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    • 专利摘要:
    Composition, cross-linked composition and article The invention provides a composition comprising a first composition comprising at least one ethylene/alpha-olefin/unconjugated polyene interpolymer; and the first composition has a mooney viscosity (ml 1+4, 125°c) greater than or equal to 10, and has a "% nmr peak area of 13c" which is the {[(nmr peak area of 13c from 21.3ppm to 21.8ppm) divided by (total integral area from 19.5ppm to 22.0ppm)] x 100}, which is greater than 3.5 percent, determined by nmr of 13c.
    公开号:BR112015010919B1
    申请号:R112015010919-5
    申请日:2013-03-15
    公开日:2021-08-17
    发明作者:Timothy E. Clayfield；Sonja M. Delatte；Colin LiPiShan
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Invention history
    [0001] There is a need for new compositions containing unconjugated ethylene/alpha-olefin/polyene interpolymers that can be used in vulcanized rubber compositions, and provide improved mixing and processability, improved mechanical properties, and improved product consistency.
    [0002] WO 2007/136494 disclosed ethylene/alpha-olefin/diene polymers prepared from a catalytic composition comprising a zirconium complex of a polyvalent aryloxy ether. WO 2006/009976 discloses processes for preparing polyolefins in the presence of a perfluorocarbon or hydrofluorocarbon with a non-metallocene catalyst of heteroaryl binder and metal in the center.
    [0003] Rubber compositions for foams and/or other applications are also disclosed in the following: WO 2011/008837, WO 2012/092491, US20060183631, WO 2011/163176, EP 1433812A1, WO 2011/041230, WO 2006/009976, WO 2000/26268, US8178031, EP 751181A1, EP 718324A1, WO 2011/0065877, JP 04132672B2 (Abstract), JP 2004035813 (Abstract), EP 1433812A1.
    [0004] However, as discussed above, there is a need for new polymeric compositions containing ethylene/alpha-olefin/unconjugated polyene interpolymers that can be used in vulcanized rubber compositions, and provide improved mixing and processability, improved mechanical properties, and Improved product consistency. Invention Summary
    [0005] The invention provides a composition comprising a first composition comprising at least one ethylene/alpha-olefin/unconjugated polyene interpolymer; and the first composition has a Mooney viscosity (ML 1+4, 125°C) greater than or equal to 10, and has a "%13C NMR peak area" which is the {[(NMR peak area of 13C from 21.3ppm to 21.8ppm) divided by (total integral area from 19.5ppm to 22.0ppm)] x 100}, which is greater than 3.5 percent, as determined by 13C NMR. Brief description of the figures
    [0006] Figure 1 shows a graph of "13C NMR peak area %" versus "C2 weight percent (13C NMR) for various inventive and comparative compositions (first composition). Detailed description of the invention
    [0007] As discussed above, the invention provides a composition comprising a first composition comprising at least one ethylene/alpha-olefin/unconjugated polyene interpolymer; and the first composition has a Mooney viscosity (ML 1+4, 125°C) greater than or equal to 10, and has a "%13C NMR peak area" which is the {[(NMR peak area of 13C from 21.3ppm to 21.8ppm) divided by (total integral area from 19.5ppm to 22.0ppm)] x 100}, which is greater than 3.5 percent, as determined by 13C NMR.
    [0008] The inventive composition may comprise a combination of two or more embodiments described herein.
    [0009] The first composition may comprise a combination of two or more embodiments described herein
    [0010] The ethylene/alpha-olefin/unconjugated polyene interpolymer may comprise a combination of two or more embodiments described herein.
    [0011] In one embodiment, the first composition has a "%13C NMR peak area" which is {[(21.3 ppm to 21.8 ppm13C NMR peak area) divided by (area total integral of 19.5 ppm to 22.0 ppm)] x 100}, which is greater than or equal to 4.0 percent, yet greater than or equal to 5.0 percent, determined by 13C NMR.
    [0012] In one embodiment, the first composition has a "%13C NMR peak area" which is {[(21.3 ppm to 21.8 ppm13C NMR peak area) divided by (area total integral of 19.5 ppm to 22.0 ppm)] x 100}, which is greater than or equal to 6.0 percent, yet greater than or equal to 7.0 percent, determined by 13C NMR.
    [0013] In one embodiment, the first composition has a "%13C NMR peak area" which is {[(21.3 ppm to 21.8 ppm13C NMR peak area) divided by (area total integral of 19.5 ppm to 22.0 ppm)] x 100}, which is greater than or equal to 8.0 percent, even greater than or equal to 9.0 percent, even greater than or equal to 10.0 per percent, determined by 13C NMR.
    [0014] In one embodiment, the first composition has a "% 13C NMR peak area" which is {[(21.3 ppm to 21.8 ppm 13C NMR peak area) divided by (area total integral of 19.5 ppm to 22.0 ppm)] x 100}, which is greater than or equal to 12.0 percent, even greater than or equal to 14.0 percent, even greater than or equal to 16.0 per percent, determined by 13C NMR.
