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    • 专利摘要:
    solution polymerization process, ethylene/(alpha)-olefin/unconjugated polyene interpolymer, composition and article. the invention provides a solution polymerization process for forming an ethylene/(alpha)-olefin/unconjugated polyene interpolymer, said process comprising polymerizing ethylene, an (alpha)-olefin, and an unconjugated polyene in the presence of a catalyst selected from formula (i) as described herein; and wherein the polymerization is conducted in a continuous process; and the interpolymer having a rheology ratio (v0.1/v100 at 190°c) greater than or equal to 20.
    公开号:BR112014014855B1
    申请号:R112014014855-4
    申请日:2012-12-20
    公开日:2022-01-11
    发明作者:Colin LiPiShan；Thomas W Karjala；Liam P Spencer；Jerzy Klosin；Michael L. Smith
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    prior art
    [001] There is a need for new ethylene/alpha-olefin/unconjugated polyene interpolymers with improved processability, melt strength, and physical properties in rubber compounds, and for new polymerization processes to form the same at higher temperatures, in order to save energy and increase production.
    [002] International publication WO2011/002998 discloses ethylenic polymers comprising low levels of total unsaturation. Compositions using such ethylene polymers, and articles of manufacture made therefrom, are also disclosed.
    [003] International publication WO2007/136497 discloses a catalyst composition comprising one or more metal complexes of a multifunctional Lewis base ligand, comprising a bulky, planar, aromatic or substituted aromatic group, and polymerization processes employing the same and, especially, a continuous, solution polymerization of one or more α-olefins at high catalyst efficiencies.
    [004] International publication WO2007/136494 discloses a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether, and the use thereof in a continuous solution polymerization of ethylene, one or more C3-30 olefins, and a conjugated diene or unconjugated to prepare interpolymers having improved processing properties.
    [005] International publication WO2007/136496 discloses metal complexes of polyvalent aryloxyethers, suitably substituted with sterically bulky substituent, which have improved solubility in aliphatic and cycloaliphatic hydrocarbons, and/or when employed as catalyst components for the polymerization of ethylene/α copolymers -olefin, produce products having reduced I10/I2.
    [006] International publication WO2011/002986 discloses ethylene polymers having low levels of long chain branching. Films and film layers made from these polymers have good hot adhesion resistance over a wide temperature range, making them good materials for packaging applications.
    [007] International publication WO2009/067337 discloses substantially isotactic propylene interpolymers comprising the following: (A) at least 60 percent by weight (% w/w) of units derived from propylene, and (B) between greater than zero and 40% ethylene derived units. The propylene interpolymer is further characterized by at least one of the following properties: (1) a g' ratio of less than 1, measured at a number average molecular weight (Mn) of the interpolymer, (2) a relative compositional shift of less than 1. than 50%, and (3) propylene chain segments having a chain isotacticity triad index of at least 70 mole percent.
    [008] International publication WO2006/020624 discloses a supported heterogeneous catalyst composition for use in addition polymerization of polymerizable monomers to form high molecular weight polymers comprising the following: 1) a substrate comprising an oxide compound solid, particulate, high surface area, surface modified inorganic, 2) a Group 4 metal complex of a bis(hydroxyaryloxy) ligand; and, optionally 3) an activating cocatalyst for the metal complex.
    [009] The international publication WO2007/136493 discloses a process for the polymerization of propylene, and further, optionally, one or more C4-30 α-olefins and/or one or more conjugated or unconjugated dienes under solution polymerization conditions, continuous, to prepare a high molecular weight polymer or interpolymer. The process comprises a hafnium complex of a polyvalent aryloxyether.
    [0010] International publication WO2001/136495 discloses a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether, and an alumoxane, and a polymerization process employing the same, and especially continuous, solution polymerization of ethylene and one or more plus C3-30 olefins or diolefins to prepare copolymers having reduced catalyst by-product content.
    [0011] International publication WO2007/136506 discloses a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether, and a polymerization process employing the same, and especially continuous solution polymerization of ethylene and one or more olefins or diolefins C3-30 to prepare interpolymers having improved processing properties.
    [0012] International publication WO2011/008837 discloses a composition comprising a first composition, which first composition comprises the following: A) a first interpolymer comprising, in polymerized form, ethylene, an α-olefin and an unconjugated polyene; B) a second interpolymer comprising, in polymerized form, ethylene, an α-olefin and an unconjugated polyene. The first composition has a [(ML(1+4, 125oC)/Mw(conv)]*1000 greater than 0.429 mol/g. The invention also provides a composition comprising a first composition comprising the following: A) a first interpolymer comprising , in polymerized form, ethylene, an α-olefin and an unconjugated polyene; B) a second interpolymer comprising, in polymerized form, ethylene, an α-olefin and an unconjugated polyene; and wherein the first composition has a Mooney viscosity [(ML(1+4, 125oC)/Mw greater than or equal to 70, and a low shear viscosity (n in 0.1 rad/sec) less than, or equal to 100,000 Pa·sec The invention also provides a composition comprising a first composition comprising the following: A) a first interpolymer comprising, in polymerized form, ethylene, an α-olefin and an unconjugated polyene; B) a second interpolymer comprising, in polymerized form, ethylene, an α-olefin and an unconjugated polyene; and wherein the first composition has a Mooney viscosity [(ML(1+4, 125oC)/Mw greater than or equal to 70, and a [(ML(1+4, 125oC)/Mw(conv)] less than 1.2.
    [0013] International publication WO2010/033601 discloses a composition comprising an unconjugated ethylene/α-olefin/diene interpolymer, which has the following properties: a Mz(abs)/Mz(conv) value greater than 1.3; a value of Mz(BB)/Mw(abs) greater than 1.6 but less than 2.5; and a value of Mw(abs) less than 350,000 g/mol; and (B) a coupling amount of (i) at least one (sulfonyl)azide or (ii) at least one peroxide; and (b) heating the resulting mixture to a temperature of at least the decomposition temperature of the cross-linking agent.
