Method for producing a polymer composition having excellent processability

Abstract

A process for preparing an alpha composition comprising a first ethylene / alpha-olefin / interpolymer fraction and a second ethylene / alpha-olefin / interpolymer fraction, the process comprising polymerizing in a single reactor a reaction mixture comprising ethylene and an alpha-olefin, a biphenylphenol metal complex selected from Structure 1 described herein, and a biphenylphenol metal complex selected from Structure 2 described herein, and the alpha composition prepared therefrom.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of priority of U.S. Patent Application No. 62 / 953,707, filed on December 26, 2019, the entire disclosure of which is incorporated herein by reference.

Background Art

[0002] Improved elastomer processability is one of the major needs of end - use manufacturers for various elastomer products such as automotive parts, photovoltaic parts, wires, and cable components. New elastomer resins with improved processability are needed, as indicated by excellent shear - thinning behavior. Such resins need to be polymerized in a cost - effective, high - efficiency process.

[0003] U.S. Patent Publication No. 2011 / 0290317 discloses the preparation and electronic uses of bimodal and multimodal ethylene - based polymers. These polymers are prepared in two reactors, adding complexity and capital costs to the overall polymerization process. International Publication No. 2018 / 022588 discloses the polymerization of multimodal elastomers synthesized mainly in the presence of biphenylphenol catalysts and constrained geometry catalysts (CGCs). One comparative example (Comparative Example C) uses two biphenylphenol catalysts and has 1.4×10 per gram of total catalyst metal 6has a low overall total catalyst efficiency of the polymer of g. Additional in-situ bimodal ethylene-based polymers and post-reactor blends are described in the following references: WO 2001 / 014434 (Constrained geometry catalyst systems), WO 2002 / 074817 (Polymerization using constrained geometry catalyst systems), US 2016 / 0115264 (Metallocene catalyst polymers), US 5,849,823 (Blends of linear or substantially linear homogeneously branched ethylene / alpha-olefin interpolymers), US 6,451,894 (Blends containing crystalline or semi-crystalline polyolefins, or copolymers of ethylene and C3-C10 olefins, and blends containing multimodal elastomers of sequentially polymerized ethylene-alpha-olefin monomers, see also US 6,610,408). However, the cited art does not promote elastomeric resins having excellent shear thinning behavior that can be polymerized in a cost-effective high efficiency process. These needs are met by the following invention. SUMMARY OF THE INVENTION

[0004] A process for preparing an alpha composition comprising a first ethylene / alpha-olefin / interpolymer fraction and a second ethylene / alpha-olefin / interpolymer fraction, the process comprising polymerizing a reaction mixture comprising ethylene, an alpha-olefin, a metal complex selected from the following a), and a metal complex selected from the following b) in one reactor, a) a biphenylphenol metal complex selected from the following Structure 1:

CHEMICAL

Chemical formula

Chemical formula

Chemical formula

[0005] A composition comprising an alpha composition comprising a first ethylene / alpha-olefin / interpolymer fraction and a second ethylene / alpha-olefin / interpolymer fraction, wherein the first composition has the following properties, i) Mz / Mn ≧ 8.0, ii) a density of 0.855 to 0.890 g / cc, iii) V100(190 °C) ≦ 600 Pa·s, and iv) V0.1(190 °C) ≧ 4,000 Pa·s.

Brief Description of the Drawings

[0006] [Figure 1] Shows the SAOS profiles (190 °C) of the alpha compositions (POE A, POE B, POE C, POE F) of the present invention and two commercially available resins (ENGAGE8457 polyolefin elastomer and ATEVA2810A). Profiles from top to bottom at "0.1 rad / s": POE F, POE C, POE B, POE A, ENGAGE8457, and ATEVA2810A.

Modes for Carrying Out the Invention

[0007] Multimodal ethylene / alpha-olefin interpolymers have been discovered to have excellent processability. These compositions exhibit low viscosity at high shear for improved processability, high viscosity at low shear, for example, low injection pressure under low shear heating during high shear rate injection molding or high shear rate mixing, and high sag resistance at the low shear rate of extruded parts. It has also been discovered that such interpolymers can be produced at high temperature (≧150°C) and with high efficiency using a multi-catalyst system (e.g., a dual catalyst system) in a single reactor. For example, under the same reactor conditions, the first catalyst produces a high molecular weight (HMW) interpolymer fraction and the second catalyst produces a low molecular weight (LMW) interpolymer fraction.

[0008] As described above, a process is provided for preparing an alpha composition comprising a first ethylene / alpha-olefin / interpolymer fraction and a second ethylene / alpha-olefin / interpolymer fraction, the process comprising polymerizing a reaction mixture comprising ethylene, an alpha-olefin, a metal complex selected from a) below, and a metal complex selected from b) below in one reactor, a) a biphenylphenol metal complex selected from Structure 1 (see Summary of the Invention (SOI) as above), and, b) a biphenylphenol metal complex selected from Structure 2 (see SOI) as above.

[0009] The process of the present invention may include combinations of two or more of the embodiments described herein. Each biphenylphenol metal complex may include combinations of two or more of the embodiments described herein. As used herein, R1 = R 1 、R2 = R 2 、R3 = R 3 and so on. Also, the notation R a(1) ~R a(n) means that in the formula, "a(1)~a(n)" represents consecutive numbers, and R a(1) 、R a(2), R a(3) ,..., R a(n) refers to. For example, R 31 ~R 35 refers to R 31 , R 32 , R 33 , R 34 , R 35 refers to, and R 51 ~R 59 refers to R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 refers to. In each of formulas (I) to (III), the wavy line represents the connection (bond) between each formula (R 1 or R 8 group) and the remaining biphenylphenol metal complex.

