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    • 专利摘要:
    COMPOSITION, ARTICLE AND PROCESS FOR PREPARING THE COMPOSITION The invention provides a composition comprising a first composition comprising an ethylene/alpha-olefin/unconjugated polyene interpolymer having the following properties: (A) a Mw greater than or equal to 150,000 g/ mol; and (B) a peak area of 21.3 ppm to 21.8 ppm that is greater than or equal to 3.0 percent of the total integral area of 19.5 ppm to 22.0 ppm, determined by 13 C NMR; and the first composition having a tg delta (tg Delta) (190°C at 0.1 rad/s) less than or equal to 1.0.
    公开号:BR112015010913B1
    申请号:R112015010913-6
    申请日:2013-03-15
    公开日:2021-05-18
    发明作者:Timothy E. Clayfield；Colin LiPiShan；Sonja M. Delatte
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Invention history
    [0001] There is a need for polymeric compositions that have improved foaming characteristics (high expansion and smooth surface quality) and reduced water absorption for the targeted foam density. The observed water absorption is directly related to the foam structure formed and the number of closed cells present in the foam. The foaming process is a delicate balance of EPDM crosslinking and expansion (from a foaming agent such as CELOGEN OT), which is highly dependent on the melt elasticity of EPDM as well as the increase in viscosity during the cycle of expansion and healing. The melt elasticity of the polymer is related to its molecular weight and the degree of long-chain branching present. Typical EPDM sponges, such as VISTALON 8800 (Exxon-Mobil) and KELTAN 7341A (Lanxess), are oil-diluted products that are high molecular weight, and that are relatively amorphous. When formulated and vulcanized into a foam article, these EPDM resins are generally considered “best of its kind” in terms of water absorption, and foam properties such as compressive and tensile deformation. Rubber compositions for foams and/or other applications are also disclosed in the following: US20110233448A1, US6384290B1, US5691413B1, US20090209672, US4722971A, US5610254, US20110160323, WO2009/072503 (Abstract), JP20066307100A (Abstract), JP2007196358 and Summary).
    [0002] However, there is a need for new polymeric compositions that have foaming characteristics (high expansion and smooth surface quality) and reduced water absorption for the targeted foam density. Invention Summary
    [0003] The invention provides a composition comprising a first composition comprising an ethylene/alpha-olefin/unconjugated polyene interpolymer having the following properties: (A) a Mw greater than or equal to 150,000 g/mol determined by conventional GPC; and (B) a peak area of 21.3 ppm to 21.8 ppm that is greater than or equal to 3.0 percent of the total integral area of 19.5 ppm to 22.0 ppm, determined by 13 C NMR; and the first composition having a tg delta (tg δ) (190°C at 0.1 rad/s) less than or equal to 1.0. Brief description of the figures
    [0004] Figure 1 shows the tg δ (0.1 rad/s, measured at 190°C) against the weight average molecular weight (Mw) for inventive and comparative polymers;
    [0005] Figure 2 shows the tg δ against frequency profiles (rad/s) at 190°C for inventive and comparative polymers;
    [0006] Figure 3, shows "water absorption (% by weight) against foam density" for foam rods at 230°C; and
    [0007] Figure 4, shows "water absorption (% by weight) versus foam density" for foam tapes at 230°C. Detailed description of the invention
    [0008] As discussed above the invention provides a composition comprising a first composition comprising an ethylene/alpha-olefin/unconjugated polyene interpolymer having the following properties: (A) a Mw greater than or equal to 150,000 g/mol; and (B) a peak area of 21.3 ppm to 21.8 ppm that is greater than or equal to 3.0 percent of the total integral area of 19.5 ppm to 22.0 ppm, determined by 13 C NMR; and the first composition having a tg delta (tg δ) (190°C at 0.1 rad/s) less than or equal to 1.0.
    [0009] The composition may comprise a combination of two or more embodiments described herein.
    [0010] The first composition may comprise a combination of two or more embodiments described herein
    [0011] The unconjugated ethylene/alpha-olefin/polyene interpolymer may comprise a combination of two or more embodiments described herein.
    [0012] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is an ethylene/α-olefin/diene interpolymer (EAODM). In a further embodiment, the ethylene/α-olefin/polyene interpolymer is an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0013] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mw greater than or equal to 180,000 g/mol. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0014] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mw greater than or equal to 200,000 g/mol. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0015] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a peak area of 21.3 ppm to 21.8 ppm which is greater than or equal to 5.0 percent, even greater than 10 per cent. percent, greater than 15 percent of the total integral area of 19.5 ppm to 22.0 ppm, determined by 13C NMR. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0016] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a peak area of 21.3 ppm to 21.8 ppm that is greater than or equal to 16 percent, even greater than 17 percent, even greater than or equal to 18 percent of the total integral area from 19.5 ppm to 22.0 ppm, determined by 13C NMR. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0017] In an incorporation, the first composition has a tg delta (190°C in 0.1 s-1) less than 1.0, even less than or equal to 0.9. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0018] In an embodiment, the first composition further comprises an oil. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    In one embodiment, the first composition has a viscosity at 0.1 rad/s, 190°C, of 150,000 to 250,000 Pa's. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0020] In an embodiment, the first composition comprises an amount greater than or equal to 90 percent by weight, even greater than or equal to 95 percent by weight, yet greater than or equal to 98% by weight of the ethylene/alpha-olefin interpolymer /unconjugated polyene, based on the weight of the first composition.
    [0021] The first composition may comprise a combination of two or more embodiments described herein.
    [0022] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190°C) greater than or equal to 40, even greater than or equal to 50, and even greater or equal to 60. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene (EPDM) terpolymer. In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB). The rheology ratio (V0.1/V100 at 190°C) is that of the pure polymer (no oil and no filler); typically, the polymer is stabilized with "ppm amounts" of one or more antioxidants and/or other stabilizers.