    [0014] However, as discussed above, there remains a need for new ethylene/alpha-olefin/unconjugated polyene interpolymers with improved properties, and for new polymerization processes to form the same. There is an additional need for such processes that can operate at higher temperatures, enabling polymers with higher molecular weights to be produced at lower intra-reactor viscosities. These needs were met by the following invention. summary
    [0015] The invention provides a solution polymerization process for forming an unconjugated ethylene/α-olefin/polyene interpolymer, said process comprising polymerizing ethylene, an α-olefin, and an unconjugated polyene in at least one reactor in the presence of a metal ligand complex selected from formula I:
    where: M is a metal of any one of Groups 3 to 6 of the Periodic Table of Elements (eg, Group 4), the metal M being in the formal oxidation state of +2, +3, +4, +5 , or +6; n is an integer from 0 to 5, where when n is 0, X is absent (ie, (X)n is absent); each X, independently, is a monodentate ligand that is neutral, monoanionic, dianionic, trianionic, or tetraanionic; or the two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; X and n are chosen in such a way that the metal-ligand complex of formula I is, on the whole, neutral; each Z, independently, is O, S, N-hydrocarbyl (C1-C40), or P-hydrocarbyl (C1-C40); L is hydrocarbylene (C1-C40) or heterohydrocarbylene (C1-C40), wherein the hydrocarbylene (C1-C40) has a moiety comprising a linker backbone of 1 carbon atom to 18 carbon atoms, preferably linker of 1 atom carbon to 12 carbon atoms, linking the Z atoms in formula (I) (to which Z atoms L are attached) and heterohydrocarbylene (C1-C40) has a moiety comprising a linker backbone of 1 atom to 18 atoms, preferably a 1 atom to 12 atom linker, linking the Z atoms in formula (I), each of the 1 to 18 atoms of the 1 to 18 atom linker backbone of the heterohydrocarbylene (C1-C40) is independently an atom or carbon heteroatom, each heteroatom independently being O, S, S(O), S(O)2, Si(Rc)2, P(RP), or N(RN), each RC being independently independently a substituted or unsubstituted (C1-C18) hydrocarbyl; heterohydrocarbyl (C1-C18); each RP, independently, is a substituted or unsubstituted (C1-C18) hydrocarbyl; heterohydrocarbyl (C1-C18); each RN, independently, is a substituted or unsubstituted (C1-C18) hydrocarbyl; heterohydrocarbyl (C1-C18) or absent (e.g., when the N to which RN is attached as -N=); each of R3a, R4a, R3b and R4b, independently, is a hydrogen atom, hydrocarbyl (C1-C40); heterohydrocarbyl (C1C40); Si(RC)3; O(RC); S(RC); N(RN)2; P(RP)2 or halogen atom; where RC, RN, and RP are as defined above; at least one of R6c, R7c, and R8c, and at least one of R6d, R7d, and R8d, independently, is hydrocarbyl (C2C40); Si(Rc)3, and each of R6c, R7c, R8c, R6d, R7d, and R8d, independently, is a hydrogen atom; hydrocarbyl (C1-C40); heterohydrocarbyl (C1-C40); Si(RC)3, O(RC); S(RC); N(RN)2; P(RP)2; or halogen atom; where RC, RN and RP are defined above; and optionally two or more R groups (from R3a to R8d) may combine together in one or more ring structures, with such ring structures having from 3 to 50 ring atoms not counting hydrogen atoms; at least one of R5c and R5f, independently, is hydrocarbyl (C1-C40); heterohydrocarbyl (C1-C40); Si(RC)3; O(RC); S(RC); N(RN)2; P(RP)2; or halogen atom; and the other of R5c and R5f, independently, is a hydrogen atom; hydrocarbyl (C1-C40); heterohydrocarbyl (C1-C40); Si(RC)3; O(RC); S(RC); N(RN)2; P(RP)2; or halogen atom; where RC, RN and RP are defined above; at least one of R5cc, and R5ff, independently, is hydrocarbyl (C1-C40); heterohydrocarbyl (C1-C40); Si(RC)3; O(RC); S(RC); N(RN)2; P(RP)2; or halogen atom; and the other of R5cc, and R5ff, independently, is a hydrogen atom; hydrocarbyl (C1-C40); heterohydrocarbyl (C1-C40); Si(RC)3; O(RC); S(RC); N(RN)2; P(RP)2; or halogen atom; where RC, RN and RP are defined above; each of R9a, R10a, R11a, R9b, R10b, R11b, R9aa R10aa R11aa R9bb R10bb and R11bb independently is an R , R , R , R , R , R , and R , independently, is a hydrogen atom; hydrocarbyl (C1-C40); heterohydrocarbyl (C1-C40); Si(RC)3; O(RC); S(RC); N(RN)2; P(RP)2; or halogen atom; where RC, RN and RP are defined above; optionally, two or more R groups of carbazoles (e.g. R9a, 10a 5a 11a 9b 10b 5f 11b R , R , R 1 , R , R , R , R ) may combine together in one or more ring structures, with such ring structures having from 3 to 50 ring atoms not counting hydrogen atoms; each of the aforementioned hydrocarbyl groups (e.g. RC, RN, RP, hydrocarbyl (C1-C40)), heterohydrocarbyl (C1-C40) groups (e.g. heterohydrocarbyl (C1-C40)), hydrocarbylene ( e.g., hydrocarbylene (C1-C40)), and heterohydrocarbylene (e.g., heterohydrocarbylene (C1-C40)), independently, is unsubstituted or substituted with at least one substituent RS (up to and including persubstitution by RS) ; the sum of carbon atoms in R5c + R5f + R7c is greater than 5 carbon atoms or the sum of carbon atoms in R5cc + R5ff + R7d is greater than 5 carbon atoms; and each RS, independently, is a halogen atom, substituted by polyfluor (that is, one of the at least one RS substituent corresponds to at least two fluorine substituents, which formally replace at least two hydrogen atoms of an unsubstituted version of the group substituted), perfluorine substitution (i.e., the one RS corresponds to as many fluorine substituents as there are hydrogen atoms of an unsubstituted version of the substituted group that is so substituted), unsubstituted (C1-C18)alkyl, F3C-, FCH2O-, F2CHO-, F3CO-, R3Si-, RO-, RS-, RS(O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O -, ROC(O)-, RC(O)N(R)-, or R2NC(O)-, or two RS are taken together to form an unsubstituted (C1-C18) alkylene, each R independently , an unsubstituted (C1-C18) alkyl; and wherein the polymerization is conducted in a continuous process; and wherein the interpolymer has a rheology ratio (V0.1/V100 at 190oC, as measured by dynamic mechanical spectroscopy) greater than or equal to 20. Description of drawings
    [0016] In the following, the invention will be better described with reference to the attached drawing, in which: Figure 1 shows C13 NMR profiles of inventive and comparative ethylene/α-olefin/unconjugated polyene interpolymers. Detailed Description
    [0017] As discussed above, the invention provides a solution polymerization process for forming an ethylene/α-olefin/unconjugated polyene interpolymer, said process comprising polymerizing ethylene, an α-olefin, and an unconjugated polyene in at least least one reactor in the presence of a metal-ligand complex (catalyst) selected from formula I
    where the substituents are as described above; and wherein the polymerization is conducted in a continuous process; and where the interpolymer has a rheology ratio (V0.1/V100 at 190oC, as measured by dynamic mechanical spectroscopy) greater than or equal to 20.
    [0018] In one embodiment, each Z is O.
    [0019] The inventive process may comprise a combination of two or more embodiments described herein.
    [0020] The ligand metal complex may comprise a combination of two or more embodiments described herein.
    [0021] In one embodiment, the interpolymer has a rheology ratio (V0.1/V100 at 190oC) greater than or equal to 30. In a further embodiment, the interpolymer has a rheology ratio (V0.1/V100 at 190oC) greater than or equal to 40.
    [0022] In one embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is EPDM. In a further embodiment, the diene is ENB.
    [0023] In one embodiment, M is a metal of any one of Groups 4 to 5 of the Periodic Table of Elements.