[0010] The term "independently selected" means that the R groups such as R 1 , R 2 , R 3 , R 4 , and R 5 may be the same or different (for example, R 1 , R 2 , R 3 , R 4 , and R 5 are all substituted alkyl, or R 1 and R 2 are substituted alkyl and R 3 may be aryl, etc.). It is used in this specification to indicate this. The use of the singular form includes the use of the plural form, and vice versa (for example, a hexane solvent includes a plurality of hexanes). The named R groups will generally have a structure recognized to correspond to the R groups having that name in the art. These definitions are intended to supplement and exemplify, rather than exclude, definitions known to those skilled in the art. When used to describe a chemical group containing a specific carbon atom, "(C x ~C y) The bracketed expression having the form of "(Cx~Cy)" means that the chemical group has x to y carbon atoms including x and y. For example, (C1~C 40 ) alkyl is an alkyl group having 1 to 40 carbon atoms.

[0011] The term "substituent" refers to the substitution of a hydrogen atom (-H) bonded to a carbon atom or a heteroatom of the corresponding unsubstituted compound by a substituent (R S ). The notation "R S " refers to a heteroatom or a chemical group containing at least one heteroatom. The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or a heteroatom of the corresponding unsubstituted compound is replaced by a substituent (R S ).

[0012] The term "-H" means a hydrogen or a hydrogen radical covalently bonded to another atom. "Hydrogen", "H", and "-H" are interchangeable and, unless otherwise specified, mean the same thing.

[0013] The term "(C1~C 40 ) hydrocarbyl" means a hydrocarbon radical having 1 to 40 carbon atoms, and the term "(C1~C 40 ) hydrocarbylene" means a hydrocarbon diradical having 1 to 40 carbon atoms. Each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic containing bicyclic and having 3 or more carbon atoms) or acyclic, and is unsubstituted or substituted by one or more RS.

[0014] In the present disclosure, (C1~C 40 ) hydrocarbyl is unsubstituted or substituted (C1~C 40 ) alkyl, (C3~C 40 ) cycloalkyl, (C3~C 20 ) cycloalkyl-(C1~C 20 ) alkylene, (C6~C 40 ) aryl, or (C6~C20 )aryl-(C1-C 20 ) alkylene. In some embodiments, each of the above (C1-C 40 ) hydrocarbyl groups has a maximum of 20 carbon atoms (i.e., (C1-C 20 ) hydrocarbyl), and in other embodiments, has a maximum of 12 carbon atoms.

[0015] "C1-C 40 alkyl", and the term (C1-C 30 ) alkyl each mean a saturated straight-chain or branched-chain hydrocarbon radical of 1 to 40 carbon atoms or 1 to 30 carbon atoms, unsubstituted or substituted by one or more R S . Examples of unsubstituted (C1-C 40 ) alkyl are unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Examples of substituted (C1-C 40 ) alkyl are substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, and trifluoromethyl.

[0016] The term "(C6-C 40 ) aryl" means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical of 6 to 40 carbon atoms, at least 6 to 14 of which are aromatic ring carbon atoms, unsubstituted or substituted (by one or more R S ). The monocyclic, bicyclic, or tricyclic radical contains 1, 2, or 3 rings, respectively, where the monocyclic ring is aromatic, and the 2 or 3 rings are independently fused or unfused, and at least 1 of the 2 or 3 is aromatic. Examples of substituted (C6-C 40 ) alkyl are unsubstituted (C6-C 20 ) alkyl unsubstituted (C6-C 18)Alkyl, 2-(C1-C5)alkylphenyl, 2,4-bis(C1-C5)alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indenyl, hexahydroindenyl, indanyl, dihydroindanyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Substituted (C6-C 40 )Examples of alkyl are substituted (C1-C 20 )alkyl, substituted (C6-C 18 )aryl, polyfluorophenyl, and pentafluorophenyl.

[0017] The term “(C3-C 40 )cycloalkyl” means a saturated cyclic hydrocarbon radical having 3 to 40 carbon atoms that is unsubstituted or substituted with one or more R S . Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) are defined in a similar manner as having x to y carbon atoms and being either unsubstituted or substituted with one or more R S . Examples of unsubstituted (C3-C 40 )cycloalkyl are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C 40 )cycloalkyl are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, and 1-fluorocyclohexyl.

[0018] (C1-C 40 )Examples of hydrocarbylene include unsubstituted or substituted (C6-C 40 )arylene, (C3-C 40 )cycloalkylene, and (C1-C 40 )alkylene (e.g., (C1-C 20Examples of (alkylene) include. In some embodiments, the diradical is on the same carbon atom (e.g., -CH2-), or on adjacent carbon atoms (i.e., 1,2-diradical), or separated by one, two, or more intervening carbon atoms (e.g., 1,3-diradical, 1,4-diradical, etc., respectively). Some diradicals include α,ω-diradicals. An α,ω-diradical is a diradical having the largest carbon skeleton spacing between the radical carbons. (C2-C 20 ) Some examples of (C2-C) alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C 40 ) Some examples of (C6-C) arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0019] The term "(C1-C 40 ) alkylene" means an unsubstituted or one or more R S -substituted saturated straight-chain or branched-chain diradical of 1 to 40 carbon atoms (i.e., the radical is not on a ring atom). Examples of unsubstituted (C1-C 40 ) alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * (H)(CH3), and unsubstituted (C1-C * ) alkylene including -(CH2)4C 20 (H)(CH3), where "C * " represents a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C 40 ) alkylene are substituted (C1-C 20 ) alkylene and -CF2-, -C(O)-. "(C3-C 40The term "cycloalkylene" means a cyclic diradical of 3 to 40 carbon atoms, which is unsubstituted or substituted by one or more Rs S (i.e., the radicals are on the ring atoms).