    [0023] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190°C) greater than or equal to 70, even greater than or equal to 80, and even greater or equal to 90. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene (EPDM) terpolymer. In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0024] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190°C) of 80 to 130. In a further embodiment, the interpolymer is an EAODM, and further an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0025] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer comprises 6 to 15 percent by weight of polyene, further from 6 to 10 percent by weight of polyene, and further from 7 to 10 percent by weight by weight of polyene, based on the weight of the interpolymer. In a further embodiment, the polyene is a diene. In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a Mooney viscosity greater than or equal to 60, even greater than or equal to 80 (ML 1+4, 125 °C). Mooney viscosity is that of pure polymer (no oil and no charge); typically, the polymer is stabilized with one or more antioxidants and/or other stabilizers. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0027] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a MWD less than or equal to 4.0, yet less than or equal to 3.6. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0028] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a weight average molecular weight (Mw) less than or equal to 500,000 g/mol, even less than or equal to 400,000 g/mol, even less than or equal to at 300,000 g/mol. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0029] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a weight average molecular weight (Mw) of 150,000 to 500,000 g/mol, further from 180,000 to 400,000 g/mol, further from 200,000 to 300,000 g /mol. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0030] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer comprises from 40 to 65 percent by weight of ethylene, further from 40 to 60 percent by weight of ethylene, and further from 45 to 58 percent by weight by weight of ethylene, based on the weight of the interpolymer. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0031] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer is present in an amount greater than 20 percent by weight, even greater than or equal to 30 percent by weight, and still greater than or equal to 40 percent by weight, based on the weight of the composition. In a further embodiment, the interpolymer is an EAODM, and furthermore an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0032] In one embodiment, an inventive composition further comprises a filler. Suitable fillers include, but are not limited to, clay, CaCO3, talc, and mineral fibers.
    [0033] In an embodiment, the filler is present in an amount of 5 to 30 percent by weight, based on the weight of the composition.
    [0034] In one embodiment, an inventive composition further comprises at least one stabilizer. Suitable stabilizers include, but are not limited to AO and UV stabilizers.
    [0035] The inventive composition may comprise a combination of two or more embodiments described herein.
    [0036] The inventive composition also provides an article comprising at least one component formed from an inventive composition as defined by any of the embodiments described herein.
    [0037] In an embodiment, the article is a foam.
    [0038] In an incorporation, the article is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, construction and building materials, sole components and tubes.
    [0039] An inventive article may comprise a combination of two or more embodiments described herein.
    The invention also provides a process for preparing the composition as defined by any of the embodiments described herein, said process comprising polymerizing, in solution, at least one of the following: ethylene, an alpha-olefin and an unconjugated polyene. In a further embodiment, ethylene, alpha-olefin and unconjugated polyene are polymerized in a continuous solution polymerization process.
    [0041] An inventive process may comprise a combination of two or more embodiments described herein. Ethylene/α-olefin/unconjugated polyene interpolymer
    [0042] The ethylene/α-olefin/unconjugated polyene interpolymer, for the inventive compositions described herein, comprises, in polymerized form, ethylene, an α-olefin, and an unconjugated polyene. Suitable examples of α-olefins include C3-C20 α-olefins, and preferably propylene. Suitable examples of unconjugated polyenes include the unconjugated C4-C40 dienes.
    [0043] The α-olefin can be an aliphatic compound or an aromatic compound. Preferably, the α-olefin is a C3-C20 aliphatic compound, preferably a C3-C16 aliphatic compound, and more preferably a C3-C10 aliphatic compound. Preferred C3-C10 aliphatic α-olefins are selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and more preferably propylene. In a further embodiment, the interpolymer is an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0044] Illustrative unconjugated polyenes include straight chain acyclic dienes such as 1,4-hexadiene and 1,5-heptadiene; branched chain acyclic dienes such as 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 3, 7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 1,9-decadiene, mixtures of dihydromyricene isomers; single ring alicyclic dienes such as 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; bridged and fused multi-ring dienes such as tetrahydroindene, methyl-tetrahydroindene, alkenyl norbornenes, alkylidene, cycloalkenyl and cycloalkylidene such as 5-methylene-2-normenene (MNB), 5-ethylidene-2-normenene (ENB), 5-vinyl-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, and 5-cyclohexylidene-2-norbornene. Preferably, the polyene is an unconjugated diene selected from the group consisting of ENB, dicyclopentadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, and preferably, ENB, dicyclopentadiene and 1,4-hexadiene, more preferably ENB and dicyclopentadiene, and even more preferably ENB.
    In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer comprises a major amount of polymerized ethylene, based on the weight of the interpolymer. In a further embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the diene is ENB.
    [0046] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a molecular weight distribution (Mw/Mn or MWD) from 1.7 to 5.0, or from 2.0 to 4.0, or from 2.1 to 3.5, or from 2.5 to 3.5. In a further embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is an ethylene/α-olefin/diene interpolymer (EAODM). In a further embodiment, the interpolymer is an EPDM. In a further embodiment, the diene is ENB.
    [0047] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mooney viscosity. ML(1+4) at 125°C, greater than or equal to 60, or greater than or equal to 70, or greater than or equal to 80, or greater than or equal to 90. In a further embodiment, the ethylene/α-olefin interpolymer /unconjugated polyene is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is an EPDM. In a further embodiment, the diene is ENB.
    [0048] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mooney viscosity. ML(1+4) at 125°C, less than 500, or less than or equal to 300, or less than or equal to 200. In a further embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is an interpolymer of ethylene/α-olefin/diene. In a further embodiment, the interpolymer is an EPDM. In a further embodiment, the diene is ENB.
    [0049] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mooney viscosity. ML(1+4) at 125°C, from 60 to 500, or from 70 to 300, or from 80 to 200. In a further embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is an ethylene interpolymer. /α-olefin/diene. In a further embodiment, the interpolymer is an EPDM. In a further embodiment, the diene is ENB.
    [0050] Mooney viscosity is that of pure interpolymer (or calculated viscosity of pure polymer for polymers that contain a filler, such as carbon black, and/or an oil). Pure polymer refers to uncharged or oil-free polymer.
    [0051] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is a dyeable interpolymer. In a further embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is an EPDM. In a further embodiment, the diene is ENB.
    [0052] An unconjugated ethylene/α-olefin/polyene interpolymer may comprise a combination of two or more embodiments described herein.
    [0053] An ethylene/α-olefin/diene interpolymer may comprise a combination of two or more embodiments described herein.