    [0024] In one embodiment, M is a Group 4 metal of the Periodic Table of Elements. In a further embodiment, the metal is Zr, Ti, or Hf. In a further embodiment, the metal is Ti or Hf. In a further embodiment, the metal is Hf.
    [0025] In one embodiment, each Z is O. In a further embodiment, the metal-ligand complex of formula (I) is a metal-ligand complex of formula (Ia):
    and R7c and R7d are each independently a (C4-C40) hydrocarbyl. Here, M, L, X, n, R3a, R4a, R3b, R4b, R5c, R5f, R5cc, and R5ff are each as defined above. In a further embodiment, the metal-ligand complex of formula (I) is a metal-ligand complex of formula (Ia-1):
    where R7c and R7d are each independently a (C4-C40) hydrocarbyl. Here, M, L, X, N, R3a, R3b, R5c, R5f, R5cc, and R5ff are each as defined above.
    [0026] In one embodiment, for a metal-ligand complex as described herein, each of R5c, R5f, R5cc, and R5ff, independently, is hydrocarbyl (C1-C40). In a further embodiment, each of R5c, R5f, R5cc, and R5ff independently is hydrocarbyl (C1-C20). In a further embodiment, each of R5c, R5f, R5cc, and R5ff independently is hydrocarbyl (C1-C10). In a further embodiment, each of R5c, R5f, R5cc, and R5ff independently is (C4-C8) alkyl or phenyl.
    [0027] In one embodiment, for a metal-ligand complex as described herein, each of R7c and R7d is independently hydrocarbyl (C4-C10). In a further embodiment, each of R7c and R7d is independently (C4-C8) alkyl.
    [0028] In one embodiment, for a metal-ligand complex as described herein, each of R3a and R3b is independently (C1-C6)alkyl, (C1-C6)alkyl-O-,((C1-C6)alkyl 2-N-, (C3-C6)cycloalkyl, fluorine atom, or chlorine atom In a further embodiment, each of R3a and R3b is independently a fluorine atom or a chlorine atom.
    [0029] In one embodiment, for the metal-3a 3b 5c 5f 5cc 5ff ligand complex as described herein, R, R, R, R, R, R, R7c, and R7d are not hydrogen atoms, and R3a and R3b are equal to each other; R7c, R7d are equal to each other; and R5c and R5f are respectively equal to R5cc and R5ff.
    [0030] In one embodiment, for the metal-binder complex as described herein, L is hydrocarbylene (C1-C20) which has a moiety comprising a linker backbone of 1 carbon atom to 6 carbon atoms linking the atoms Z in formula (I). In a further embodiment, L is CH2CH2CH2-.
    [0031] In one embodiment, for the metal-binder complex as described herein, L is hydrocarbylene (C1-C20) additionally a hydrocarbylene (C1-C10), additionally a hydrocarbylene (C1-C5). In a further embodiment, L is CH2CH2CH2-. Hydrocarbylene - formed by removing two hydrogen atoms from a hydrocarbon.
    [0032] In one embodiment, for the metal-ligand complex as described herein, each X is independently a (C1-C8) alkyl, a (C1-C6) alkyl, or a (C1-C4) alkyl, additionally a (C1-C4) alkyl. (C1-C3), or a (C1-C2) alkyl, and additionally a (C1-C3) alkyl.
    [0033] In one embodiment, for the metal-ligand complex as described herein, M is a Group 4 metal of the Periodic Table of Elements, the Group 4 metal being hafnium, zirconium, or titanium. In a further embodiment, M is hafnium, the hafnium, and additionally hafnium being in the +4 formal oxidation state; and n is 2 or 3. In a further embodiment, each X is independently a (C1-C8) alkylene, a (C1-C6) alkylene, a (C1-C4) alkylene, or a (C1-C3) alkylene. In a further embodiment, L is CH2CH2CH2-.
    [0034] In a further embodiment, the metal-ligand complex of formula (I) is a metal-ligand complex of formula (Ia-1):
    wherein each of R5c, R5f, R5cc, and R5ff is independently a hydrocarbyl (C1-C40), additionally a hydrocarbyl (C1C20), and additionally a hydrocarbyl (C1-C10), and additionally each of R5c, R5f, R5cc, and R5ff is independently (C4-C8) alkyl or phenyl; wherein each of R7c and R7d is independently hydrocarbyl (C4C10), and further each of R7c and R7d is independently (C4-C8) alkyl; wherein each of R3a and R3b is independently (C1-C6) alkyl, (C1-C6) alkyl-O-, (C1-C6 alkyl)2-N-, (C3-C6) cycloalkyl, fluorine atom or chlorine atom, and additionally is a fluorine atom; wherein L is (C1-C20) hydrocarbylene, additionally a (C1-C10) hydrocarbylene, additionally a (C1-C5) hydrocarbylene, and additionally, L is CH2CH2CH2-; wherein M is the metal of Group 4 of Table Periodic of the Elements, the group 4 metal being hafnium, zirconium, or titanium, and additionally M is hafnium, n is 2 or 3, and additionally n is 2; and wherein each X is independently a (C1-C8) alkyl, a (C1-C6) alkyl, a (C1-C4) alkyl, or a (C1-C3) alkyl, additionally a (C1-C3) alkyl, and additionally methyl.
    [0035] In one embodiment, the ligand metal complex of formula (I) is (2',2”-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-ter- butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium, (1).
    [0036] In one embodiment, the ligand metal complex of formula (I) is [[2',2”'-[1,3-propanediylbis(oxy-kO))]bis[3-[3,6-bis ((1,1-dimethylethyl)-9H-carbazol-9-yl]-5'-fluor-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]]-olate-kO] ](2-)]-hafnium dimethyl.
    [0037] In one embodiment, the polymerization takes place at a polymerization temperature of 80oC to 220oC. In a further embodiment, the polymerization takes place at a polymerization temperature of 90°C to 200°C.
    [0038] In one embodiment, the polymerization takes place at a polymerization temperature of 100oC to 200oC. In a further embodiment, the polymerization takes place at a polymerization temperature of 120°C to 190°C. In a further embodiment, the polymerization takes place at a polymerization temperature of 140°C to 190°C.
    [0039] In one embodiment, the polymer concentration in the reactor is greater than 5% w/w, preferably greater than 10% w/w, and more preferably greater than 15% w/w, based on the total feed to the reactor.
    [0040] In one embodiment, polymerization takes place in two reactors in series. In an additional embodiment, the temperature of the second reactor is greater than 150oC, and in an additional embodiment, greater than 160oC.
    [0041] In one embodiment, the temperature of the first reactor is from 90oC to 160oC, and the temperature of the second reactor is from 150oC to 200oC.
    [0042] The invention also provides an unconjugated ethylene/α-olefin/polyene interpolymer formed by the process of any embodiment as described herein. In a further embodiment, the unconjugated ethylene/α-olefin/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.
    [0043] In one embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer has a "peak area of 21.3 ppm to 21.8 ppm" greater than 3 percent of the total integral area of 19.5 ppm to 22.0 ppm as determined by C13 NMR. In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is EPDM. In a further embodiment, the diene is ENB.