    [0015] In one 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 percent by weight of the ethylene/alpha-interpolymer. olefin/unconjugated polyene, based on the weight of the first composition.
    [0016] In an embodiment, the first composition comprises an amount greater than or equal to 30 percent by weight, even greater than or equal to 40 percent by weight, or even greater than or equal to 50 percent by weight of the ethylene/alpha interpolymer - Olefin/unconjugated polyene, based on the weight of the first composition.
    In one embodiment, the first composition further comprises a second ethylene/alpha-olefin/unconjugated polyene interpolymer. In a further embodiment, the first composition comprises an amount greater than or equal to 90 percent by weight, yet greater than or equal to 95 percent by weight, yet greater than or equal to 98 percent by weight of the weight/sum of the second ethylene/alpha interpolymer. -olefin/unconjugated polyene and the ethylene/alpha-olefin/unconjugated polyene interpolymer, based on the weight of the first composition.
    In one embodiment, the first composition further comprises a second ethylene/alpha-olefin/unconjugated polyene interpolymer. In a further embodiment, the first composition comprises an amount greater than or equal to 30 percent by weight, even greater than or equal to 40 percent by weight, yet greater than or equal to 50 percent by weight of the weight/sum of the second ethylene/alpha interpolymer. -olefin/unconjugated polyene and the ethylene/alpha-olefin/unconjugated polyene interpolymer, based on the weight of the first composition.
    In one embodiment, the first composition satisfies the following ratio: %13C NMR peak area >-0.40(C2) + 33%; where the "% 13C NMR peak area" is the {[(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22 .0ppm)] x 100}, which is greater than 3.5 percent, determined by 13C NMR; and "C2" is the weight percentage of polymerized ethylene in the first composition, based on the weight of the first composition.
    In one embodiment, the first composition comprises from 40 to 80 percent by weight of ethylene, further from 45 to 75 percent by weight of ethylene, based on the weight of the first composition.
    [0021] In an embodiment, the first composition comprises from 0.5 to 15 percent by weight, further from 0.5 to 12 percent by weight, further from 0.5 to 10 percent by weight, further from 0.5 to 8 percent by weight, further from 0.5 to 6 percent by weight of the polyene, based on the weight of the first composition. In a further embodiment, the polyene is a diene, plus ENB.
    [0022] In one embodiment, the first composition has a viscosity at 0.1 rad/s, 190°C, greater than or equal to 40,000 Pa^s, even greater than or equal to 45,000 Pa»s, even greater than or equal to 50,000 Pa "s.
    [0023] In one embodiment, the first composition has a Mooney viscosity greater than or equal to 15, even greater than or equal to 20 (ML 1+4, 125°C).
    [0024] In one embodiment, the first composition has a Mooney viscosity greater than or equal to 30, even greater than or equal to 40 (ML 1+4, 125°C).
    [0025] In one embodiment, the first composition has a Mooney viscosity greater than or equal to 50, even greater than or equal to 60, even greater than or equal to 70 (ML 1+4, 125°C).
    In one embodiment, the first composition has a Mooney viscosity of 15 to 100, further 20 to 80 (ML 1+4, 125 °C).
    [0027] In an incorporation, the first composition has a MWD less than or equal to 4.0, even less than or equal to 3.5, even less than or equal to 3.0.
    [0028] In an incorporation, the first composition has a MWD greater than or equal to 2.0, even greater than or equal to 2.1.
    [0029] In an embodiment, the first composition has a rheology ratio (V0.1/V100 at 190°C) greater than or equal to 20, even greater than or equal to 23, and even greater than or equal to 25.
    [0030] In one embodiment, the first composition has a rheology ratio (V0.1/V100 at 190°C) of 20 to 50, still 22 to 45, still 25 to 40.
    In one embodiment, the first composition has a viscosity at 0.1 rad/s, 190°C, from 30,000 to 130,000 Pa's, further from 35,000 to 125,000 Pa's, further from 40,000 to 120,000 Pa's.
    [0032] In an embodiment, the first composition has a weight average molecular weight (Mw) less than or equal to 350,000 g/mol, even less than or equal to 300,000 g/mol, even less than or equal to 250,000 g/mol.
    [0033] In an embodiment, the first composition has a weight average molecular weight (Mw) of 50,000 to 350,000 g/mol, still from 60,000 to 300,000 g/mol, still from 70,000 to 250,000 g/mol.
    [0034] In an embodiment, the first composition has a tg delta (0.1 rad/s, 190°C) from 0.70 to 1.90, still from 0.75 to 1.80, still from 0.77 to 1.70.
    [0035] In one embodiment, the first composition has a tg delta (0.1 rad/s, 190°C) of 1.00 to 1.90, further from 1.10 to 1.80.