    [0054] An EPDM terpolymer may comprise a combination of two or more embodiments described herein. Oils
    [0055] Oils include, but are not limited to petroleum oils such as aromatic and naphthenic oils; polyalkylbenzene oils; organic acid monoesters such as alkyl and alkoxy-alkyl oleates and stearates; diesters of organic acids such as phthalates, terephthalates, sebacates, adipates, and dialkyl, dialkoxy-alkyl, and alkylaryl glutarates; diesters of glycols such as tri, tetra, and poly(ethylene glycol) dialkanoates; trialkyl trimellites; trialkyl, trialkoxy-alkyl, alkylaryl and triaryl phosphates; chlorinated paraffin oils; coumarone-indene resins; pine tar; vegetable oils such as castor, rapeseed, palm, and soy oils and esters and epoxidized derivatives thereof; and the like.
    In an embodiment, the oil is present in an amount of 5 to 70 percent by weight, further from 5 to 50 percent by weight, based on the weight of the composition.
    [0057] In an embodiment, the oil is selected from the group consisting of non-aromatic oils, paraffinic oils, naphthenic oils, and combinations thereof. Suitable oils include, but are not limited to, PARALUX 6001, HYDROBRITE 550, and CALSOL 5550. Additions
    [0058] An inventive composition may comprise one or more additional additives. Suitable additives include, but are not limited to, fillers, antioxidants, UV stabilizers, filler retardants, dyes or pigments, and combinations thereof.
    [0059] Fillers include, but are not limited to, silicates of aluminium, magnesium, calcium, sodium, potassium and mixtures thereof; calcium, magnesium carbonates and mixtures thereof; silicon, calcium, zinc, iron, titanium, and aluminum oxides; calcium, barium, and lead sulfates; trihydrated alumina; magnesium hydroxide; natural fibers, synthetic fibers, and the like.
    [0060] Some antioxidants and antiozonants include, but are not limited to, hindered phenols, bisphenols, and thiobisphenols; and substituted hydroquinones. Foaming agents such as azodicarbonamide can be used to prepare a foam structure. applications
    [0061] The compositions of the present invention can be used to prepare or manufacture a variety of articles, or portions thereof or component parts. The inventive compositions can be converted into a finished article of manufacture by any of a number of conventional processes and apparatus. Illustrative processes include, but are not limited to, extrusion, calendering, compression molding, and other typical thermoset material molding processes.
    [0062] Articles include, but are not limited to, sheets, foams, molded products, and extruded parts. Additional items include automotive parts, sealing strips, belts, hoses, construction profiles, wire and cable coating, floor materials, gaskets, tires and tire components, computer parts, building materials and footwear components. An expert technician can quickly grow this list without undue experimentation.
    [0063] The inventive compositions are especially suitable for use as foams for automotive sealants. For example, an inventive composition can be used as a door seal, for example a main door seal, to insulate the cabin from air and water intake. A main door seal should have good surface quality, high deformation resistance, high tensile strength, low foam density, and low water absorption.
    [0064] Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight, and all methods are current as of the filing date of this disclosure.
    [0065] As used herein, the term "composition" includes a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or trace amounts.
    [0066] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers, either of the same type or of different types. Thus, the generic term polymer includes the term homopolymer (used to refer to polymers prepared from a single type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymeric structure), and the term interpolymer as defined below. Traces of impurities, such as catalyst residues, can be incorporated into the polymer.
    [0067] As used herein, the term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. Thus, the generic term interpolymer includes copolymers (used to refer to polymers made from two different types of monomers), and polymers made from more than two different types of monomers.
    [0068] As used herein, the term "ethylene-based polymer" refers to a polymer comprising at least a majority weight percentage of ethylene (based on polymer weight), and optionally may comprise one or more comonomers.
    [0069] As used herein, the term "ethylene-based interpolymer" refers to a polymer that comprises, in polymerized form, a majority weight percentage of ethylene (based on the weight of the interpolymer), and comprises at least one comonomer.
    As used herein, the term "ethylene/α-olefin/unconjugated polyene interpolymer" refers to a polymer comprising, in polymerized form, ethylene, an α-olefin, and an unconjugated polyene. In one embodiment, the "ethylene/α-olefin/unconjugated polyene interpolymer" comprises a majority weight percentage of ethylene (based on the weight of the interpolymer).
    [0071] As used herein, the term "ethylene/α-olefin/diene interpolymer" refers to a polymer comprising, in polymerized form, ethylene, an α-olefin, and a diene. In one embodiment, the "ethylene/α-olefin/diene interpolymer" comprises a majority weight percentage of ethylene (based on the weight of the interpolymer).
    [0072] As used herein, the term "ethylene/α-olefin/diene terpolymer" refers to a polymer comprising, in polymerized form, ethylene, an α-olefin, and a diene, as the only types of monomers . In one embodiment, the "ethylene/α-olefin/diene terpolymer" comprises a majority weight percentage of ethylene (based on the weight of the interpolymer).
    [0073] As used herein, the term "ethylene/α-olefin copolymer" refers to a copolymer comprising, in polymerized form, a major amount of ethylene monomer (based on the weight of the copolymer), and an α -olefin, as the only two types of monomers.
    [0074] As used herein, the term "propylene-based polymer" refers to a polymer that comprises at least a majority weight percent of propylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
    [0075] As used herein, the term "propylene/α-olefin copolymer" refers to a copolymer comprising, in polymerized form, a major amount of propylene monomer (based on the weight of the copolymer), and an α -olefin, as the only two types of monomers.
    [0076] As used herein, the term "incorporated oil" refers to oil contained in an ethylene/α-olefin/unconjugated polyene interpolymer.
    [0077] The terms "comprising", "including", "having", and its derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. For the avoidance of doubt, all compositions claimed by the use of the term "comprising" may include any additive, adjuvant, or additional compound, whether polymeric or not, unless stated otherwise. In contrast, the term “consisting essentially of” excludes from the scope of any subsequent mention any other component, step or procedure, except those that are not essential for operability. The term “consisting of” excludes any component, step or procedure not specifically listed or described. Mooney Viscosity
    [0078] The Mooney viscosity (ML1+4 at 125°C) of the interpolymer [ethylene/alpha-olefin/unconjugated polyene interpolymer (e.g., unfilled and oil-free EPDM) or ethylene/alpha-interpolymer was measured. olefin/unconjugated polyene (with thinner oil)] according to ASTM 1646, using the large rotor with a preheat time of one minute and a rotor runtime of four minutes. The instrument was a Mooney 2000 viscometer from Alpha Technologies.