    [0044] In one embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer has a "peak area of 21.3 ppm to 21.8 ppm" greater than 3.5, additionally greater than or equal to 5 .0 percent of the total integral area from 19.0 ppm to 22.0 ppm, as determined by C13 NMR. In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is EPDM. In a further embodiment, the diene is ENB.
    [0045] In one embodiment, the interpolymer is a substantially linear homogeneously branched ethylene/α-olefin copolymer.
    [0046] In one embodiment, the interpolymer has an "ethylene to α-olefin" molar ratio of 70/30 to 40/60.
    [0047] In one embodiment, the interpolymer has an "ethylene to α-olefin" molar ratio of 85/15 to 65/35.
    [0048] In one embodiment, the interpolymer has a % by weight polyene content of from 0.1 to 15% w/w, preferably from 0.4 to 10% w/w, based on the total weight of the interpolymer.
    [0049] The invention also provides an unconjugated ethylene/α-olefin/polyene interpolymer having a rheology ratio (V0.1/V100 at 190oC) greater than or equal to 20, and a "peak area of 21. 3 ppm to 21.8 ppm” greater than 3 percent, additionally greater than 3.5 percent, additionally greater than, or equal to, 5.0 percent, of the total integral area from 19.5 ppm to 22.0 ppm as determined by C13 NMR. In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is EPDM. In a further embodiment, the diene is ENB.
    [0050] In one embodiment, the interpolymer has a rheology ratio (V0.1/V100 at 190oC) greater than or equal to 30. In a further embodiment, the ethylene/α-olefin/unconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190°C) greater than or equal to 40. In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer is an ethylene/α-olefin/diene interpolymer . In a further embodiment, the interpolymer is EPDM. In a further embodiment, the diene is ENB.
    [0051] In one embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer is an ethylene/α-olefin/diene interpolymer. In a further embodiment, the interpolymer is EPDM. In a further embodiment, the diene is ENB.
    [0052] In one embodiment, the interpolymer is a substantially linear homogeneously branched ethylene/α-olefin copolymer.
    [0053] In one embodiment, the interpolymer has an "ethylene to α-olefin" molar ratio of 70/30 to 40/60.
    [0054] In one embodiment, the interpolymer has an "ethylene to α-olefin" molar ratio of 85/15 to 65/35.
    [0055] In one embodiment, the interpolymer has a % by weight polyene content of from 0.1 to 15% w/w, preferably from 0.4 to 10% w/w, based on the total weight of the interpolymer.
    [0056] An inventive unconjugated ethylene/α-olefin/polyene interpolymer may comprise a combination of two or more embodiments described herein.
    [0057] The invention also provides a composition comprising an unconjugated ethylene/α-olefin/polyene interpolymer according to any embodiment as described herein. In one embodiment, the composition comprises at least one additive.
    [0058] In one embodiment, the composition comprises greater than or equal to 40 weight percent, or greater than or equal to 50 weight percent, or greater than or equal to 60 weight percent of the interpolymer, based on the weight of the composition.
    [0059] In one embodiment, the composition comprises greater than or equal to 80 weight percent, or greater than or equal to 90 weight percent, or greater than or equal to 95 weight percent of the interpolymer, based on the weight of the composition.
    [0060] In one embodiment, the composition comprises at least one filler. In a further embodiment, the filler is selected from the group consisting of carbon black, CaCO3, silica, and combinations thereof. In a further embodiment, the filler is selected from the group consisting of carbon black, CaCO3, and combinations thereof.
    [0061] In one embodiment, the composition comprises at least one filler. In a further embodiment, the composition comprises less than 70 weight percent, or less than 60 weight percent, or less than 50 weight percent, of the filler, based on the weight of the composition. In a further embodiment, the filler is carbon black.
    [0062] In one embodiment, the composition comprises at least one filler. In a further embodiment, the composition comprises greater than 20 weight percent, or greater than 25 weight percent, or greater than 30 weight percent, of the filler, based on the weight of the composition. In a further embodiment, the filler is carbon black.
    [0063] The invention also provides a crosslinked composition formed from the inventive composition.
    [0064] The invention also provides an article comprising at least one component formed from the inventive composition. In one embodiment, the article is a foam. In a further embodiment, the article is an automotive part. In another embodiment, the article is a profile for civil construction.
    [0065] The invention also provides an article comprising at least one component formed from the inventive composition. In one embodiment, the article is a foam. In a further embodiment, the article is a profile for building construction.
    [0066] An inventive process may comprise a combination of one or more embodiments described herein.
    [0067] The metal-ligand complex of formula (I) may comprise a combination of two or more embodiments described herein.
    [0068] The metal-ligand complex of formula (Ia) may comprise a combination of two or more embodiments described herein.
    [0069] The metal-ligand complex of formula (Ia-1) may comprise a combination of two or more embodiments described herein.
    [0070] An inventive unconjugated ethylene/α-olefin/polyene interpolymer may comprise a combination of two or more embodiments described herein.
    [0071] An inventive composition may comprise a combination of two or more embodiments described herein.
    [0072] An inventive cross-linked composition may comprise a combination of two or more embodiments described herein.
    [0073] An inventive article may comprise a combination of two or more embodiments described herein.
    [0074] The inventive polymerization described here has been found to produce EPDM's that are higher in molecular weight, and contain higher levels of long-chain branching, and higher levels of ENB incorporation. The higher levels of long chain branching in the polymer enable EPDM polymers to be used in processes that require good melt strength, such as calendering and foaming sponges. Polymers with a combination of high molecular weight, high long-chain branching, and high levels of ENB are typically used in weather-sealing sponges, such as those used in primary seals on doors in automotive applications. Ethylene/α-Olefin Interpolymers /Unconjugated Polyenes
    [0075] Unconjugated ethylene/α-olefin/polyene interpolymers comprise, in polymerized form, ethylene, an α-olefin, and an unconjugated polyene. Suitable examples of α-olefins include C3-C10 α-olefins, and preferably propylene. Suitable unconjugated polyenes include unconjugated dienes. Examples of suitable unconjugated dienes include C4-C40 unconjugated dienes.
    [0076] The α-olefin may be an aliphatic or aromatic compound. The α-olefin is preferably a C3-C20 aliphatic compound, preferably a C3-C16 aliphatic compound, and more preferably a C3-C10 aliphatic compound. Preferred C3-C10 aliphatic compounds are selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and more preferably propylene. In a preferred embodiment, the interpolymer is an ethylene/propylene/diene terpolymer (EPDM). In a further embodiment, the diene is 5-ethylidene-2-norbornene (ENB).
    [0077] 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, 5,7-dimethyl-1,7-octadiene, 1,9-decadiene, and mixed isomers of dihydromyricene; single ring alicyclic dienes such as 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclodecadiene; fused or bridged multi-ring alicyclic dienes such as tetrahydroindene, methyl tetrahydroindene, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, and 5-cyclohexylidene-2-norbornene. The diene is preferably 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.
    [0078] In one embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer comprises a major amount of polymerized ethylene, based on the weight of the interpolymer. In a further embodiment, the unconjugated ethylene/α-olefin/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.