[0020] The term "heteroatom" refers to an atom other than hydrogen or carbon. The term "heteroatom group" refers to a heteroatom or a chemical group containing one or more heteroatoms. Examples of heteroatom groups include, but are not limited to, O, S, S(O), S(O)2, Si(R C )3, P(R P )2, N(R N )2, -N=C(R C )2, -Ge(R C )2-, or -Si(R C )2-, wherein each R C and each R P is independently an unsubstituted (C1-C 30 ) hydrocarbyl or -H, and wherein each R N is an unsubstituted (C1-C 30 ) hydrocarbyl.

[0021] The term "heterohydrocarbon" refers to a molecule or molecular backbone in which one or more carbon atoms are substituted by heteroatoms. The term "(C1-C 40 ) heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 40 carbon atoms, and the term "(C1-C 40 ) heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 40 carbon atoms, with each heterohydrocarbon having one or more heteroatoms. The radicals of heterohydrocarbyl are present on carbon atoms or heteroatoms, and the diradicals of heterohydrocarbylene can be present on (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and one heteroatom. Each (C1-C 40 ) heterohydrocarbyl and (C1-C 40 ) heterohydrocarbylene is unsubstituted or (one or more Rs SIt may be substituted, aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0022] (C1-C 40 ) The heterohydrocarbyl may be unsubstituted or substituted. (C1-C 40 ) Non-limiting examples of the heterohydrocarbyl include (C1-C 40 ) heteroalkyl, (C1-C 40 ) hydrocarbyl-O-, (C1-C 40 ) hydrocarbyl-S-, (C1-C 40 ) hydrocarbyl-S(O)-, (C1-C 40 ) hydrocarbyl-S(O)2-, (C1-C 40 ) hydrocarbyl-Si(R C )2-, (C l -C 40 ) hydrocarbyl-N(R N )-, (C l -C 40 ) hydrocarbyl-P(R P )-, (C2-C 40 ) heterocycloalkyl, (C2-C 19 ) heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 ) cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 ) heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 )) heteroaryl, (C1-C 19 )) heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 ) aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 ) heteroaryl-(C1-C 20 ) heteroalkylene.

[0023] "(C1-C 40) The term "heteroaryl" means an unsubstituted or substituted (by one or more R S ) monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having a total of 1 to 40 carbon atoms and one or more heteroatoms, wherein the monocyclic, bicyclic, or tricyclic radical contains 1, 2, or 3 rings, respectively, and the 2 or 3 rings are independently fused or unfused, and at least one of the 2 or 3 rings is heteroaromatic. Other heteroaryl groups (e.g., (C x ~C y ) heteroaryl, generally (C1~C 12 ) heteroaryl) have x to y carbon atoms (such as 1 to 12 carbon atoms), and are unsubstituted or substituted by one or two or more R SIt is defined in a manner similar to that replaced by. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals are pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, h is the number of heteroatoms and can be 1 or 2, and the heteroatom can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals are pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0024] The aforementioned heteroalkyl is (C1-C 40It may be a saturated straight-chain or branched radical containing a carbon atom of or less carbon atoms and one or more heteroatoms. Similarly, heteroalkylene may be a saturated straight-chain or branched diradical containing 1 to 50 carbon atoms and one or two or more heteroatoms. Examples of heteroatom groups include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, SR C , S(O), and S(O)2. The heteroalkyl group and the heteroalkylene group are unsubstituted or substituted by one or more R S .

[0025] Examples of unsubstituted (C2-C 40 ) hetero-cycloalkyl include unsubstituted (C2-C 20 )-hetero-cycloalkyl, unsubstituted (C2-C 10 ) hetero-cycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thia-cyclononyl, and 2-aza-cyclodecyl.

[0026] The term "halogen atom" or "halogen" means a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" means an anionic form of a halogen atom such as fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - ).

[0027] The term "pre-catalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with the pre-catalyst to convert the pre-catalyst into a catalytically active catalyst. As used herein, the terms "co-catalyst" and "activator" are interchangeable terms.

[0028] In some embodiments, the catalyst systems comprising the metal-ligand complexes of Structures 1 and 2 can each be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the metal-ligand complexes of Structures 1 and 2 may each become catalytically active by contacting the complex with an activating co-catalyst or by combining the complex with an activating cocatalyst. Suitable activating co-catalysts for use herein include alkylaluminum, polymers, or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A preferred activating technique is bulk electrolysis. Combinations of one or more of the foregoing activating co-catalysts and techniques are also contemplated. The term "alkylaluminum" means monoalkylaluminum dihydride or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide, or trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, methylalumoxane modified with triisobutylaluminum, and isobutylalumoxane.

[0029] The Lewis acid activator (co-catalyst) comprises a Group 13 metal compound containing 1 to 3 (C1-C 20 ) hydrocarbyl substituents, as described herein. In one embodiment, the Group 13 metal compound is tri((C1-C 20 ) hydrocarbyl) substituted aluminum or tri((C1-C 20)-Hydrocarbyl)-boron compound. In other embodiments, the Group 13 metal compound is tri(hydrocarbyl)substituted aluminum, tri(hydrocarbyl)-boron compound, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 )aryl)boron compound, and its halogenated (including perhalogenated) derivatives. In a further embodiment, the Group 13 metal compound is tris(fluorosubstituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tetrakis((C1-C 20 )hydrocarbyl)borate (e.g., trityltetrafluoroborate) or tri((C1-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borate (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" means a nitrogen cation of ((C1-C 20 )hydrocarbyl)4N + a((C1-C 20 )hydrocarbyl)3N(H) + , a((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C 20 )hydrocarbylN(H)3 + , or N(H)4 + , and each (C1-C 20 )hydrocarbyl, when more than two are present, may be the same or different.