    [0079] It is possible to estimate the Mooney viscosity (uncharged, without oil) against Mw (weight average molecular weight) by the following equation: MV(ML 1 + 4 at 125°C) = 147.82ln(Mw) - 1697, 3.
    [0080] One can estimate the Mooney viscosity diluted in oil (MV OE) against Mooney viscosity (no load, no oil) by the following equation: MV OE(ML 1+4 at 125°C) = {[ MV(ML 1 +4 at 125°C)] x [100/(100 + phr oil)]2,8}. Conventional gel permeation chromatography
    [0081] The chromatographic system consisted of a chromatograph of a Model PL-210 or a Model PL-220 both from Polymer Laboratories. Column and carousel compartments were operated at 140°C. The columns used were three 10 micron Mixed-B columns obtainable from Polymer Laboratories. The solvent used was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of “0.1 g polymer in 50 ml solvent”. The solvent used to prepare the samples contained “200 ppm butylated hydroxy toluene (BHT)”. Samples were prepared by gently shaking at 160°C for two hours. The injection volume used was 100 μL, and the flow rate was 1 mL/min.
    [0082] The set of GPC columns was calibrated with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 to 8,400,000 arranged in 6 "cocktail" mixtures with at least a ten weight separation individual molecular molecules. Standards were purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards were prepared in "0.025 g in 50 mL of solvent" for molecular weights greater than or equal to 1,000 kg/mol and in "0.05 g in 50 mL of solvent" for molecular weights less than 1,000 kg/mol. Polystyrene standards were dissolved at 80°C with gentle agitation for 30 minutes. Narrow standard mixtures were used first, and in order to lower maximum molecular weight component to minimize degradation. The maximum molecular weights of standard polystyrene are converted to molecular weights of polyethylene using the following equation: Mpolyethylene = A x (Mpolystyrene)B, where M is the molecular weight, A has a value of 0.431, and B is equal to 1, 0 (as described in Williams and Ward, J. Polym. Sc., Polym. Let., 6, 621 (1968). Polyethylene equivalent molecular weight calculations were performed using VISCOTEK TriSEC version 3.0 software. FTIR for EPDM composition analysis
    [0083] Terpolymers containing ethylene, propylene, and 5-ethylidene-2-norbornene were analyzed using ASTM D3900 for its ethylene content, and ASTM D6047 for its ethylidene-norbornene or dicyclopentadiene content. 13C NMR Method for EPDM Composition Analysis
    [0084] Samples were prepared by adding approximately "2.6 g" of a "50/50 mixture of tetrachloroethane-d2/ortho-dichlorobenzene" which is "0.025M" in chromium acetyl acetonate (relaxing agent) to " 0.2 g sample” in a 10 mm NMR tube. The samples were dissolved, and homogenized, by heating the tube and its contents to 150°C. Data were collected using a Bruker 400 MHz spectrometer equipped with a double Bruker DUL high temperature cryogenic probe. Data was acquired using “160 scans per data file”, a six-second pulse repetition delay, with a sample temperature of 120°C. The acquisition was performed using a spectral width of 25,000 Hz and a data point file size of 32K.
    [0085] NMR spectral analysis of the composition of the examples was performed using the following analytical method. The quantification of monomers present in EPDM can be calculated using the following equations (1 to 9).
    [0086] The calculation of moles of ethylene normalizes the spectral range from 55.0-5.0 ppm to 1000 integral units. The contribution of the normalized integral area only explains 7 of the ENB carbons. The ENB diene peaks at 111 and 147 ppm are excluded from the calculation due to concerns that double bonds may react at high temperatures. (1000-3*moles of P-7*moles of ENB)

    [0087] Additional NMR spectral analysis of the EPDMs used in the inventive compositions, exhibits a peak area of 21.321.8 ppm greater than 3.0% of the total integral area of 19.5 to 22.0 ppm. Similar spectral analysis of EPDMs (except NORDELL IP 5565) used in the comparative compositions show less than 3.0% of the total integral area from 19.5 to 22.0 ppm. Spectral data for EEE backbone at 30 ppm is mentioned. Peak responses in this region are typically related to differences in tacticality of propylene (% mm) that have been incorporated into EPDM. A similar analysis was performed for another type of ethylene/α-olefin/unconjugated polyene interpolymer. Dynamic-mechanical spectroscopy (DMS)
    [0088] Small angle oscillatory shear (cast DMS) was performed using ARES from TA Instruments, equipped with “25mm parallel plates”, in a nitrogen purge. The time between sample loading and test start was set to five minutes for all samples. The experiments were carried out at 190°C, over a frequency range from 0.1 to 100 rad/s. The deformation amplitude was adjusted based on the response of the samples, from 1 to 3%. The voltage response in terms of amplitude and phase was analyzed, from which the storage modulus (G’), loss modulus (G”), dynamic viscosity n*, and tg delta (tg δ) were calculated. The specimens for dynamic-mechanical spectroscopy were compression-molded discs "25 mm in diameter x 3.3 mm thick", formed at 180°C, and a molding pressure of 10 MPa, for five minutes, and then quickly cooled between chilled plates (15-20°C) for two minutes. The rheology ratio of viscosity at 0.1 rad/s to viscosity at 100 rad/s (V0.1/V100 at 190°C; also referred to as “RR”) was recorded. Typically, a linear molecule (no detectable long chain branching) has an RR less than or equal to 8. It is recognized that the presence of oil in the polymer can decrease the observed RR, so the following equation was used to estimate the RR of a polymer (RRpolymer) from the RR value of an oil-containing polymer (RROE_polymer): RRpolymer= RROE_polymer/(% by weight of oil * (-0.01988) + 1.0321). Differential Scanning Calorimetry (DSC)
    [0089] Differential scanning calorimetry (DSC) was used to measure the crystallinity in ethylene (PE) based samples (including EPDM). A polymer sample (0.5 g) was compression molded into a film at 5000 psi, 190°C, for two minutes. About 5 to 8 mg of film sample was weighed and placed in a DSC pan. The lid has been nailed into the pan to ensure a closed atmosphere. The sample pan was placed in a DSC cell, and then heated, at a rate of approximately 10°C/min to a temperature of 180°C for PE. The sample was kept at this temperature for three minutes. Then, the sample was cooled at a rate of 10°C/min to -90°C for PE, and held isothermally at that temperature for three minutes. Then, the sample was heated at a rate of 10°C/min until complete melting (second heating). Percent crystallinity was calculated by dividing the heat of fusion (Hf), determined from the second heating curve, by a theoretical heat of fusion of 292 J/g for PE, and multiplying this amount by 100 (eg % crystallinity = (Hf/292 J/g) x 100 (for PE)).