    [0079] In one embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer has a distribution of at least (Mw/Mn) of 1.5 to 3.5, or 1.8 to 3.0, or from 2.0 to 2.5. In a further embodiment, the unconjugated ethylene/α-olefin/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.
    [0080] In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer has a Mooney viscosity, ML(1+4) at 125oC, greater than, or equal to, 15, or greater than, or equal to , 30, or greater than, or equal to, 50, or greater than, or equal to, 70. In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer is an ethylene/α-olefin/ diene. In a further embodiment, the interpolymer is an EPDM. In a further embodiment, the diene is ENB.
    [0081] In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer has a Mooney viscosity, ML(1+4) at 125oC, less than 200, or less than 150, or less than 100. In a further embodiment, the unconjugated ethylene/α-olefin/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.
    [0082] In a further embodiment, the unconjugated ethylene/α-olefin/polyene interpolymer has a Mooney viscosity, ML(1+4) at 125°C, from 15 to 200, or from 50 to 150, or from 70 to 100 In a further embodiment, the unconjugated ethylene/α-olefin/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.
    [0083] Mooney viscosity is that of the pure interpolymer (or calculated pure polymer viscosity for polymers that contain a filler, such as carbon black, and/or an oil).
    [0084] An unconjugated ethylene/α-olefin/polyene interpolymer may comprise a combination of two or more combinations as described herein.
    [0085] An ethylene/α-olefin/diene interpolymer may comprise a combination of two or more combinations as described herein.
    [0086] An EPDM may comprise a combination of two or more combinations as described herein. Additions
    [0087] An inventive composition may comprise one or more additives. Additives include, but are not limited to, fillers, antioxidants, UV stabilizers, flame retardants, plasticizers or oils, crosslinking agents, colorants or pigments, and combinations thereof.
    [0088] Fillers include, but are not limited to, carbon black; aluminum, magnesium, calcium, sodium, potassium silicates and mixtures thereof; calcium carbonates, magnesium carbonates and mixtures thereof; oxides of silicon, calcium, zinc, iron, titanium, and aluminum; calcium, barium and lead sulfates; trihydrate alumina; magnesium hydroxide; phenol-formaldehyde, polystyrene, and poly(alphamethyl)-styrene resins, natural fibers, synthetic fibers, and the like.
    [0089] Plasticizers, include, but are not limited to, petroleum oils, such as aromatic and naphthenic oils; polyalkylbenzene oils; diesters of organic acids, such as phthalates, teterphthalates, sebacates, adipates, and dialkyl, dialkoxyalkyl, and alkyl aryl glutarates; glycol diesters such as polyethylene glycol dialkanoates; trialkyl trimellilates; trialkyl, trialkoxyalkyl, alkyl diaryl, and triaryl phosphates; chlorinated paraffin oils; coumarone-indene resins; pine pitches; vegetable oils, such as castor, tallow, safflower, and soybean oils and epoxidized esters and derivatives thereof; and the like.
    [0090] Antioxidants and antiozonants include, but are not limited to, hindered phenols, bisphenols, and thiobisphenols; substituted hydroquinones; tri(alkylphenyl) phosphites; dialkyl thiodipropionates; 2-(4-hydroxy-3,5-t-butylaniline)4,6-bis(octylthio)1,3,5-triazine, hexahydro-1,3,5-tris-β-(3,5-di- t-butyl-4-hydroxyphenyl)propionyl-s-triazine, 2,4,6-tris(n-1,4-dimethylpentylphenylene-diamino)-1,3,5-triazine, tris-(3,5- di-t-butyl-4-hydroxybenzyl), nickel dibutyldithiocarbamate, 2-mercaptotolylimidazole and its zinc salt, petroleum waxes, and the like.
    [0091] Crosslinking agents include, but are not limited to, a number of vulcanizing and polymerizing agents that contain α,α'-bis(t-butylperoxy)-diisopropylbenzene, and are commercially available from Hercules, Inc. under the tradename of VULCUP, a number of such agents containing dicumyl peroxide are commercially available from Hercules, Inc. under the tradename DI-CUP as well as LUPERSOL peroxides made by Atochem North America or TRIGONOX organic peroxides made by Akzo Nobel. LUPERSOL peroxides include LUPERSOL 101 (2,5-dimethyl-2,5-di(t-butylperoxy)hexane, LUPERSOL 130 (2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3) and LUPERSOL 575 (t-amylperoxy-2-ethylhexonate) Other suitable peroxides include 2,5-dimethyl-2,5-di-(t-butyl peroxy)hexane, 2,5-di-t-butyl peroxide, 2,5 -di(t-amyl peroxy)-2,5-dimethylhexane, 2,5-di(t-amyl peroxy)-2,5-diphenylhexane, bis(alpha-methylbenzyl) peroxide, benzoyl peroxide, t-perbenzoate butyl, 3,6,9-triethyl-3,6,9-tri,ethyl-1,4,7-triperoxane and bis(t-butylperoxy)-diisopropylbenzene.
    [0092] In one embodiment, the composition additionally comprises at least one oil. In a further embodiment, the oil will be present in an amount greater than 10 percent by weight, or greater than 15 percent by weight, or greater than 20 percent by weight, based on the weight of the composition.
    [0093] In one embodiment, the oil will be present in an amount of less than 60 weight percent, or less than 50 weight percent, or less than 40 weight percent, based on the weight of the composition. applications
    [0094] The compositions of the present invention may be used to prepare a variety of articles of manufacture, or component parts or portions thereof. The inventive compositions may 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 thermosetting material forming processes. For example, articles may be prepared by extrusion, extrusion followed by additional heat treatment, low pressure molding, compression molding, and the like.
    [0095] The invention provides an article comprising at least one component formed from the inventive composition.
    [0096] Articles include, but are not limited to, sheets, foams, molded products, and extruded parts. Additional items include automotive parts, weather seals, belts, hoses, building profiles, wire and cable sheathing, flooring materials, gaskets, tires and tire components, computer parts, building materials and shoe components. The knowledgeable person can readily add to this list without undue experimentation. Definitions
    [0097] Unless otherwise noted, implied by context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this specification.
    [0098] A continuous polymerization process is a process conducted in a steady state, with continuous feeds and continuous product removal. Such processes include, but are not limited to, one or more well-mixed loop reactor(s) and/or stirred tank reactors and/or plug flow reactors, and where multiple reactors may be operated in sequence and/or in parallel. .
    [0099] A batch process is conducted in a batch manner, such as the reactants and monomers being added all at once, and then being consumed partially or completely during the reaction. Batch reactors are operated in non-stationary states as the reactants are consumed over time.
    [00100] A semi-batch process is operated with both continuous and batch inputs and outputs. One chemical reagent is loaded into the reactor vessel and a second chemical is added slowly (over time). For example, ethylene and propylene are fed continuously to the polymerization, while the solvent and thermonomer are added only at the beginning of the reaction. Half-batch reactors are operated in non-steady states, as some reactants are consumed over time.
    [00101] The term "hydrocarbyl" as used herein refers to a univalent group that is formed by removing a hydrogen atom from a hydrocarbon (chemical group containing only carbon and hydrogen atoms).