    [0036] In one embodiment, the first composition comprises from 40 to 90 percent by weight of ethylene, further from 50 to 90 percent by weight of ethylene, further from 55 to 85 percent by weight of ethylene, and further from 60 to 80 weight percent ethylene, based on the weight of the first composition.
    [0037] In an embodiment, the first composition is present in an amount greater than or equal to 20 percent by weight, even greater than or equal to 30 percent by weight, and even greater than or equal to 40 percent by weight, based on weight of makeup.
    [0038] The first composition may comprise a combination of two or more embodiments described herein.
    [0039] The ethylene/alpha-olefin/unconjugated polyene interpolymer may comprise a combination of two or more embodiments described herein.
    [0040] 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).
    [0041] In an embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190°C) greater than or equal to 20, even greater than or equal to 30, even greater or equal to 40, even greater than or equal to 50. 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).
    [0042] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190°C) from 20 to 80, still from 30 to 70, still from 40 to 60 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).
    [0043] The rheology ratio (V0.1/V100 at 190°C) of the ethylene/α-olefin/unconjugated polyene interpolymer is that of the pure polymer (no oil, no charge). The polymer can be stabilized with "ppm amounts" of one or more antioxidants and/or other stabilizers.
    [0044] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a viscosity at 0.1 rad/s, 190°C, from 120,000 to 200,000 Pa's, further from 130,000 to 190,000 Pa's, still from 140,000 to 180,000 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).
    [0045] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer comprises from 3.0 to 12.0 percent by weight of polyene, further from 4.0 to 10.0 percent by weight of polyene, and further from 5.0 to 7.0 weight percent 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).
    [0046] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mooney viscosity greater than or equal to 30, even greater than or equal to 35, even greater than or equal to 40 (ML 1+4, 125°C ). Mooney viscosity is that of pure polymer (no oil, no charge). The polymer can be stabilized with "ppm amounts" of 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).
    [0047] In an embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a MWD less than or equal to 3.5, even less than or equal to 3.0, even less than or equal to 2.5. 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).
    [0048] In an embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a MWD greater than or equal to 1.2, even greater than or equal to 1.5, even greater than or equal to 1.5, even greater or equal to 1.8. 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).
    [0049] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a MWD greater than or equal to 1.7, even greater than or equal to 2.0, even greater than or equal to 2.2. 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).
    [0050] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a weight average molecular weight (Mw) less than or equal to 400,000 g/mol, even less than or equal to 300,000 g/mol, even less than or equal to at 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).
    [0051] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer has a weight average molecular weight (Mw) of 80,000 to 300,000 g/mol, further from 100,000 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).
    [0052] In one embodiment, the ethylene/alpha-olefin/unconjugated polyene interpolymer comprises from 40 to 90 percent by weight of ethylene, further from 50 to 90 percent by weight of ethylene, and further from 55 to 85 percent by weight by weight of ethylene, and further from 60 to 80 percent 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).
    [0053] 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).
    [0054] The unconjugated ethylene/alpha-olefin/polyene interpolymer, further an EAODM, and further an EPDM, may comprise a combination of two or more embodiments described herein.
    [0055] In an embodiment, the composition further comprises a cross-linking agent.
    [0056] In an embodiment, the composition further comprises an oil.
    [0057] In one embodiment, an inventive composition further comprises a filler. Suitable fillers include, but are not limited to, clay, CaCO3, talc, and mineral fibers.
    [0058] In an embodiment, the filler is present in an amount of 5 to 30 percent by weight, based on the weight of the composition.
    [0059] In one embodiment, an inventive composition further comprises at least one stabilizer. Suitable stabilizers include, but are not limited to AO and UV stabilizers.
    [0060] The inventive composition may comprise a combination of two or more embodiments described herein.
    [0061] The invention also provides a crosslinked composition formed from an inventive composition as defined by one or more embodiments described herein.
    The invention also provides an article comprising at least one component formed from an inventive composition as defined by any of the embodiments described herein. In a further embodiment, the article is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, construction and building materials, shoe components and tubes.
    [0063] In an embodiment, the article is an automotive part.
    [0064] The invention also provides an article comprising at least one component formed from a cross-linked composition as defined by one or more embodiments described herein. In a further embodiment, the article is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, construction and building materials, shoe components and tubes.
    [0065] The inventive composition may comprise a combination of two or more embodiments described herein.
    [0066] An inventive article may comprise a combination of two or more embodiments described herein. Ethylene/α-olefin/unconjugated polyene interpolymers
    [0067] Ethylene/α-olefin/non-conjugated polyene interpolymers (including the second ethylene/α-olefin/non-conjugated polyene interpolymers), for the inventive compositions described herein, comprise, in polymerized form, ethylene, an α- olefin, and an unconjugated polyene. Suitable examples of α-olefins include C3-C20 α-olefins, further C3-C10 α-olefins, and preferably propylene. Suitable examples of unconjugated polyenes include the unconjugated C4-C40 dienes.