    [0090] Unless stated otherwise, the melting point (Tm) of each polymer was determined from the second heating curve, and the crystallization temperature (Tc) was determined from the first cooling curve. Compression deformation
    Compression strain was measured according to ASTM D395 at 23°C and 100°C. Discs "29 mm (±0.5 mm)" in diameter and "12.7 mm (±0.5 mm)" in thickness were drilled from compression molded plates, prepared as described in the compression molding section ( see Experimental section). Each button sample was inspected for nicks, non-uniform thickness and inhomogeneity, and selected buttons (without those defects) were tested. Deformation by compression was performed on two specimens for each sample, at the specified temperatures, and the average of the two specimens was recorded. The button specimen was placed in the compression device having two metal plates, which were pressed together, and locked in place at 75% of the original height of the button specimen. The compressive device, with the compressed samples, was placed in an oven, and equilibrated at the appropriate temperature for a specified time (22 hours for 23°C or 100°C). In this test, tension was released at the test temperature, and the sample thickness was measured after a 30-minute equilibration period at room temperature. Compression strain is a measure of the degree of recovery of a sample after compression, and is calculated according to the equation CS= (H0-H2)/(H0-H1) where H0 is the original thickness of the sample, H1 is the thickness of the spacer bar used, and H2 is the final thickness of the sample after removal of the compressive force. Tensile-deformation resistant internal tension properties
    [0092] Tensile-related properties were measured using die-cut specimens using a dog bone-shaped micro-tensile matrix having dimensions described in ASTM D-1708. The die-cut specimens were cut from the compression molded plates, which were prepared as described in the compression molding section (see Experimental section). The tensile properties (tensile strength and elongation) were measured, at room temperature, following the method of ASTM D-412, in the machine direction of an INSTRON Model 1122, manufactured by INSTRU-MET. Shore A hardness
    [0093] Specimen specimens were cut from compression molded plates, which were prepared as described in the compression molding section (see the Experimental section). Shore A hardness was measured ASTM D2240, on a Shore A Model 2000 durometer manufactured by INSTRON, with a Model 902 durometer base. This method allows hardness measurements based on its initial indentation or indentation after a specific period of time, or both. When used herein, indentation was measured at a specified time of ten seconds. Relative density
    [0094] The relative density of foam samples was measured according to ASTM D792. Water absorption by the vacuum method
    [0095] The water absorption determination was measured according to ASTM D1056. This test method determines the water absorption properties of closed cell foam by measuring the change in weight (mass) after a specified soak period. This test method is indirectly a measure of the cell structure/closed cell content of the sample.
    [0096] Cured foams were conditioned at room temperature for at least 1 day. The thermometer inside a vacuum oven cavity was kept at ambient reading prior to testing. Cured foam samples were cut into 1” rods or 1” strips. Three sets of 1” sections were cut per sample. Each sample was weighed to three decimal places, and its Initial Weight was recorded. A plastic container containing deionized water was used to submerge the samples. A plastic mesh was placed over the mouth of the plastic container, and the samples were dropped onto the mesh until the plastic mesh touched the bottom of the container. The samples were at least 2” below the surface of the water. The sample container was placed in a vacuum oven (VWR Oven Model 1410), and vacuum was applied, and reduced to 25 inches Hg. The test time measurement began as soon as the vacuum of “25 inches of Hg) was reached. The vacuum pump was turned off after three minutes. The furnace cavity was returned to atmospheric pressure by turning off the pump and venting the furnace chamber to atmospheric pressure. The container remained in the oven for another three minutes before removing the samples from the plastic container. Excess surface water was removed from each sample before weighing the tested samples. Each sample tested was weighed as quickly as possible to avoid loss of water through evaporation, and its Final Weight recorded. The percentage change in mass was calculated as follows:
    where W= change in mass, %; A= final mass of specimen in air, g; and B= initial mass of specimen in air, g. Experimental I. Representative Synthesis of Experimental EPDM Continuous Polymerization
    [0097] The inventive polymers were produced using continuous solution polymerizations by performing them in a computer-controlled autoclave reactor equipped with an internal stirrer. The 3.8 L reactor was fed with purified alkanes blend solvent (ISOPAR E obtainable from ExxonMobil Chemical Company), ethylene, propylene, 5-ethylidene-2-norbornene, and hydrogen. The reactor was equipped with a temperature control jacket and an internal thermocouple. Solvent feed into the reactor was measured by a mass flow controller. A variable speed diaphragm pump controlled the solvent flow rate and pressure to the reactor. At pump discharge, a side stream was used for flows to the catalyst and cocatalyst injection lines, and to the reactor agitator. These flows were measured by Micro-Motion mass flowmeters, and controlled by control valves or by manual adjustment of needle valves. The remaining solvent was combined with ethylene, propylene, 5-ethylidene-2-norbornene, and hydrogen (where used) and fed into the reactor. The mass flow controller was used to release, when necessary, hydrogen into the reactor. See U.S. Patent Nos. 5,977,251 and 6,545,088, and references therein, for reactors and other conditions associated with continuous polymerizations.
    [0098] The temperature of the solvent/monomer solution was controlled by using a heat exchanger before entering the reactor. This current entered through the bottom of the reactor. Catalyst component solutions were metered using pumps and mass flowmeters, and were combined with catalyst jet solvent, and introduced into the bottom of the reactor. The reactor ran full of liquid at 3.45 MPa (500 psig) with vigorous agitation. Product was removed through outlet lines at the top of the reactor. All reactor output lines were run with steam and insulated. Polymerization was stopped by adding a small amount of water to the outlet line, along with any stabilizers, or other additives, and passing the mixture through a static mixer. Also to reduce the process viscosity, a thinner oil (eg HYDROBRITE 550) in the specified amount was added. The product stream was then heated by passing it through a heat exchanger prior to devolatilization. The polymeric product was recovered by extrusion using a devolatilizing extruder and a water-cooled pelletizer. Process details and results are shown in Tables 1A and 1B.