    [00102] The term "composition", as used herein, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product will typically be present in trace or residual amounts.
    [00103] The term "polymer" as used herein refers to a polymeric compound prepared by polymerizing monomers, either of the same or different types. The generic term polymer, therefore, encompasses the term homopolymer (used to refer to only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term interpolymer as defined below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and/or within the polymer.
    [00104] The term "interpolymer" as used herein refers to polymers prepared by polymerizing at least two different types of monomers. The term interpolymer includes the term copolymer (used to refer to polymers prepared from two different monomers) and polymers prepared from more than two different types of monomers.
    [00105] The term "ethylene-based polymer" as used herein refers to a polymer that comprises, in polymerized form, a major weight percent of ethylene (based on the weight of the polymer), and optionally may comprise one or more more comonomers.
    [00106] The term "ethylene-based interpolymer" as used herein refers to a polymer that comprises, in polymerized form, a majority weight percent ethylene (based on the weight of the interpolymer), and at least one monomer.
    [00107] The term "non-conjugated ethylene/α-olefin/polyene interpolymer" as used herein 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 major weight percentage of ethylene (based on the weight of the interpolymer).
    [00108] The term "ethylene/α-olefin/diene interpolymer" as used herein 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 major weight percentage of ethylene (based on the weight of the interpolymer).
    [00109] The term "ethylene/α-olefin copolymer", as used herein, refers to a copolymer that comprises, in polymerized form, a major amount of ethylene (based on the weight of the copolymer), and an α- olefin, as the only two types of monomers.
    [00110] The term “comprising”, “including”, “having” and derivatives thereof, are not intended to exclude the presence of any additional component, step or procedure, whether or not disclosed herein. For the avoidance of doubt, all compositions claimed herein by the use of the term "comprising" may include any additional additive, adjuvant, or compound, polymeric or otherwise, unless expressly noted otherwise. By contrast, the term “consisting essentially of” excludes from the scope of any further observation any other component, step or procedure, except those not essential for operability. The term “consisting of” excludes any component, step or procedure not specifically outlined or listed. Test Methods FTIR Method for EPDM Composition Analysis
    [00111] Terpolymers containing ethylene, propylene, and ethylidenenorbornene were analyzed using ASTM D9300 for their ethylene content, and ASTM D6047 for their ethylidenenorbornene and dicyclopentadiene content. C13 NMR Method for EPDM Composition Analysis
    [00112] Samples were prepared by adding approximately “2.6g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene containing 0.025M in chromium acetylacetonate (relaxing agent)” to a “0.2g sample” in a “10 mm” NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 150oC. Data were collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe. Data was acquired using 160 scans per data file, a pulse repetition delay of 6 seconds, with a sample temperature of 120oC. Acquisition was performed using a spectral width of 25,000 Hz and a file size of 32K data points.
    [00113] NMR spectral analyzes of the composition of the examples were performed using the following analysis method. The quantification of monomers present in EPDM can be calculated using the following equations (1 to 9).
    [00114] Calculation of moles of ethylene normalizes the spectral range of 55.0-5.0 ppm to 1000 integral units. The contribution under the normalized integral area corresponds to only 7 of the ENB carbons. ENB diene peaks at 111 and 147 ppm are excluded from the calculation due to concerns that double bonds might react at high temperatures.
    Additional NMR spectral analyzes of some inventive interpolymers show a peak area of 21.3 ppm to 21.8 ppm, greater than 3% of the total integral area of 19.5 ppm to 22.0 ppm. A similar spectral analysis of a comparative example showed less than 3% of the total integral area from 19.5 ppm to 22.0 ppm (see Figure 1). Spectral data are referenced to the EEE backbone at 30 ppm. Peak responses in this region were typically related to differences in the tacticity of propylene incorporated into the polymer. Dynamic Mechanical Spectroscopy (DMS)
    [00115] A low angular oscillatory shear (molten DMS) was performed using a TA Instruments ARES equipped with 25 mm parallel plates under a nitrogen purge. The time between sample loading and starting was set to five minutes for all samples. The experiments were performed at 190oC over a frequency range from 0.1 to 100 rad/s. The strain amplitude was adjusted based on the sample response, from 1 to 3%. The strain response was analyzed in terms of amplitude and phase, from which storage modulus (G'), loss modulus (G") , dynamic viscosity n* and tan delta were calculated. Test specimens for Dynamic Mechanical Spectroscopy were compression molded discs having “25 mm diameter x 3.3 mm thickness”, formed at 180°C and molding pressure of 10 MPa, for five minutes, and then cooled abruptly between cold platelets. (15-20oC) for two minutes. The rheology ratio, the complex viscosity ratio measured at 0.1 rad/s and the complex viscosity measured at 100 rad/s (V0.1/V100 measured at 190oC; also referred to as “RR”) were recorded. A linear molecule (undetectable long-chain branches) typically has an RR of 8 or less. Mooney viscosity
    [00116] The Mooney viscosity of the interpolymer (EPDM unfilled and unoiled) is measured in accordance with ASTM 1646-04, with a preheat time of one minute and a rotor run time of four minutes. The instrument is an Alpha Technologies MDR 2000 Rheometer.
    [00117] For polymerizations in double reactors in series, the Mooney viscosity of the second reactor component is determined by the following equation: log ML = n(A)log ML(A) + n(B)log ML(B); where ML is the Mooney viscosity of the final reactor product, ML(A) is the Mooney viscosity of the polymer from the first reactor, n(A) is the polymer weight fraction of the first reactor, and n(B) is the weight fraction of the polymer from the first reactor. polymer from the second reactor. Each measured Mooney viscosity is measured as discussed above. The polymer weight fraction of the second reactor is determined as follows: n(B) = 1-n(A, where n(A) is determined by the known mass of the first polymer transferred to the second reactor. Gel Permeation Chromatography
    [00118] The gel permeation chromatographic system consisted of either a Polymer Laboratories Model PL210 instrument or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments are operated at 140°C. The columns were three 10 micron Mixed-B columns from Polymer Laboratories. The solvent used was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of "0.1 gram of polymer in 50 milliliters of solvent". The solvent used to prepare the samples contained 200 ppm of butylated hydroxytoluene (BHT). Samples were prepared by gently shaking for 2 hours at 160°C. The injection volume used was 100 microliters and the flow rate was 1.0 mL/minute.