[0030] Combinations of non-polymeric, non-coordinating, ion-forming compounds with polymers or oligomeric aluminoxanes include combinations of polymers or oligomeric aluminoxanes (also known as aluminoxanes) with halogenated tetrakisborate compounds, particularly bis(hydrogenated tallow alkyl)methyltetrakis(penta-fluorophenyl)borate (1 -) A mixture containing an amine is included. The molar ratio of (metal-ligand complex):(bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate(1 - ) amine):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tetrakis(pentafluorophenyl)borate):(alumoxane)] can be 1:1:1 to 1:10:500, and in other embodiments, 1:1:1.5 to 1:5:100. Other embodiments are combinations of neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes.

[0031] An active catalyst composition can be formed by activating a catalyst system containing the metal-ligand complexes of Structure 1 and Structure 2 and combining one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible non-coordinating ion-forming compounds. Exemplary suitable cocatalysts include modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate(1 - ) amine, and combinations thereof, but are not limited thereto.

[0032] In some embodiments, one or more of the foregoing activating cocatalysts are used in combination with each other. A particularly preferred combination is a mixture of ammonium borate and an oligomeric or polymeric aluminoxane compound. In some embodiments, the ratio of the total molar amount of one or more metal-ligand complexes of Structure 1 and Structure 2 to the total molar amount of one or more activating cocatalysts is at least 1:500, or 1:300, or 1:100, or 1:50, or 1:10, or 1:5. When an aluminoxane alone is used as the activating cocatalyst, the molar amount of the aluminoxane used is preferably at least 10 times the combined molar amount of the metal-ligand complexes of Structure 1 and Structure 2.

[0033] It should be understood that the catalyst systems of the present disclosure may be implemented in different forms and should not be construed as limited to the specific embodiments described in the present disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the subject matter to those skilled in the art. Here, specific embodiments of the catalyst system are described.

[0034] In one embodiment, or a combination of two or more embodiments, each as described herein, for Structure 2, Y is -(CH2) n -, where n = 0 to 2, further n = 1 or 2, further n = 1, -CR a R b -, where R a and R b are each independently (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, or -H, and is either -Ge(R D )2- or -Si(R D )2, where each R D is independently selected from the group consisting of -H, (C1-C 40 ) hydrocarbyl, and (C1-C 40 ) heterohydrocarbyl.

[0035] In one embodiment, or a combination of two or more embodiments, each as described herein, for Structure 1, -Z1 - and -Z 2 - each is -O-.

[0036] In each of one embodiment, or a combination of two or more embodiments, each described herein, for Structure 2, -Z 1 - and -Z 2 - each is -O-.

[0037] In each of one embodiment, or a combination of two or more embodiments, each described herein, for Structure 1, R 1 and R 8 are the same and are selected from the group consisting of a radical having formula (I), a radical having formula (II), and a radical having formula (III).

[0038] In each of one embodiment, or a combination of two or more embodiments, each described herein, for Structure 2, R 1 and R 8 are the same and are selected from the group consisting of a radical having formula (I), a radical having formula (II), and a radical having formula (III).

[0039] In each of one embodiment, or a combination of two or more embodiments, each described herein, for Structure 1, R 1 or R 8 at least one of which is selected from a radical having formula (II) or a radical having formula (I).

[0040] In each of one embodiment, or a combination of two or more embodiments, each described herein, for Structure 2, R 1 or R 8 at least one of which is selected from a radical having formula (II).

[0041] In each of one embodiment, or a combination of two or more embodiments, each described herein, for Structure 1, i) -CH2Si(R a )(R b)CH2- or -CH2Ge(R a )(R b )CH2-, wherein R a and R b are each, independently, (C1 - C 30 ) hydrocarbyl or (C1 - C 30 ) heterohydrocarbyl, ii) 1,3 - dimethylpropane - 1,3 - diyl, iii) bis(methylene)cyclohexane - 1,2 - diyl, iv) propane - 1,4 - diyl, or butane - 1,4 - diyl is selected from.

[0042] In each being one embodiment, or a combination of two or more embodiments described herein, for Structure 2, Y is, i) -SiR c R d -, or -GeR c R d (-, wherein R c and R d are each independently, (C1 - C 30 ) hydrocarbyl or (C1 - C 30 ) heterohydrocarbyl, ii) -(CH2) n -, wherein n = 0 - 2, further n = 1 or 2, further n = 1, or iii) -CR a R b (-, wherein R a and R b are each, independently, (C1 - C 30 ) hydrocarbyl, (C1 - C 30 ) heterohydrocarbyl, or -H, is selected from.

[0043] In each being one embodiment, or a combination of two or more embodiments described herein, for Structure 1, R2 = R4 = R5 = R7 = R9 = R11 = R12 = R13 = R14 = R16 = H.

[0044] In each embodiment described herein, or in a combination of two or more embodiments, for Structure 2, R2 = R4 = R5 = R7 = R9 = R11 = R12 = R13 = R14 = R16 = H.

[0045] In each embodiment described herein, or in a combination of two or more embodiments, Structure 1 is one of the following Structures 1a to 1c:

Chemical formula

[0046] In each embodiment described herein, or in a combination of two or more embodiments, Structure 2 is one of the following Structures 2a or 2b:

Chemical formula

[0047] In each embodiment described herein, or in a combination of two or more embodiments, the process is carried out at a reactor temperature of 150 °C or higher, or 155 °C or higher, or 160 °C or higher, or 165 °C or higher, with an overall catalyst efficiency [(grams of alpha composition) per (gram of total catalyst metal)] of 2.8×10 6 or higher, 3.0×10 6 or higher, or 3.2×10 6 or higher, or 3.4×10 6 or higher, or 3.6×10 6 or higher.