    [0099] Catalyst 1 {[[[2',2'''-propanediyl-bis(oxy-kO)]bis[3-[3,6-bis(1,1-dimethyl ethyl)-9H-carbazol-9 -yl]-5'-fluor-5-(1,1,3,3-tetramethyl butyl)[1,1'-biphenyl]-2-olate-kO]](2-)]-dimethyl hafnium was fed into the reactor separately, and activated on site using cocatalyst 1 and cocatalyst 2. Cocatalyst 1 was a mixture of methyl-di(C14-18 alkyl) ammonium salts of tetrakis(pentafluor-phenyl)borate, prepared by reaction of a trialkylamine long-chain (ARMEEN M2HT, obtainable from Akzo Nobel, Inc.), HCl and Li[B(C6F5)4], substantially as disclosed in USP 5,919,988 (Example 2). Cocatalyst 1 was purchased from Boulder Scientific, and used for further purification. Cocatalyst 2 (modified methylaluminoxane (MMAO)) was purchased from Akzo Nobel, and used without further purification.
    [0100] The reactor output stream was consequently a mixture of polymer, solvent, and reduced levels of the initial monomeric streams. The molecular weight of the polymer was controlled by adjusting the reactor temperature, the monomer conversion, and/or the addition of a chain terminating agent, such as hydrogen. The polymerization reactions were carried out under steady state conditions, that is, constant concentration of reactants and continuous input of solvent, monomers, and catalyst, and removal of unreacted monomers, solvent and polymer. The reactor system was cooled and pressurized to prevent the formation of a vapor phase.
    [0101] Tables 1A and 1M show the reaction conditions used to produce some of the inventive examples.

    II. EPDM Polymer Compositions
    [0102] Table 2 summarizes the properties of some of the comparative examples. Note that all of these examples, except for NORDEL IP 5565, were produced in a process using a vanadium based catalyst (such as VOCl3 or VOCl4, low efficiency catalysts); EPDM ROYALENE, EPDM VISTALON and EPDM KELTAM are made-to-measure products that have been produced in a single reactor or a double reactor, and in the presence of additional branching agents (such as 1,4-hexadiene or 5-vinyl-norbornene).
    [0103] Table 3 summarizes the properties of all experimental EPDMs prepared for this study.

    1 Measured value without oil. 2 * Value measured with oil. 3 ** Mooney (no oil) estimated using the equation, MV OE (ML 1+4 at 125°C) = {[MV(ML 1+4 at 125°C)]x[100/(100 + phr oil )]2,8} where MV OE is the Mooney of the polymer with oil and MV is the Mooney of the polymer without oil. 4 *** Rheology ratio (without oil) estimated using the equation, RRpolymer= RROE_polymer/(% by weight of oil*(-0.01988)+1.0321), where RRpolymer is the rheology ratio of polymer (without oil), and RROE is the rheology ratio of the polymer to oil. NA= Not applicable a) Incorporated oil measured by mass balance, and equal to the percentage by weight of oil added to the polymerized polymer, at the end of the polymerization process. The weight percentage is based on the total weight of polymer and oil.
    3 ** Mooney (no oil) estimated using the equation, MV OE (ML 1+4 at 125°C) = {[MV(ML 1+4 at 125°C)]x[100/(100 + phr oil )]2,8} where MV OE is the Mooney of the polymer with oil and MV is the Mooney of the polymer without oil. 4 *** Rheology ratio (without oil) estimated using the equation, RRpolymer= RROE_polymer/(% by weight of oil*(-0.01988)+1.0321), where RRpolymer is the rheology ratio of polymer (without oil), and RROE is the rheology ratio of the polymer to oil. a) Incorporated oil measured by mass balance, and equal to the percentage by weight of oil added to the polymerized polymer, at the end of the polymerization process. The weight percentage is based on the total weight of polymer and oil.
    [0104] Figure 1 shows the "Mw against tg delta (δ)" for comparative composition and inventive compositions (EPDM 04 and EPDM 07). As shown, the inventive compositions contain EPDMs that have weight average molecular weights greater than 200,000 g/mol, and these compositions show lower tg delta in dynamic-mechanical spectroscopy, frequency scanning at 190°C, indicating a higher degree of elasticity of melt, conferred by a greater amount of long-chain branching. High molecular weight and long chain branching are required for high melt elasticity, which is important for sponge expansion to result in a foam article with low open cell content.
    [0105] Figure 2 compares the tg delta response of the noted EPDM compositions. A response range of tg delta is shown with EPDM 04 and EPDM 07, showing high melt elasticity (tg delta < 1 in 0.1 rad/s), and EPDM 01 showing low melt elasticity (tg delta > 1 in 0.1 rad/sec). The inventive examples EPDM 04 and EPDM 07 show tg delta values less than one from the beginning to the end of the entire frequency range. The comparative example NORDEL IP 5565 has a tg delta value greater than one, up to about 5 rad/s, and EPDM 01 has a tg delta value greater than one, up to about 2 rad/s. Comparing the "tg delta versus frequency" response of the inventive and comparative examples leads to the observation that the inventive examples have high levels of branching and high molecular weights. Data representation (not shown) using a Van-Gurp Palmen plot (phase angle versus G*), further supports this observation (Trinkle, S.; Friedrich, C.; “Van Gurp-Palmenplot: a way to characterize polydispersity of linear polymers”, Rheologica Act, 40, 322-328 (2001)).
    [0106] Each inventive EPDM composition also contains an EPDM that has an unexpectedly high amount of propylene tacticity, indicated by "% NMR peak area between 21.3 and 21.8 ppm, greater than 3%" relates to % tacticity mm (meso dyads) in EPDM. Table 2 shows that commercially obtainable EPDM material (such as ROYALENE 525, VISTALON 8600, 8800, or LANXESS (KELTAN 7341A)), prepared with vanadium based catalysts, does not exhibit this characteristic. This tactical feature provides a homogeneous melt, improving the compatibility and dispersion of EPDM with other components. During the production of a foam article, the improved compatibility provides an increase in cell formation homogeneity, with more uniform cell sizes produced throughout the foam. III. foams
    [0107] Table 4 shows the foam formulation used in this study. Table 5 shows specific foam formulations. Both the inventive and comparative examples are composed with the recipes shown in Table 5. The comparative examples contained NORDEL IP 5565, VISTALON 8600, VISTALON 8800, and EPDM 01. The inventive examples contained EPDM 04 and EPDM 07. recipes for VISTALON 8800, EPDM 04, and EPDM 07 were adjusted to the amounts of pre-incorporated oil that were present in the polymer.