    [00119] Calibration of the GPC column set was performed with 21 polystyrene standards with narrow molecular weight distribution with molecular weights ranging from 580 to 8,400,000, arranged in 6 “cocktail” mixes with at least a decade of separation between individual molecular weights. Standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared with “0.025 grams in 50 milliliters of solvent” for molecular weights equal to or greater than 1,000 kg/mol, and with “0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000 kg/mol . Polystyrene standards were dissolved at 80 degrees Celsius with gentle agitation for 30 minutes. Narrow pattern mixtures were processed first, and in descending order from the highest molecular weight component in order to minimize degradation. The peak molecular weights of the polystyrene standards were converted to the 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 . Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSec Version 3.0 software. Measurement of the Fusion Index
    [00120] The melt index (I2) of an ethylene based polymer is measured according to ASTM D 1238, Condition 190°C/2.16 kg. The melt index (I5) of an ethylene based polymer is measured according to ASTM D 1238, Condition 190°C/5.0 kg. The melt index (I10) of an ethylene based polymer is measured according to ASTM D 1238, Condition 190°C/10 kg. The high loading melt index (I21) of an ethylene-based polymer is measured in accordance with ASTM D 1238, Condition 190°C/21.0 kg. Polymer Density
    [00121] Polymer density is measured in accordance with ASTM D-792. Experimental Ethylene/Propylene/ENB Terpolymerizations in a Semi-Batch Reactor
    [00122] CAT-37 [[2',2”'-[1,3-propanediylbis(oxy-kO))]bis[3-[3,6-bis((1,1-dimethylethyl)-9H-carbazole -9-yl]-5'-fluor-5-(1,1,3,3-tetramethylbutyl)[1,1'-biphenyl]]-olate-kO]](2-)]-dimethyl hafnium (used in inventive polymerization).
    [00123] CAT-01 [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,3a,8a-n)-1,5,6,7-tetrahydro- 2-Methyl-s-indacen-1-yl]silanaminate(2-)-KN]][(1,2,3,4-n)-1,3-pentadiene]-titanium (comparative polymerization).
    [00124] CAT-37 and CAT-01 were used in a semi-batch reactor to produce EPDM polymers under five different reaction conditions. These conditions, shown in Table 1, were chosen in such a way that the concentration of each monomer, in the liquid phase in which polymerization takes place, was kept approximately constant as the temperature was varied from 175oC to 95oC. For each sample, produced with each catalyst, a one-gallon stirred autoclave reactor was initially charged with amounts of 5-ethylidene-2-norbornene, ISOPAR E solvent (mixed alkanes), and propylene (see table 1). The reactor was then heated to the desired temperature, while being charged with hydrogen (20 mmol). Finally, the appropriate amount of ethylene was added to bring the total pressure to the desired value listed in Table 1.
    [00125] The catalyst composition was prepared in a desiccator under an inert atmosphere, in the case of CAT-37, 100 equivalents of triisobutylaluminum-modified alumoxane (MMAO-3A), 1.2 equivalents of catalyst activator (bis(alkyl hydrogenated tallow) )methyl amines), and 1 equivalent of catalyst, with additional solvent, to give a total volume of approximately 10 mL. For CAT-01, 10 equivalents of MMAO-3A were mixed with 3 equivalents of catalyst activator (tris(2,3,4,5,6-pentafluorophenyl)borane), one equivalent of catalyst, and additional solvent, to give a total volume of approximately 10 mL. The activated catalyst mixture was injected into the reactor over 4 minutes by a pump system, or rapidly injected through a catalyst cylinder. Catalyst pressure and temperature were kept constant by feeding ethylene during polymerization and cooling the reactor as needed. After 10 minutes, the ethylene feed was stopped, and the solution transferred to a nitrogen-purged resin vat. An additive solution, containing a phosphorus stabilizer and phenolic antioxidant (IRGAFOS 168 and IRGANOX 1010 at a ratio of “2:1 by weight” in toluene) is added, to give a total additive content of approximately 0.1% by weight. /p in the polymer. The polymer is completely dried in a vacuum oven. The reactor is thoroughly rinsed with hot ISOPAR-E between polymerizations.
    [00126] Table 2 lists the amount of catalyst injected into the reactor for each batch reactor sample, as well as the observed catalyst efficiency. The reaction conditions used at each temperature are given in Table 1. The numerical (Mn) and weight (Mw) average molecular weights of each sample were measured using Gel Permeation Chromatography (GPC), and the weight fraction of each monomer in the final terpolymer was determined using C13 NMR. The glass transition temperature was determined using Differential Scanning Calorimetry. Table 1: Batch Reactor Conditions (EPDM)
    A: estimated values Table 2: Properties of Polymers

    [00127] CAT-37 and CAT-01 were used in a continuous polymerization process to produce EPDM polymers with the same composition of ethylene, propylene, and ENB.
    [00128] In general terms, it is desirable to produce the inventive polymer under conditions as explained in U.S. Patent Nos. 5,977,251 and 6,545,088, and references herein. The polymer products were produced in a solution polymerization process using a continuously mixed loop reactor.
    [00129] Ethylene was introduced into a mixture of a solvent of ISOPAR-E (a mixture of C8-C10 saturated hydrocarbons, commercially available from ExxonMobil), propylene, and 5-ethylidene-2-norbornene (ENB), forming the reactor power. The catalyst is fed to the reactor separately and activated in situ, using co-catalyst 1 (bis(hydrogenated tallow alkyl)methyl amines) and co-catalyst 2 (triisobutylaluminum-modified alumoxane (MMAO-3A)). The reactor output was consequently a mixture of polymer, solvent, and reduced levels of the initial monomer streams. The molecular weight of the polymer may be 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, ie, constant reactant concentration and continuous feeding 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.
    [00130] After polymerization, a small amount of water was introduced into the reactor as catalyst poison, and the reactor outlet stream was introduced into a flashing vessel, in which the solids concentration was increased to at least 100 percent . A portion of the unreacted monomers, ie, ENB, ethylene, and propylene, and unused diluent were then collected, and recycled back to the reactor feeds as appropriate. Typically, prior to devolatilization, an additive solution containing phosphorus stabilizer and phenolic antioxidant (IRGAFOS 168 and IRGANOX 1010 at a "2:1 weight ratio") is added, to give a total additive content of approximately 0. 1% w/w in polymer.
    [00131] Tables 3a and 3b show the polymerization conditions used in the terpolymerization of ethylene/propylene and ENB using CAT-37 and CAT-01 at 162oC and 94oC, respectively. Table 4 shows the resulting properties of the polymers.
    [00132] Comparing the data from these two polymerizations, the inventive example shows similar catalyst efficiency to that of the comparative example (1.3 MM lb of polymer/lb of metal), despite having been polymerized at a significantly higher temperature (162oC vs. 94oC).
    [00133] Inventive example 2, polymerized at 162oC, had an average molecular weight of 160,881 g/mol, and incorporated 70.6 weight percent ethylene, 21.8 weight percent propylene, and 7.6 weight percent in weight of ENB. Example 2, polymerized at 94°C, had an average molecular weight of 221,870 g/mol, and incorporated 70.3 weight percent ethylene, 25.0 weight percent propylene, and 4.7 weight percent ENB. . Surprisingly, the rheology ratio of Example 2 is 48.5 while the rheology ratio of Example B* is 30.3.
    [00134] Another novel feature is that the Mooney viscosity of inventive example 2 is high enough at 80(ML1+4, 125oC), indicating that it is high in viscosity as a result of its molecular weight and long chain branching. The Mooney viscosity of comparative example B is 134 (ML1+4, 125oC), indicating it to be of high viscosity, however, from the rheology ratio of 30, it can be inferred that the level of long chain branching is significantly lower than that of the inventive example. Despite the difference in molecular weight between these two polymers (but both polymers having a polydispersity (Mw/Mn) of 2.3), it was found that the inventive polymer, with a lower molecular weight, has a rheology ratio ( V0.1/V100 at 190oC) significantly higher. To increase the molecular weight of the polymer, the rheology is expected to increase slightly, but not as dramatically shown, when comparing the molecular weight and rheology ratio of the inventive and comparative examples.