    [0068] 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).
    [0069] 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.
    [0071] 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, further from 1.8 to 4.0, still from 2.0 to 3.5, still from 2.0 to 3.0. 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.
    [0072] 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 20, even greater than or equal to 30, even greater than or equal to 35. In a further embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer is an o ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is an EPDM. In a further embodiment, the diene is ENB.
    [0073] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mooney, ML(1+4) viscosity at 125 °C, less than 100, or less than or equal to 80, or less than or equal to 60. 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.
    [0074] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mooney, ML(1+4) viscosity at 125°C, from 20 to 100, or from 30 to 80, or from 35 to 60 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.
    [0075] In one embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a Mooney, ML(1+4) viscosity at 125°C, from 10 to 100, or from 15 to 90, or from 20 to 85 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.
    [0076] 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.
    [0077] An unconjugated ethylene/α-olefin/polyene interpolymer may comprise a combination of two or more embodiments described herein.
    [0078] An ethylene/α-olefin/diene interpolymer may comprise a combination of two or more embodiments described herein.
    [0079] An EPDM terpolymer may comprise a combination of two or more embodiments described herein. crosslinking agents
    Vulcanizing agents include, but are not limited to, sulfur containing compounds such as elemental sulfur, 4,4'-dithio-dimorpholine, thiourama di- and polysulfides, alkyl-phenol disulfides, and 2-morpholine-dithio -benzothiazole; peroxides such as di-tert-butyl peroxide, tert-butyl-cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexane, di-(tert-butyl peroxy isopropyl)benzene, tert-butyl peroxybenzoate and 1 ,1-di-(tertiarybutyl peroxy)-3,3,5-trimethyl-cyclohexane; metal oxides such as zinc, magnesium, and lead oxides; dinitrous compounds such as p-quinone dioxime and p,p'-dibenzoyl-quinone dioxime; and phenol-formaldehyde resins containing hydroxymethyl or halomethyl functional groups. The suitability of any of these vulcanizing agents for use in the invention will largely be governed by the choice of polymers, as is well known to those skilled in the art. The sulfur can be a crystalline elemental sulfur or an amorphous elemental sulfur, and either type can be in pure form or supported on an inert carrier. An example of a supported sulfur is RHENOGRAN S-80 (80% sulfur and 20% inert carrier) from Rhein Chemie.
    [0081] In an embodiment of the invention, sulfur-containing compounds and peroxides are the preferred vulcanizing agents, and sulfur-containing compounds are most preferred. It is understood that mixtures of these vulcanizing agents can be employed, although it is not generally preferred. The amount of the vulcanizing agent can range from about 1 to 10 parts by weight, based on 100 parts of the polymers in the composition.
    [0082] The vulcanization time and temperatures employed are typical. Temperatures ranging from about 121°C (250°F) to about 227°C (440°F), and times ranging from about one minute to about 120 minutes may be employed.
    [0083] Additional crosslinking agents include, but are not limited to, phenolic resins, azides, aldehyde/amine reaction products, vinyl silanes, hydrosilylation, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, and combinations thereof. See “Encyclopedia of Chemical Technology”, volume 17, 2nd edition, Interscience Publishers, 1968; see also “Organic Peroxides”, Daniel Seern, volume 1, Wiley-Interscience, 1970), which are hereby incorporated entirely by reference.
    [0084] The crosslinking agent can be a phenolic curing agent or a peroxide curing agent, with an optional coagent, or hydrosilylation crosslinking agent with a hydrosilylation catalyst, or dibutyl tin dilaurate ("DBTDL"), with an optional trihydrated alumina ("ATH") coagent for silane grafted interpolymer. Phenolic resin and SnCl2 are used to cure EPDM (peroxide, or sulfur or hydrosilylation cure systems can also be used).
    Suitable peroxides include, but are not limited to aromatic dactyl peroxides, aliphatic dactyl peroxides, dibasic acid peroxides, ketene peroxides, alkyl peroxyesters, alkyl hydroperoxides (e.g., diacetyl peroxide, dibenzoyl peroxide, bis-2,4-dichloro-benzoyl peroxide, di-tertiobutyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert-butyl-cumyl peroxide, 2,5-bis(tert-butyl peroxy)-2,5-dimethyl-hexane, 2, 5-bis(tertiarybutyl peroxy)-2,5-dimethyl-hexine-3, 4,4,4',4'-tetra(tertiarybutyl peroxy)-2,2-dicyclohexyl-propane, 1,4-bis- (tertiobutyl peroxy isopropyl)-benzene, 1,1-bis-(tertiobutyl peroxy)-3,3,5-trimethyl-cyclohexane, lauroyl peroxide, succinic acid peroxide, cyclohexanone peroxide, tertiobutyl peracetate, butyl hydroperoxide, and the like.