    Ohm, RF; The Vanderbilt Rubber Handbook, 13th edition, Ed., RF Ohm, RT Vanderbilt Company, Inc., Norwalk, CT USA, 1990.
    Mixture of rubber compositions
    [0108] Each foam formulation was shear mixed in a BANBURY mixer (starting from room temperature), and then milled into flat layers using a roller mill.
    [0109] The formulation (without the blowing agent) was blended using a FARREL BR BANBURY blender (1.5 L volume) using an upside-down blending method. The polymer was weighed with the sulfur and other dry ingredients, and free-flowing at low speed for 2.5 minutes at 66°C (150°F), the accelerator added, and then the mixture flowed further, and then dropped to 99°C (210°F).
    [0110] To prepare the foaming composition, the above composition, together with the blowing agent, was introduced into the BANBURY, and flowed for 2.5 minutes, and released at 93°C (200°F). A reliable 6” roll mill was then used to complete the mix, and to grind an uncured layer of the desired composition. Compression molded plates
    [0111] The physical properties of the compositions that did not form foam (do not contain the sponging agent) were measured from plates, cured in a compression molder (for tensile test, compression deformation). The samples were compression molded in accordance with ASTM D3182 using a PHI (100 ton press).
    [0112] The desired mold (6” x 6” plate or compression knobs) was in the press. Each sample (uncured layer) was cut slightly smaller than the dimensions of the individual mold cavity. The grinding direction was marked, and the sample was labeled. It was lightly spray brushed with a dilute silicone solution and applied to the mold. The samples were placed in the preheated mold, taking care to place them properly in the milling direction. The boards were closed. Normal operating pressure was 100 tons, or as shown on the gauge as 200,000 pounds. When the cure was over, the bottom plate was automatically opened. The samples were removed, and immediately placed in water to stop curing. Samples were conditioned for 24 hours at room temperature before testing. To vulcanize the samples, they were conditioned at 200°C using t95 data plus three minutes for plates, and t95 data plus 15 minutes for compression-deformed buttons.
    [0113] Table 7 lists Mooney, Shore A, tensile and compression deformation properties of compression molded plates that did not contain the blowing agent. The Shore A hardness of the cured compounds ranged from 22 to 27 ShA. The compression set at 100°C of the inventive examples was the smallest of all the examples; EPDM 04 had a value of 23%, and EPDM 07 had a value of 26%. The compression set at 100°C of the comparative examples ranged from 28% to 39%. MDR Analysis
    [0114] MDR cure properties of each formulation were measured according to ASTM D-3182, using an MDR 2000 rheometer from Alpha Technologies. The MDR test was performed at 200°C for a period of 12 minutes.
    [0115] The rheology of uncured formulations (which do not contain the sponging agent) of uncured layer, cured in a rheometer (for MDR analysis) was measured so that the physical properties and curing properties could be tested . Samples were conditioned for 24 hours at room temperature before testing. Table 6 shows the curing properties for each of the formulations. The “t95 cure times (time to cure 95%) are less than or around three minutes at 200°C. At 230°C, the cure time is expected to be well under three minutes so that crosslinking is complete within the time frame of the foaming experiment.
    Compound Extrusion
    [0116] For the foaming tests, the uncured formulation containing 3 phr of blowing agent (CELOGEN OT) was mixed in the roller mill to form an uncured formulation layer. The uncured EPDM layers were cut into strips, and then extruded into strips of rods, using a CW Brabender Intelli-Torque Plasti-Corder, equipped with a single screw extruder with a rod die or 1” tape die. The temperature profile was 70°C, 80°C, and 90°C in the matrix. The extruder was operated at 50 rpm. Tapes made with the inventive compositions were observed to have a smooth appearance with no visible defects. Foaming
    [0117] The resulting rods and ribbons were cured at 230°C for four minutes, in a sand bath (for rods) and hot air oven (for ribbons). Due to the thickness of the rods, a sand bath (Techne Fluidized Sand Bath, Model #: IFB-51) was used filled with aluminum oxide powder to ensure good heat transfer; rods approximately “20 cm long” were suspended near the center of the sand bath. The "20 cm x 2.54 cm x 1.5 mm thick" tapes were suspended vertically in a hot air oven. After heat treatment, the crosslinked foam samples were cooled in a freezer set to -20°C. The crosslinked foam samples were conditioned for 24 hours at room temperature before testing.
    [0118] Table 7 shows the properties of the formulations, and rods and strips transformed into foam. The rod expansion ratio (based on the diameters of the unexpanded rod, and the expanded rod after heat treatment at 230°C, 4 minutes) of the inventive compositions containing EPDM 04, and EPDM 07 were respectively 1.33 and 1 .37. The expansion ratios of the comparative compositions ranged from 1.20 to 1.41. The inventive compositions show good expansion, and better expansion than compositions containing NORDEL 5565 and EPDM 01, which have weight average molecular weights less than 200,000 g/mol and tg delta values greater than 1.
    [0119] The tape expansion ratio (based on the width of the unexpanded tape, and the expanded tape after heat treatment at 230°C, 4 minutes) of the inventive compositions containing EPDM 04, and EPDM 07 were respectively 1, 39 and 1.51. The expansion ratios of the comparative compositions ranged from 1.29 to 1.57. The inventive compositions show good expansion, with the composition containing EPDM 07 having greater expansion than compositions containing NORDEL 5565 and EPDM 01, which have weight average molecular weights less than 200,000 g/mol and tg delta values greater than 1.
    *Mooney cured formulation without blowing agent.
    [0120] Figure 3 shows the water absorption for foam rods. The foam (spongy) formulations based on the inventive polymers of EPDM 04 and EPDM 07 resulted in low foam densities (0.4-0.55 g/cm3), and exhibited the lowest percentage water absorption of all. the samples tested. As seen in Figure 3, the water absorptions of foam rods prepared from the inventive compositions containing EPDM 04 and EPDM 07 are less than 4% by weight, and significantly less than that of the comparative compositions. The comparative composition containing NORDEL IP 5565 had a water absorption of about 13% by weight, and the comparative compositions containing VISTALON 8800 and 8600 had water absorptions of 17% by weight and 16% by weight, respectively. The comparative composition containing EPDM 01 had a water absorption of 19% by weight.
