTAN K7341A: ENB / chain = 63;

[0187] EPDM available from Exxon under the trade name VISTALON 7500: ENB / polymer chain = 34.

[0188] Example 2 and Comparative Examples C6 to C10:

[0189] The polymers of Example 1 and Comparative Examples C1 to C5 were compounded by an internal mixer (GK1,5E1 from Harburg-Freudenberger Maschinenbau GmbH; punch pressure of 8 bar, 50 rpm, degree of filling of 72% and total mixing time of 5 min). The curing system was added on an open mill (roller diameter of 200 mm; 20 rpm, roller temperature of 40°C and friction force).

[0190] Table 2: Ingredients for the manufacture of EPDM rubber compounds.

[0191]

[0192]

[0193] The resulting EPDM compounds were tested for compound properties. Example 2 is a compound made with the polymer of Example 1. Comparative Examples C6 to C10 are compounds obtained with the polymers of Comparative Examples C1 to C5.

[0194] Test specimens were prepared by curing test plaques of thickness 2 mm and 6 mm at 180°C for a time equivalent to 1.10 and 1.25 times t90 (t90 is the time to reach 90% of the maximum torque during rheometer measurement). The test results are shown in Table 3.

[0195] Table 3: Compound test results.

[0196]

[0197]

[0198] As can be seen from Table 3, compounds prepared from the polymers according to the present disclosure have good mechanical strength as shown by the tensile at break and good elastic properties as shown by the high elongation at break. The compounds have good shape retention as evidenced by the low compression set values. The compression set is also low over a wide temperature range. The compounds made from the polymers of the present disclosure also have improved elastic and dynamic properties as shown by the high rebound values and low tan delta values. The compounds made from the polymers of the present disclosure also exhibit excellent rebound resilience as shown by the low dynamic stiffness values in Table 3. Low dynamic stiffness values are particularly desirable for shock absorption and noise reduction and are particularly useful properties for sealing applications and for making foamed seals or sponge materials.

Claims

1. A composition comprising an ethylene copolymer, said ethylene copolymer containing (i) Units derived from ethylene, ranging from 38% to a maximum of 52% by weight; (ii) From 17% to a maximum of 57% by weight of derivatives of at least one C3-C 20 α-olefin units, wherein at least one C3-C 20 α-olefins include propylene; (iii) Units derived from 5-ethylidene-2-norbornene (ENB) ranging from 8 to 20% by weight, Wherein the weight percent in (i) to (iii) is based on a total weight of 100% by weight of the copolymer, and wherein, as determined according to formula (I), each polymer chain of the copolymer has more than 95 and up to and includes 125 units derived from ENB: Units derived from ENB = ([ENB] × 10 × polymer Mn) / 120 g / mol(I) Wherein [ENB] is the content of ENB units in the polymer as a percentage of total weight (100% by weight), and polymer Mn refers to the number-average molecular weight Mn of the polymer, expressed in kg / mol. (iv) 0.1 to 3% by weight of units derived from 5-vinyl-2-norbornene VNB based on 100% by weight of the total weight of the copolymer; And among them, The ethylene copolymer is oil-extended, and the total amount of oil in the composition is 5-25 phr, wherein the composition comprises at least 97% by weight of the ethylene copolymer and oil, based on 100% by weight of the composition.

2. The composition of claim 1, wherein, The ethylene copolymer has a branching level, expressed as Δδ, between 5 and 20, determined by dynamic mechanical spectrometry (DMS) at 125°C and 10% strain. Δδ, expressed in degrees, is the difference between a phase angle δ at a frequency of 0.1 rad / s and a phase angle δ at a frequency of 100 rad / s.

3. The composition of claim 1 or 2, wherein the ethylene copolymer is determined by gel permeation chromatography and the ethylene copolymer has a weight-average molecular weight Mw of at least 400,000 g / mol.

4. The composition according to claim 1 or 2, wherein, In the ethylene copolymer, each polymer chain has a content of more than 95 and up to and including 120 units derived from ENB.

5. The composition according to claim 1 or 2, wherein, The ethylene copolymer comprises 0.2 to 1.2% by weight of units derived from 5-vinyl-2-norbornene VNB, based on a total weight of 100% of the copolymer.

6. The composition according to claim 1 or 2, wherein, The ethylene copolymer has a content of ENB-derived units of 8 to 15% by weight of 100% of the total weight of the ethylene copolymer.

7. The composition according to claim 1 or 2, wherein, According to ISO 289, the composition has a Mooney viscosity of at least 80 ML 1+8 at 150°C.

8. The composition according to claim 1 or 2, wherein, In phase angle δ, relative absolute modulus [G] As determined in the figure, the composition has a minimum phase angle δ greater than 1 and less than 4.

00. min .

9. The composition of claim 1 or 2, having a Mooney viscosity ML 1+8 of 80 and up to 150 at 150°C.

10. The composition of claim 1, wherein, The ethylene copolymer has a branching level, expressed as Δδ, between 10 and 25, which is determined by dynamic mechanical spectrometry (DMS) at 125°C and 10% strain. Δδ, expressed in degrees, is the difference between a phase angle δ at a frequency of 0.1 rad / s and a phase angle δ at a frequency of 100 rad / s.

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