[0048] In each embodiment described herein, or in a combination of two or more embodiments, the process is carried out at an alpha composition density of 0.855 - 0.890 g / cc, or 0.860 - 0.890 g / cc, or 0.865 - 0.890 g / cc, or 0.865 - 0.885 g / cc (1 cc = 1 cm 3 ), with an overall catalyst efficiency [(grams of alpha composition) per (gram of total catalyst metal)] of 2.8×10 6 or higher, 3.0×10 6 or higher, or 3.2×10 6 or higher, or 3.4×10 6as described above, or 3.6×10 6 has an overall catalyst efficiency [(gram alpha composition) per (gram total catalyst metal)] of 3.6×10

[0049] In each embodiment, or a combination of two or more embodiments, as described herein, the mass flow rate ratio of (ethylene reactor feed) to (hydrogen reactor feed) is 6.00×10 -4 g / g or less, or 5.50×10 -4 g / g or less, or 5.00×10 -4 g / g or less, or 4.50×10 -4 g / g or less.

[0050] In each embodiment, or a combination of two or more embodiments, as described herein, the process is carried out at a reactor temperature of 150 °C or higher, or 155 °C or higher, or 160 °C or higher, or 165 °C or higher.

[0051] Also provided is a composition comprising an alpha composition comprising a first ethylene / alpha-olefin interpolymer fraction and a second ethylene / alpha-olefin interpolymer fraction, the alpha composition having the following properties: i) Mz / Mn ≧ 8.0, ii) a density of 0.855 to 0.890 g / cc, iii) V100(190 °C) ≦ 600 Pa·s, and iv) V0.1(190 °C) ≧ 4,000 Pa·s.

[0052] The present invention also provides a crosslinked composition formed from each embodiment, or a combination of two or more embodiments, as described herein. The present invention also provides an article comprising at least one component formed from the composition of any one embodiment, or a combination of two or more embodiments, as described herein.

[0053] The composition of the present invention may include a combination of two or more embodiments described herein. The alpha composition may include a combination of two or more embodiments described herein.

[0054] The alpha composition includes at least two ethylene / alpha-olefin interpolymer fractions having different one or more polymer properties. Each ethylene / alpha-olefin interpolymer fraction independently includes, in polymerized form, ethylene and an alpha-olefin, and may optionally include a polyene, more preferably a non-conjugated polyene. The alpha-olefin may be either an aliphatic or aromatic compound. The alpha-olefin is preferably C3-C 20 an aliphatic compound, preferably C3-C 16 an aliphatic compound, and more preferably C3-C 10 an aliphatic compound. Preferred C3-C 10Examples of the aliphatic alpha-olefin include propylene, 1-butene, 1-hexene, 1-octene, and 1-decene, and more preferably 1-octene. Preferable examples of the non-conjugated polyene include linear acyclic dienes such as 1,4-hexadiene and branched acyclic dienes such as 1,5-heptadiene, 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 dihydromyrcene, monocyclic alicyclic dienes such as 1,4-cyclo-hexadiene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene, polycyclic alicyclic condensed and bridged ring dienes such as tetrahydroindene and methyltetrahydroindene, and alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, and 5-cyclohexylidene-2-norbornene. The polyene is preferably a non-conjugated diene selected from ENB, VNB, and dicyclopentadiene, and preferably ENB.

[0055] In each embodiment, or combination of two or more embodiments, described herein, the composition of the present invention independently further comprises a thermoplastic polymer that is different from each of the first and second interpolymer fractions in one or more characteristics such as monomer type(s) and / or amount, Mn, Mw, Mz, MWD, V0.1, V100, RR (=V0.1 / V100), or any combination thereof. Polymers include, but are not limited to, ethylene-based polymers, propylene-based polymers, and olefin multiblock 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), homogeneously branched linear ethylene-based polymers, and homogeneously branched substantially linear ethylene-based polymers (i.e., homogeneously branched long chain branched ethylene polymers). Examples of propylene-based polymers include polypropylene homopolymers and propylene / ethylene copolymers.

[0056] Definitions Unless otherwise indicated, all parts and percentages are by weight and all test methods are current as of the filing date of the present disclosure, implicitly from the context or not customary in the art.

[0057] As used herein, the term "composition" includes a mixture of materials, including the composition and reaction products and decomposition products formed from the materials of the composition. Any reaction products or decomposition products are typically present in trace or residual amounts.

[0058] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the general term "polymer" includes the term "homopolymer" (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace impurities may be incorporated into the polymer structure), and the term "interpolymer" as defined hereinbelow. Trace impurities such as catalyst residues can be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very small amounts (in the "ppm" range) of one or more stabilizers.

[0059] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different monomers. Thus, the term "interpolymer" includes the term "copolymer" (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0060] As used herein, the term "propylene-based polymer" refers to a polymer that, in polymerized form, contains a majority weight percent of propylene (based on the weight of the polymer) and optionally may contain one or more comonomers.

[0061] As used herein, the term "ethylene-based polymer" refers to a polymer that, in polymerized form, contains 50 weight percent or a majority weight percent of ethylene (based on the weight of the polymer) and optionally may contain one or more comonomers.

[0062] As used herein, the term "ethylene / alpha-olefin / interpolymer" refers to a random interpolymer that, in polymerized form, contains ethylene and an alpha-olefin. In one embodiment, the "ethylene / alpha-olefin interpolymer" contains 50 weight percent or a majority weight percent of ethylene (based on the weight of the interpolymer) in polymerized form.

[0063] As used herein, the term "ethylene / alpha-olefin / non-conjugated polyene interpolymer" refers to a random interpolymer in polymerized form that includes ethylene, an alpha-olefin, and a non-conjugated polyene (e.g., a non-conjugated diene). In one embodiment, the "ethylene / alpha-olefin / non-conjugated polyene interpolymer" in polymerized form includes 50 wt% or more than half weight percent of ethylene (based on the weight of the interpolymer).