    [0121] Figure 4 shows the water absorption of the foam tapes. Tapes made with the inventive compositions, containing EPDM 04 and EPDM 07 have water absorptions less than 1.5% by weight, and are significantly lower than those of the comparative compositions. The comparative composition containing NORDEL IP 5565 had a water absorption of 5.7% by weight, and the comparative compositions containing VISTALON 8800 and 8600 exhibited water absorptions of 3.1% by weight and 4.1% by weight, respectively. . The comparative composition containing EPDM 01 had a greater water absorption of 2.3% by weight.
    [0122] The inventive compositions were found to provide an unexpected combination of low water absorption and low foam density. An inventive composition provides a homogeneous dispersion of the high molecular weight and highly branched ethylene/alpha-olefin/polyene interpolymer with other additives. High levels of % mm tacticity are believed to lead to improved compatibility with additional components in the foam recipe (eg oil, dressings, accelerators, other polymers). A foam article has a smooth surface film and a cell morphology with low open cell content. The foam article has good compression deformation, low relative density, and very low water absorption.
    权利要求:
    Claims (12)
    [0001]
    1. Composition, characterized in that it comprises a first composition comprising an ethylene/alpha-olefin/non-conjugated polyene interpolymer having the following properties: (A) a Mw greater than or equal to 200,000 g/mol; and (B) a peak area of 21.3 ppm to 21.8 ppm that is greater than 15 percent of the total integral area of 19.5 ppm to 22.0 ppm, as determined by 13 C NMR; and the first composition having a tan delta (190°C at 0.1 rad/sec) less than or equal to 1.0, and the interpolymer comprising from 40 to 60 weight percent ethylene, with based on the weight of the interpolymer.
    [0002]
    2. Composition according to claim 1, characterized in that the first composition further comprises an oil.
    [0003]
    3. Composition according to any one of claims 1 or 2, characterized in that the interpolymer has a rheology ratio (V0.1/V100 at 190°C) greater than or equal to 40.
    [0004]
    4. Composition according to any one of claims 1 to 3, characterized in that the interpolymer has a rheology ratio of 80 to 130.
    [0005]
    5. Composition, according to any one of claims 1 to 5, characterized in that the first composition has a viscosity of 0.1 rad/s, 190°C, from 150,000 to 250,000 Pa^s.
    [0006]
    6. Composition according to any one of claims 1 to 5, characterized in that the interpolymer has a polyene content of 6 to 15 percent by weight, based on the weight of the interpolymer.
    [0007]
    7. Composition according to any one of claims 1 to 6, characterized in that the interpolymer has a Mooney viscosity greater than or equal to 60 (ML 1+4, 125°C).
    [0008]
    8. Composition according to any one of claims 1 to 7, characterized in that the interpolymer has a MWD less than or equal to 4.0.
    [0009]
    9. Article, characterized in that it comprises at least one component formed from the composition, as defined by any one of claims 1 to 8.
    [0010]
    10. Article according to claim 9, characterized in that it is a foam.
    [0011]
    11. Article according to claim 9, characterized in that it is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, construction and building materials, sole components and tubes.
    [0012]
    12. Process for preparing the composition, as defined by any one of claims 1 to 8, characterized in that it comprises polymerizing, in solution, at least one of the following: ethylene, an alpha-olefin and an unconjugated polyene.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4722971A|1985-08-02|1988-02-02|Exxon Chemical Patents Inc.|Easy processing ethylene propylene elastomers|
    US6545088B1|1991-12-30|2003-04-08|Dow Global Technologies Inc.|Metallocene-catalyzed process for the manufacture of EP and EPDM polymers|
    US5691413A|1994-09-29|1997-11-25|Japan Synthetic Rubber Co., Ltd.|Ethylene-α-olefin-non-conjugated diene copolymer rubber composition|
    TW383314B|1994-12-20|2000-03-01|Mitsui Petrochemical Ind|Ethylene-alpha-olefin-nonconjugated polyene random copolymer, rubber composition, and process for preparing the random copolymer|
    US5777177A|1996-02-07|1998-07-07|Arco Chemical Technology, L.P.|Preparation of double metal cyanide-catalyzed polyols by continuous addition of starter|
    US5977251A|1996-04-01|1999-11-02|The Dow Chemical Company|Non-adiabatic olefin solution polymerization|
    TWI230723B|1999-06-30|2005-04-11|Sumitomo Chemical Co|Oil-extended copolymers for sponge|
    CN1137155C|1999-12-06|2004-02-04|中国石油化工集团公司|Catalyst system for polymerization or copolymerization of olefine|
    CA2427239A1|2000-10-04|2002-04-11|Grant B. Jacobsen|Supported catalyst compositions|
    US6960635B2|2001-11-06|2005-11-01|Dow Global Technologies Inc.|Isotactic propylene copolymers, their preparation and use|
    US20050124753A1|2002-04-26|2005-06-09|Mitsubishi Chemical Corporation|Polypropylene type aqueous dispersion, polypropylene type composite aqueous emulsion composition and its use|
    JP2004107539A|2002-09-19|2004-04-08|Mitsubishi Chemicals Corp|Polypropylene-based resin coated molded product|
    JP4568546B2|2004-07-16|2010-10-27|株式会社リコー|Image forming apparatus and process cartridge|
    JP2006033584A|2004-07-20|2006-02-02|Alps Electric Co Ltd|Fsk detection circuit|
    JP2006307100A|2005-05-02|2006-11-09|Bridgestone Corp|Thermoelastomer composition and sealing member with low stiffness using the same|
    JP4603423B2|2005-06-01|2010-12-22|三井化学株式会社|Rubber composition for sponge and method for producing sponge|
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    CN110234701A|2016-12-26|2019-09-13|陶氏环球技术有限责任公司|Ethylene/alpha-olefin/nonconjugated polyene interpolymer composition and product prepared therefrom|
    EP3672811A1|2017-08-24|2020-07-01|Dow Global Technologies LLC|Ethylene/c5-c10 alpha-olefin/ polyene interpolymers|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261731869P| true| 2012-11-30|2012-11-30|
    US61/731,869|2012-11-30|
    PCT/US2013/032468|WO2014084892A1|2012-11-30|2013-03-15|Ethylene/alpha-olefin/nonconjugated polyene based compositions and foams formed from the same|
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