    [0086] The vulcanizing elastomer can be grafted onto a vinyl silane monomer in the presence of a low level of peroxide via a separate reactive extrusion process. Suitable vinyl silanes include, but are not limited to, vinyl trimethoxysilane, vinyl triethoxysilane. The grafted elastomer can then react with water to cure the polymer in the presence of a catalyst such as dibutyl tin dilaurate during the dynamic vulcanization process. Appropriate sources of water include, but are not limited to, water vapor, water/ethylene glycol mixtures, aluminum hydroxide, and magnesium hydroxide. Ethylene/alpha-olefin copolymers or ethylene/alpha-olefin/polyene terpolymers are suitable vulcanizing elastomers for this curing system.
    [0087] Silicon hydride having at least two SiH groups in the molecule can react with the multiple carbon-carbon bonds of the unsaturated rubber component in the presence of a hydrosilylation catalyst to form useful crosslinks during dynamic vulcanization. Suitable silicon hydrides include, but are not limited to, methyl hydrogen polysiloxanes, methyl hydrogen/dimethyl siloxane copolymers, methyl hydrogen alkyl methyl polysiloxanes, bis(dimethyl silyl)alkanes and bis(dimethyl silyl)benzene. The amount of silicon hydride useful in compounding can range from about 0.1 to about 10.0 molar equivalents of SiH per carbon-carbon double bond in the rubber component of the thermoplastic elastomer. Suitable catalysts for the hydrosilylation vulcanization reaction include Group VIII transition metals such as palladium, rhodium, platinum and the like, including complexes of these metals. The use of hydrosilylation crosslinking to dynamically vulcanize EPDM to produce TPVs has been disclosed in U.S. Patent No. 6,251,998 (Medsker, et al., June 26, 2001, which is incorporated herein entirely by reference.
    [0088] A crosslinking agent may comprise a combination of two or more embodiments disclosed herein. Oils
    [0089] 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 from 5 to 70 percent by weight, further from 5 to 50 percent by weight, based on the weight of the composition.
    [0091] 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.
    [0092] An oil may comprise a combination of two or more embodiments described herein. Additions
    [0093] An inventive composition may comprise one or more additional additives. Suitable additives include, but are not limited to, fillers, antioxidants, UV stabilizers, flame retardants, dyes or pigments, and combinations thereof.
    [0094] 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.
    [0095] 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.
    [0096] In one embodiment, an inventive composition further comprises a thermoplastic polymer. Polymers include, but are not limited to, propylene-based polymers, ethylene-based polymers, and multiblock olefinic interpolymers. Suitable ethylene-based polymers include, but are not limited to, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), polymers homogeneously branched linear ethylene polymers, and homogeneously branched substantially linear ethylene polymers (i.e., homogeneously branched long chain branched ethylene polymers). applications
    [0097] 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.
    [0098] 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. Definitions
    [0099] 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.
    [0100] 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.
    [0101] 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.
    [0102] 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.
    [0103] 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.
    [0104] 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.
    [0105] 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).
    [0106] 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).
    [0107] 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.
    [0108] 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.
    [0109] 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.
    [0110] As used herein, the term "propylene/ethylene copolymer" refers to a copolymer comprising, in polymerized form, a major amount of propylene monomer (based on the weight of the copolymer), and ethylene, such as two unique types of monomers.
    [0111] 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. Test Methods Gel permeation chromatography
    [0112] 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.
    [0113] 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 separation between individual molecular weights. 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 Method for EPDM Composition Analysis
    [0114] 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
    [0115] 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.
    [0116] 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).
    [0117] 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.


    [0118] Additional NMR spectral analysis of the EPDMs used in the inventive compositions, exhibits a peak area of 21.321.8 ppm greater than 3.5% of the total integral area of 19.5 to 22.0 ppm. Similar spectral analysis of the EPDMs showed less than 3.5% 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)
    [0119] 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. Compression deformation
    [0120] 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
    [0121] 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
    [0122] Specimen specimens were cut from compression molded plates, which were prepared as described in the compression molding section (see 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. Compression molded plates
    [0123] The physical properties of non-foaming compositions (do not contain the sponging agent) were measured from plates, cured in a compression molder (for tensile test, compression set). The samples were compression molded in accordance with ASTM D3182 using a PHI (100 ton press).
    [0124] 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. Mooney Viscosity
    [0125] Mooney viscosity (ML1+4 at 125°C) was measured according to ASTM 1646, with a preheat time of one minute and a rotor operating time of four minutes. The instrument was a Mooney 2000 viscometer from Alpha Technologies.