[0064] As used herein, the term "ethylene / alpha-olefin copolymer" refers to a copolymer in polymerized form that includes, as only two monomer types, 50 wt% or more than half weight percent of ethylene monomer (based on the weight of the copolymer), and an alpha-olefin.

[0065] As used herein, the term "solar cell (or photovoltaic cell)" refers to a device that converts solar radiation into electricity. Solar cells are typically presented in an array pattern.

[0066] As used herein, the term "solar cell module (or solar panel or solar module)" refers to a photovoltaic panel that includes an assembly of solar cells.

[0067] As used herein, the term "reaction mixture" refers to a mixture that includes one or more monomer types and at least one metal complex. Typically, the reaction mixture also includes a solvent, one or more cocatalysts, and hydrogen (H2).

[0068] As used herein, the term "overall catalytic efficiency (in units of 10^6 g of polymer composition per 1 g of total catalyst metal)" with respect to a polymerization process refers to the production rate (e.g., lb / hr) of the polymer composition formed during the polymerization process (or polymerization run) divided by the total feed rate (e.g., lb / hr) of the catalyst metal (e.g., metal(s) from one or more metal complexes) used during the same polymerization process (or polymerization run). Typically, the polymerization is a steady-state process.

[0069] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. To avoid doubt, all compositions claimed through use of the term "comprising" may contain, whether polymeric or not, any additional additives, adjuvants, or compounds, unless the contrary is stated. In contrast, the term "consisting essentially of" excludes those elements that are not essential to the operation and excludes any other components, steps, or procedures from the scope of any subsequent description. The term "consisting of" excludes any component, step, or procedure not specifically specified or enumerated.

[0070] List of some compositional features A] A process for preparing an alpha composition comprising a first ethylene / alpha-olefin / interpolymer fraction and a second ethylene / alpha-olefin / interpolymer fraction, the process comprising polymerizing a reaction mixture comprising ethylene, an alpha-olefin, a metal complex selected from a) below, and a metal complex selected from b) below in one reactor, a) As described above in the Summary of the Invention (SOI), a biphenylphenol metal complex selected from Structure 1 below,

Chemical formula

[0071] Test method Small Amplitude Oscillatory Shear (SAOS) The rheology of each composition was analyzed by SAOS (or DMS) using an ARES-G2 rheometer equipped with a "25 mm diameter" stainless steel parallel plate under nitrogen purge. A constant temperature dynamic frequency sweep was performed at 190 °C in the range of 0.1 to 100 rad / s or 500 rad / s. The processability of the composition was evaluated using the data at 190 °C.

[0072] A sample of approximately "25 mm diameter × 3.3 mm thickness" was cut from a compression molded disk (see below). The sample was placed on the lower plate and melted for 5 minutes. Then, the plate was closed to a "2.0 mm" gap and the sample was trimmed to a diameter of "25 mm". Before starting the test, the sample was thermally equilibrated for 5 minutes. The complex viscosity was measured at a sufficient constant strain amplitude within the linear viscoelastic range (e.g., 10%). The stress response was analyzed from the viewpoints of amplitude and phase, and from which the storage modulus (G'), loss modulus (G"), dynamic viscosity η * , and tan delta could be calculated. The compression molded disk was formed in an ambient atmosphere at a molding pressure of 180 °C and 10 MPa for 5 minutes, and then quenched between cooling plates (15-20 °C) for 2 minutes. The viscosities (V0.1, V1.0, V100, each at 190 °C) were recorded.

[0073] Gel Permeation Chromatography The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160 °C and the column compartment was set at 150 °C. The columns were four AGILENT “Mixed A” 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent was 1,2,4-trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters and the flow rate was 1.0 milliliter per minute.

[0074] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards with molecular weights in the range of 580 to 8,400,000 and arranged in six “cocktail” mixtures with at least a 10-fold interval between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights of 1,000,000 and above and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved with gentle stirring at 80 degrees Celsius for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A×(M ポリエチレン ) B (Equation 1), where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0075] A fifth-degree polynomial was used to fit each polyethylene equivalent calibration point. A slight adjustment (about 0.375 to 0.445) was made to A, and the column resolution and band broadening effect were corrected so that a linear homopolymer polyethylene standard substance could be obtained at 120,000 Mw.

[0076] The total plate count of the GPC column set was performed using decane (prepared at 0.04 g in 50 milliliters of TCB, dissolved for 20 minutes with gentle stirring). The plate count (Equation 2) and symmetry (Equation 3) were determined by injecting 200 microliters using the following equations:

Number

Number

[0077] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, with a target weight of 2 mg / ml for the sample. Through a PolymerChar high-temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a septum-capped vial previously sparged with nitrogen. The samples were dissolved at 160 degrees Celsius for 2 hours while shaking at "low speed".

[0078] Mn (GPC) , Mw (GPC) , and Mz (GPC)The calculation was performed based on the GPC results using PolymerChar GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) of Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4 - 6. Equations 4 - 6 are as follows.

Number

[0079] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (apparent flow rate) of each sample by matching each decane peak (RV(FM sample)) in the sample with that of the decane peak in the narrow standard calibration (RV(FM calibrated)). Subsequently, any temporal change in the decane marker peak was assumed to be related to a linear shift in the flow rate (effective flow rate) throughout the experiment. To facilitate the highest accuracy in RV measurement of the flow marker peak, a least squares fitting routine was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. Subsequently, the first derivative of the quadratic equation was used to determine the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate was calculated as Equation 7: Flow rate (effective) = Flow rate (apparent) * (RV(FM calibrated) / RV(FM sample)) (Equation 7).

[0080] The processing of the flow marker peak was performed by PolymerChar GPCOne (trademark) software. For the allowable flow rate correction, the effective flow rate should be within + / - 0.7% of the apparent flow rate.