    [00135] The rheology ratio (V0.1/V100 at 190oC) of the inventive example also demonstrates that the polymer is highly branched, to influence the shear viscosity at both low and high rates. High viscosity at low shear rate is important for polymer melt strength and compound green strength, and low viscosity at high shear rate is critical for mixing and dispersing the components used to formulate EPDM compounds. . Hence, high “EPDM rheology ratio” can result in better processability and higher melt strength, which are especially needed in applications such as sponge blowing and extruded profiles. Other benefits include faster mixing and dispersing of the polymer along with other ingredients such as carbon black, healing oils and other additives. Faster and easier mixing results in less torque and power consumption by the mixer and equipment. The EPDM polymer that readily disperses in the compounds may also result in better looking articles with improved surface quality (which is important for a weather-sealing profile).
    [00136] Examples EPDM01-R1, EPDM01, EPDM02, and EPDM03 also demonstrate the inventive features that were produced using CAT-37, in a continuous polymerization operation, in either a single or double reactor process. EPDM01 was produced using two consecutive loop reactors (first reactor:loop; second reactor (final):loop). EPDM02 and EPDM03 were each prepared using a loop reactor followed by a continuous stirred tank reactor (first reactor:loop; second reactor (final):loop; CSTR). Examples designated with “-R1” are from materials sampled from the first reactor. For example, polymers EPDM01-R1 and EPDM01 were produced at high temperatures of 147oC and 175oC, respectively. Compared to example 2, these polymers have lower Mooney viscosity, 40.5 Mooney units and 21.5 Mooney units, respectively. Despite the lower Mooney viscosity, the rheology ratio (V0.1/V100) of these polymers is unprecedentedly high, with values of 65.5 and 37.7. EPDM01 is the polymer composition leaving the second reactor, and includes the polymer composition produced in both the first and second reactors. It may be understood that this polymer composition contains high levels of long chain branching.
    [00137] EPDM02-R1, EPDM02, and EPDM03-R1 illustrate examples produced at lower temperatures, 90oC for the first reactor, and between 130-140oC for the second reactor. The final Mooney viscosity of the EPDM02 and EPDM03 examples were 76.0 Mooney units and 73.9 Mooney units, respectively. The rheology ratios (V0.1/V100) of these dual reactor polymers, EPDM01 and EPDM03 are also high, with values of 29.4 and 26.2. Table 3a: Polymerization Conditions (EPDM, Continuous Polymerization)
    Table 3b: Polymerization Conditions (continued)
    Table 4: Polymer Properties (EPDM, Continuous Polymerization)
    * Measured by FTIR ** Measured by C13 NMR
    [00138] As discussed above, Figure 1 shows that inventive interpolymers, similar to example 2, exhibit a higher percentage area in the region of 19.5 ppm to 22.0 ppm (7% for two peaks at 21.4 ppm and 21.6 ppm), compared to example B* (2% percent area in the region of 19.5 ppm to 22.0 ppm). For other polymers such as propylene based homopolymers and copolymers, these two distinct peaks present at 21.6 and 21.4 ppm are typically related to differences in the tacticity of the propylene sequences that were incorporated into the polymer. Table 4 shows the % peak area by NMR of 21.3 to 21.8 ppm for the examples and as shown, the inventive examples all exhibit % Peak Areas by NMR greater than 3.5%, and greater than in the example comparative B (2.0% w/w). For the examples containing 70% w/w C2 in the polymer, the Peak Area % by NMR is 5.0 to 8.0 percent, while in the examples containing 50% w/w C2 in the polymer, the Area Peak per NMR is around 18 percent.
    [00139] The inventive examples were found to have a very high rheology ratio when compared to that of those interpolymers produced in the batch process, discussed above, at high temperatures (greater than 150oC). It has been found that CAT-37, when used in a continuous process, results in a polymer with significantly high rheology ratios (indicative of long-chain branching), while maintaining high catalyst activity during polymerization.
    权利要求:
    Claims (10)
    [0001]
    1. Solution polymerization process to form an ethylene/α-olefin/non-conjugated polyene interpolymer, said process being characterized in that it comprises polymerizing ethylene, an α-olefin, and a non-conjugated polyene in at least one reactor in the presence of a metal-ligand complex selected from formula I:
    [0002]
    2. Process according to claim 1, characterized in that each Z is O.
    [0003]
    3. Process according to claim 2, characterized in that the metal-ligand complex of formula (I) is the metal-ligand complex of formula (Ia):
    [0004]
    4. Process according to claim 3, characterized in that the metal-ligand complex of formula (I) is a metal-ligand complex of formula (Ia-1):
    [0005]
    5. Process according to claim 1, characterized in that each of R5c, R5f, R5cc and R5ff, independently, is a hydrocarbyl (C1-C40).
    [0006]
    6. Process according to claim 1, characterized in that each of R7c and R7d, independently, is a hydrocarbyl (C4-C10).
    [0007]
    7. Process according to claim 1, characterized in that each of R3a and R3b, independently, is a (C1-C6) alkyl, a (C1-C6) alkyl-O-one ((C1-C6) alkyl ))2=-N-, a (C3-C6) cycloalkyl, a fluorine atom, or a chlorine atom.
    [0008]
    8. Process according to claim 1, characterized in that L is hydrocarbylene (C1-C40) that has a moiety that comprises a main chain linker of 1 carbon atom to 6 carbon atoms linking the Z atoms in the formula (I).
    [0009]
    9. Process according to claim 1, characterized in that the polymer concentration in the reactor is greater than 5% w/w, based on the weight of the total feed to the reactor.
    [0010]
    10. Process according to claim 1, characterized in that the temperature of the first reactor is from 90oC to 160oC, and the temperature of the second reactor is from 150oC to 200oC.
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    同族专利:
    公开号 | 公开日
    KR20140107263A|2014-09-04|
    KR101989206B1|2019-09-24|
    ES2835807T3|2021-06-23|
    US9422383B2|2016-08-23|
    CN104169313B|2016-09-21|
    BR112014014855A2|2017-06-13|
    US20150322185A1|2015-11-12|
    JP2015500920A|2015-01-08|
    JP6189325B2|2017-08-30|
    WO2013096573A1|2013-06-27|
    EP2794693A1|2014-10-29|
    CN104169313A|2014-11-26|
    IN2014CN04444A|2015-09-04|
    EP2794693B1|2020-09-23|
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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]|
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-01| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-07-20| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-11| 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 20/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161577720P| true| 2011-12-20|2011-12-20|
    US61/577,720|2011-12-20|
    US201261731891P| true| 2012-11-30|2012-11-30|
    US61/731,891|2012-11-30|
    PCT/US2012/070859|WO2013096573A1|2011-12-20|2012-12-20|Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same|
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