    [0126] The viscosity of each of the formulated compositions was measured using an uncured layer (see experimental section), so that the viscosity of the uncured composition could be examined. Samples were conditioned for 24 hours at room temperature before testing. Mooney pre-vulcanization
    [0127] Pre-vulcanization property of each composition was measured according to ASTM D-1646, using a Mooney 2000 viscometer from Alpha Technologies. The Mooney viscometer was set to 125°C. Mooney prevulcanization values were reported for a small rotor, and represented the time to increase “x Mooney units” above the minimum viscosity (eg t5 is a “five Mooney units” increase in viscosity). The total test time was 30 minutes, with a preheat time of 1 minute. The viscosities of the compositions were measured from an uncured layer, cured in the viscometer, so that the prevulcanization properties could be examined. Samples were conditioned for 24 hours at room temperature before testing. MDR Analysis
    [0128] 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 160°C for a period of 30 minutes. The rheology of each formulated uncured layer sample composition was measured, which was then cured during the MDR analysis. Samples were conditioned for 24 hours at room temperature before testing. During the cure cycle, viscoelastic properties such as low mooney, high mooney, low tg delta, high tg delta, and time to reach a certain percentage of the cure state were measured (for example, t95 corresponds to the time in minutes to reach 95% cure state). temperature retraction
    [0129] Temperature shrinkage properties of the specimens cured according to ASTM D-1329 were measured. Shrinkage at lower temperatures using MODEL # TR-6 (BENZ Materials). This method describes a temperature shrinkage procedure for rapid evaluation of crystallization effects and for comparing viscoelastic properties of rubber and materials such as rubber at low temperatures. The initial specimen had dimensions of “48 mm by 120 mm by 2 mm” and was die cut according to the manner described in ASTM D-1329. This test method was performed by stretching the specimen to 150%, locking the specimen in the elongated condition, freezing the specimen to a state of reduced elasticity (-45°C), balancing the specimen by ten minutes, releasing the frozen specimen, and allowing free retraction of the specimen during temperature increase at a rate of 1°C/min, measuring the length of the specimen at regular temperature intervals, during its retraction, and computing the percentage of shrinkage at these temperatures from the data obtained. In practice, temperatures corresponding to 10% and 70% shrinkage, which are designated respectively as TR10 and TR70, are of particular importance. Break test C
    [0130] Break properties C were measured using specimens that were die cut, using a die having the dimensions described in ASTM D-624. The die cut specimens were cut from compression molded and cured plates, which were prepared as described in the section "Compression molding". The specimens were conditioned under ASTM conditions (23 +/- 2°C and 50% relative humidity (RH)) for at least 16 hours, before they were die-cut and tested. Breakage properties were measured at room temperature following the ASTM D-624 method, and were measured in the milling direction using model 1122 INSTRON, manufactured by INSTRU-MET. The length between the clamps was set to be 50.8 mm, and the test was run at a speed of 508 mm/min. The mean breaking strength C was recorded in N/mm. Experimental I. Representative Synthesis of Experimental EPDM Continuous Polymerization
    [0131] The polymeric products were produced in a solution polymerization process using a series of continuously mixed reactors; continuous stirred tank reactor configured in a single or double reactor configuration. See also U.S. Patent Nos. 5,977,251 and 6,545,088, and references therein, for reactors and associated equipment and polymerization conditions.
    [0132] Ethylene was introduced into an ISOPAR E solvent mixture (a mixture of C8-C10 saturated hydrocarbons obtainable from ExxonMobil), propylene and 5-ethylidene-2-norbornene (ENB), forming the reactor feed streams. Catalyst was individually fed into each reactor separately, and activated on site using cocatalyst 1 and cocatalyst 2. The output of each reactor was, consequently, a mixture of polymer, solvent, and reduced levels of initial monomeric streams; the output of the first reactor was fed directly into the second reactor (unless experimented otherwise). The molecular weight of the polymer can be controlled by adjusting each reactor temperature, 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 vapor phase formation.
    [0133] After polymerization, a small amount of water was introduced into the reactor output stream as a catalyst poison, and the reactor output stream was introduced into an expansion chamber, in which the solids concentration increased by minus 100 percent. A portion of the unreacted monomers, ie ENB, ethylene, and propylene, and the unused diluent were then collected, and where appropriate, recycled back to reactor feeds.
    [0134] Tables 1A and 1B show the reaction conditions used to produce some of the inventive examples. EPDM 01 was prepared using two consecutive circulation reactors (first reactor: circulation; second reactor (final): circulation). EPDM 02 and EPDM 03 were prepared using a circulation reactor followed by a continuous stirred tank reactor (first reactor: circulation; second reactor (final): CSTR). Examples designated as "R1" are from the materials sampled from the first reactor and are representative of the polymer composition that is fed into the second reactor. Table 2 shows the polymeric properties. Table 3 shows comparative resins. Table 1A: Reaction Conditions for Experimental EPDM
    *The catalyst is {[[[2',2'''-propanediyl-bis(oxy-kO)]bis[3-[3,6-bis(1,1-dimethyl ethyl)-9H-carbazol-9- yl]-5'-fluoro-5-(1,1,3,3-tetramethyl butyl)[1,1'-biphenyl]-2-olate-kO]](2-)]-dimethyl hafnium. Table 1B: Reaction Conditions for Experimental EPDM
    Table 2: Properties of Experimental EPDM Compositions
    *Based on weight of second (final) reactor product. Table 3: Property data for comparative compositions
    *Based on the weight of the second (final) reactor product
    [0135] Each curing formulation contained sulfur, accelerators, carbon black, zinc oxide, oil as shown in Table 4. Table 4: Amounts in phr, based on the weight of the first composition.