[0081] GPC Deconvolution The GPC data was deconvoluted to obtain the most likely fit for two molecular weight components. The algorithm used is optimized for the deconvolution problem of the two most likely molecular weight distributions (plus an adjustable error term). To allow for variations in the underlying distribution due to the incorporation of macromers and small variations in reactor conditions (i.e., temperature, concentration), the basis functions were modified and a normal distribution term was incorporated. This term allows the basis functions of each component to be "blurred" to various degrees along the molecular weight axis. The advantage is that at the limits (low LCB, complete concentration and temperature control), the basis functions become the simplest and most likely Flory distribution.

[0082] Three components (j = 1, 2, 3) were derived, with the third component (j = 3) being an adjustable error term. The GPC data needs to be normalized and correctly transformed to "weight fraction versus Log10 molecular weight vector". In other words, each potential curve for deconvolution should consist of a height vector, h i reported at known intervals of "Log10 molecular weight", where the hi values are correctly transformed from the elution volume domain to the "Log10 molecular weight" domain and the h i values are normalized. Further, these data need to be made available in the Microsoft EXCEL application. Several assumptions are made for deconvolution. Each component, j, consists of the most likely Flory distribution convoluted using the parameter σ j and a normal or Gaussian diffusion function. The three resulting basis functions are used in the chi-square, Χ 2 minimization routine to identify the parameters that best fit the n points of the GPC data vector, h i .

Number

[0083] Variable, CumND j,kis calculated using the EXCEL function "NORMDIST(x, mean, standard_dev, cumulative)" with parameters set as follows: x = μ j +(k - 10) * σ j / 3, mean = μ j and standard dev = σ j and cumulative = TRUE. Table A below summarizes these variables and their definitions. For this task, the use of the EXCEL software application, SOLVER, is appropriate. Add constraints to SOLVER to ensure correct minimization.

[0084]

Table 1

[0085] The eight parameters derived from chi - square minimization are μ1, μ2, μ3, σ1, σ2, σ3, w1, and w2. The term w3 is then derived from w1 and w2 since the sum of the three components needs to equal 1. Table B is a summary of the SOLVER constraints used in the EXCEL program.

[0086]

Table 2

[0087] It should be understood that additional constraints, for which the SOLVER routine does not move any of the μ j to values less than approximately 0.005, include the limit that only μ j greater than 0 are allowed, even though the constraints need not be entered if the SOLVER is initialized correctly. Also, it is understood that all w j are positive. This constraint can be processed outside of SOLVER. w jIf it is understood that it results from the selection of two points along the time interval of 0.0 < P1 < P2 < 1.0, whereby w1 = P1, w2 = P2 - P1 and w3 = 1.0 - P2, then the constraints on P1 and P2 are equivalent to the constraints required for the above w j and are as follows. Table C is a summary of the SOLVER settings under the Options tab.

[0088]

Table 3

[0089] By assuming two ideal Flory components that give the observed weight-average, number-average, and z-average molecular weights of the observed GPC distribution, first guess values of μ1, μ2, w1, and w2 can be obtained.

Number

[0090] Next, the values of μ1, μ2, w1, and w2 are calculated. These should be carefully adjusted to allow for a small error term, w3, and to satisfy the constraints of Table B before inputting them into the SOLVER for the minimization step. The starting value of σ j is set to 0.05 for all.

[0091] Differential Scanning Calorimetry (DSC) Differential scanning calorimetry (DSC) is used to measure the Tm, Tc, Tg, and crystallinity of ethylene-based (PE) samples and propylene-based (PP) samples. Each sample (0.5 g) was compression molded into a film at 190 °C and 5000 psi for 2 minutes. Approximately 5 - 8 mg of the film sample was weighed and placed in a DSC pan. The lid was crimped over the pan to ensure a sealed atmosphere. The sample pan was placed in the DSC cell and heated to a temperature of 180 °C for PE (230 °C for PP) at a rate of approximately 10 °C / min. The sample was held at this temperature for 3 minutes. Next, the sample was cooled to -90 °C for PE (-60 °C for PP) at a rate of 10 °C / min and held isothermally at that temperature for 3 minutes. Next, the sample was heated at a rate of 10 °C / min until completely melted (second heating). Unless otherwise stated, the melting point (Tm) and glass transition temperature (Tg) of each polymer were determined from the second heat curve, and the crystallization temperature (Tc) was determined from the first cooling curve. The respective peak temperatures for Tm and Tc were recorded. The percent crystallinity can be calculated by dividing the heat of fusion (Hf) determined from the second heat curve by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this amount by 100 (e.g., % crystallinity = (Hf / 292 J / g) × 100 for PE).

[0092] Melt Index The melt flow index I2 of ethylene-based polymers is measured according to ASTM D-1238, condition 190 °C / 2.16 kg (melt index I5 at 190 °C / 5.0 kg, melt index I10 at 190 °C / 10.0 kg, high load melt index I21 at 190 °C / 21.0 kg). The melt flow rate (MFR) of propylene-based polymers - ASTM D-1238, condition 230 °C / 2.16 kg.

[0093] Polymer Density The polymer density is measured according to ASTM D-792.

[0094] Experiment Catalyst, cocatalyst, polymer synthesis (alpha composition), and properties The BPP catalysts and useful cocatalysts are listed in Table 1. Each alpha composition was prepared in a 1-gallon polymerization reactor filled with hydraulic pressure and operated under steady-state conditions. The catalysts and cocatalysts are listed above. According to the process conditions outlined in Table 1A, Table 1B, and Table 1C, the solvent, hydrogen, catalyst, and cocatalyst were fed into the reactor to produce the alpha composition. The solvent was ISOPAR E supplied by ExxonMobil Chemical Company. The reactor temperature was measured at or near the outlet of the reactor. The overall properties are shown in Tables 2 - 4, and the molecular weight properties of the interpolymer fraction are shown in Table 5.