    [0136] Each formulation was shear mixed in a BANBURY mixer (starting from room temperature), and then milled into flat layers using a roller mill. The formulation was mixed using a FARREL BR BANBURY mixer (1.5 L volume) using an upside-down mixing method. The polymer was weighed with sulfur and other dry ingredients, and free-flowing at low speed for 2.5 minutes at 66°C (150°F); the accelerator was added, and then the mixture flowed further, and then dropped to 99°C (210°F). A reliable 6” roll mill was then used to produce foam products. Different and additional crosslinking agents such as peroxides can be used.
    [0137] Samples of the uncured layers were heated and cured in a compression molding machine (see Test Methods section), and properties were tested on the cured specimen. Samples from the uncured layers were heated in a rheometer (see Test Methods section), and the curing rates of the samples were examined. Tables 5 and 6 show the properties. Table 5: Properties after crosslinking
    Table 6: Rheological properties

    [0138] Figure 1 shows a graph of "% 13C NMR peak area" versus "C2 weight percent (13C NMR) for various inventive and comparative compositions (first composition). For this figure, comparative compositions are listed in Table 7, and inventive compositions are listed in Table 8. The tactical increase is a result of the catalyst and process, and the specific polymer that is produced. As shown in Figure 1, for the inventive compositions, % tacticity mm increases with decreasing ethylene content in the polymer. Table 7: 13C NMR Data for Comparative Examples
    *Prepared with Ziegler-Natta vanadium. **Prepared with metallocene (eg bis-metallocene). Table 8: 13C NMR Data for Inventive Examples

    [0139] The inventive compositions were found to have high levels of % mm tacticity. Comparative compositions, and those produced from other commercial processes and catalysts, do not exhibit this same characteristic. It is believed that the high levels of % mm tacticity lead to propylene sequences that join together within the polymer backbone. At the same level of crystallinity and Mooney viscosity as an EPDM, this higher tactical level is believed to increase the compatibility of components in a rubber formulation. Increased compatibility with oils, fillers, dressings, and other polymers allows for improved dispersion of formulation components, resulting in smoother surfaces of extruded, molded, laminated, or calendered articles, and fewer imperfections and defects due to undispersed components. Improved dispersion allows for shorter mixing times; shorter mixing times allow for simpler mixing equipment, which can be used to achieve the degree of dispersion required for typical applications.
    [0140] The examples show that the incorporation of this “% tacticity mm” into the polymer does not adversely affect the properties of a formulated rubber. When comparing compositions containing around 70% by weight of ethylene (C2), the respective inventive composition containing EPDM 01 had physical properties and curing properties similar to those of the composition containing EPDM 25. Also, when comparing compositions containing around 50% by weight of ethylene (C2), the respective inventive compositions containing EPDM 02 and EPDM 03 had similar physical properties and curing properties as the composition containing EPDM 70.
    [0141] The dispersion and mixing of the polymer is also a function of the polymer rheology, indicated by the low shear viscosity at 0.1 (rad/s) and the rheology ratio (V0.1 (viscosity at 0.1 rad/s) s)/V100(viscosity at 100 rad/s)). In some embodiments, high rheology ratios are preferred because they result in lower viscosity as shear conditions in the mixture are increased. Compared with the polymer of the first reactor of the first composition of EPDM 25 (first reactor), it was observed that the polymer of EPDM01-R1 (first reactor) had a rheology ratio of 38, whereas EPDM01-R1 (first reactor) had a rheology ratio of 65.5. Likewise, EPDM 25 (final polymer composition) had a rheology ratio of 16.0, while EPDM01-R1 (first reactor) had a rheology ratio of 37.7.
    [0142] In some incorporations, it is preferred tg delta smaller by 0.1 rad/s, because it gives greater melt elasticity at low shear rates. During the initial stages of mixing, the high melt elasticity can aid in the dissolution and dispersion of other components, acting as a shear promoter that helps maintain a high viscosity, even reducing the melt and dispersion stresses of the polymer. EPDM 25 has a delta tg, at 0.1 rad/s, of 2.0, while the delta tg, at 0.1 rad/s for EPDM 01 is 1.27. Compared to EPDM 25 (first reactor), EPDM01-R1 (first reactor) has delta tg, at 0.1 rad/s lower. The first reactor polymer of EPDM 25 had a delta tg, at 0.1 rad/s, of 1.0, while the delta tg, at 0.1 rad/s, for EPDM01-R1 is 0.79.
    [0143] Viscosity and rheological characteristics, together with “% tacticity mm” provide unique viscosity and compatibility that results in a polymer composition that disperses easily in a rubber compound. Such characteristics are important to obtain fine dispersion of the components added in a rubber formulation, such as carbon black, oils, dressings, talc, calcium carbonate, and other additives. Benefits are expected in rubber mixing operations and in the processing of final articles such as extruded profiles, injection molded articles, laminated and calendered articles.
    权利要求:
    Claims (13)
    [0001]
    1. Composition, characterized in that it comprises a first composition comprising at least one ethylene/propylene/5-ethylidene-2norbonene interpolymer; and the first composition having a Mooney viscosity (ML 1+4, 125°C) greater than or equal to 10, and the first composition having a "13C NMR peak area %" which is a { [(13C NMR peak area of 21.3 ppm to 21.8 ppm) divided by (total integral area of 19.5 ppm to 22.0 ppm)] x 100}, which is greater than or equal to 5 .0 percent, as determined by 13 C NMR; the first composition further comprising a second ethylene/propylene/5-ethylidene-2-norbonene interpolymer; where the first composition has a MWD less than or equal to 4.0; the 13 C NMR peak area being measured as per the description; wherein the MWD is measured according to the description and the Mooney viscosity is measured according to ASTM 1646.
    [0002]
    2. Composition according to claim 1, characterized in that the ethylene/propylene/5-ethylidene-2-norbornene interpolymer has a rheology ratio (V0.1/V100 at 190°C) greater than or equal to 20.
    [0003]
    3. Composition according to any one of claims 1 or 2, characterized by the fact that the ethylene/propylene/5-ethylidene-2-norbornene interpolymer has a rheology ratio from 20 to 80.
    [0004]
    4. Composition, according to any one of claims 1 to 3, characterized in that the first composition meets the following ratio: % of peak area of 13C NMR >-0, 40 (C2) + 33%; where the "% 13C NMR peak area" is the {[(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22 .0ppm)] x 100}, as determined by 13 C NMR; and the "C2" is the weight percentage of polymerized ethylene in the first composition, based on the weight of the first composition.
    [0005]
    5. Composition according to any one of claims 1 to 4, characterized in that the ethylene/propylene/5-ethylidene-2-norbornene interpolymer comprises 40 to 90 percent by weight of ethylene, based on weight of ethylene/propylene/5-ethylidene-2-norbornene interpolymer.
    [0006]
    6. Composition according to any one of claims 1 to 5, characterized in that the ethylene/propylene/5-ethylidene-2-norbornene interpolymer comprises from 3.0 to 12.0 percent by weight of 5- ethylidene-2-norbornene, based on the weight of the ethylene/propylene/5-ethylidene-2-norbornene interpolymer.
    [0007]
    7. Composition according to any one of claims 1 to 6, characterized in that the first composition has a viscosity of 0.1 rad/s, 190°C, greater than or equal to 40,000 Pa»s.
    [0008]
    8. Composition according to any one of claims 1 to 7, characterized in that the first composition has a Mooney viscosity greater than or equal to 20 (ML 1+4, 125°C).
    [0009]
    9. Composition according to any one of claims 1 to 8, characterized in that the ethylene/propylene/5-ethylidene-2-norbornene interpolymer has a MWD from 1.7 to 5.0.
    [0010]
    10. Composition according to any one of claims 1 to 9, characterized in that it further comprises a crosslinking agent.
    [0011]
    11. Cross-linked composition, characterized in that it is formed from the composition as defined in any one of claims 1 to 10.
    [0012]
    12. Article, characterized in that it comprises at least one component formed from the composition, as defined in any one of claims 1 to 11.
    [0013]
    13. Article according to claim 12, characterized in that it is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, construction and building materials, shoe components, and tubes.
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    US20200239674A1|2020-07-30|Ethylene/c5-c10 alpha-olefin/ polyene interpolymers
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    同族专利:
    公开号 | 公开日
    CN104812783A|2015-07-29|
    EP2925798A1|2015-10-07|
    CN104812783B|2021-07-16|
    BR112015010919A2|2017-07-11|
    KR20150090084A|2015-08-05|
    US10160819B2|2018-12-25|
    KR20190143463A|2019-12-30|
    JP6320407B2|2018-05-09|
    SG11201504003XA|2015-06-29|
    EP2925798B1|2019-04-24|
    KR102059709B1|2019-12-26|
    JP2015535552A|2015-12-14|
    WO2014084893A1|2014-06-05|
    KR102215306B1|2021-02-16|
    US20150274867A1|2015-10-01|
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    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]|
    2021-02-09| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|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
    US201261731891P| true| 2012-11-30|2012-11-30|
    US61/731,891|2012-11-30|
    PCT/US2013/032480|WO2014084893A1|2012-11-30|2013-03-15|Ethylene/alpha-olefin/polyene based compositions|
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