[0095] [Table 4]

[0096] [Table 5]

[0097] [Table 6]

[0098] [Table 7]

[0099] [Table 8]

[0100] [Table 9]

[0101] [Table 10]

[0102]

Table 11

[0103] Figure 1 shows the SAOS (190 °C) profiles of the alpha compositions (POEA, POEB, POEC, POEF) of the present invention and two commercially available resins (ENGAGE 8457 polyolefin elastomer and ATEVA 2810A (EVA (benchmark resin))). As can be seen in Figure 1, compared to ENGAGE 8457, the alpha compositions of the present invention exhibit lower viscosities at high shear rates (V > 10 rad / s) for improved processability and higher viscosities at lower shear rates (V < 1 rad / s) for improved mechanical strength. Most of the samples of the present invention also exhibit equivalent or better shear thinning viscosity for excellent processability compared to those of ATEVA 2810A, and all have higher "low shear viscosities". Each composition of the present invention can be prepared in a cost-effective one-reactor synthesis having excellent overall catalyst efficiency. It should be noted that the present invention includes the following aspects. [Aspect 1] A process for preparing an alpha composition comprising a first ethylene / alpha-olefin / interpolymer fraction and a second ethylene / alpha-olefin / interpolymer fraction, the process comprising polymerizing a reaction mixture comprising ethylene, an alpha-olefin, a metal complex selected from the following a), and a metal complex selected from the following b) in one reactor, a) A biphenylphenol metal complex selected from the following Structure 1:

Chemical formula

Chem.

Chem.

Chem.

Chem.

Claims

1. A process for preparing an alpha composition comprising a first ethylene / alpha-olefin / interpolymer fraction and a second ethylene / alpha-olefin / interpolymer fraction, wherein the process comprises polymerizing a reaction mixture comprising ethylene, an alpha-olefin, a metal complex selected from the following a), and a metal complex selected from the following b) in one reactor, a) a biphenylphenol metal complex selected from the following Structure 1: 【Chemical 1】 (wherein, M is a metal selected from zirconium (Zr) or hafnium (Hf), and the metal is in a formal oxidation state of +2, +3, or +4, n is 0, 1, or 2, when n is 1, X is a monodentate ligand or a bidentate ligand, when n is 2, each X is an independently selected monodentate ligand, the metal complex is overall charge-neutral, -Z １ -and -Z ２ -each of which is independently -O-, -S-, -N(R Ｎ ), or -P(R Ｐ ), and is selected from R １ and R ８ are each independently selected from the group consisting of -H, (C １ ~C ４０ )-hydrocarbyl, (C １ ~C ４０ )heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ) ２ NC(O)-, halogen, a radical having formula (I), a radical having formula (II), and a radical having formula (III). [Chemical Formula 2] wherein R ３１～３５ , R ４１～４８ , and R ５１～５９ each independently is selected from (C １ - C ４０ ) hydrocarbyl, (C １ - C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -N=CHR Ｃ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ )-, (R Ｃ ) ２ NC(O)-, halogen, or -H, R ２～７ and R ９～１６ each independently is selected from (C １ to C ４０ ) hydrocarbyl, (C １ to C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -N=CHR Ｃ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ )-, (R Ｃ ) ２ NC(O)-, halogen, or -H, L is (C １ ~C ４０ ) hydrocarbylene or (C １ ~C ４０ ) heterohydrocarbylene, and the (C １ ~C ４０ ) hydrocarbylene contains a linker skeleton of 1 to 10 carbon atoms and has a portion connecting two Z groups (to which L is attached) of Structure 1, or the (C １ ~C ４０ ) heterohydrocarbylene contains a linker skeleton of 1 to 10 carbon atoms and has a portion connecting the two Z groups of Structure 1, and each of 1 to 10 atoms of the 1 to 10 atom linker skeleton of the (C １ ~C ４０ ) heterohydrocarbylene is independently a carbon atom or a heteroatom group, and each heteroatom group is independently O, S, S(O), S(O) ２ , Si(R Ｃ ) ２ , Ge(R Ｃ ) ２ , P(R Ｃ ), or N(R Ｃ ), and independently each R Ｃ is (C １ ~C ３０ ) hydrocarbyl, or (C １ ~C ３０ ) heterohydrocarbyl, Each R in Structure 1 Ｐ , R Ｎ , and the remaining R Ｃ are each independently (C １ to C ３０ ) hydrocarbyl, (C １ to C ３０ ) heterohydrocarbyl, or -H). b) a biphenylphenol metal complex selected from Structure 2: [Chemical 3] (wherein, M is Zr or Hf, and the metal is in a formal oxidation state of +2, +3, or +4, n is 0, 1, or 2, when n is 1, X is a monodentate ligand or a bidentate ligand, when n is 2, each X is an independently selected monodentate ligand, the metal complex is overall charge-neutral, -Z １ -and -Z ２ -each of which is independently -O-, -S-, -N(R Ｎ )-, or -P(R Ｐ )-selected from, R １ and R ８ are each independently selected from the group consisting of -H, (C １ ~C ４０ ), hydrocarbyl, (C １ ~C ４０ ), heterohydrocarbyl, -Si(R Ｃ ), ３ -Ge(R Ｃ ), ３ -P(R Ｐ ), ２ -N(R Ｎ ), ２ -OR Ｃ -SR Ｃ -NO ２ -CN, -CF ３ R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ), ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R)-, (R Ｃ ), ２ NC(O)-, halogen, a radical having formula (I), a radical having formula (II), and a radical having formula (III). 【Chemical 4】 wherein R ３１～３５ , R ４１～４８ , and R ５１～５９ each independently is selected from (C １ - C ４０ ) hydrocarbyl, (C １ - C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -N=CHR Ｃ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ - , (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ )-, (R Ｃ ) ２ NC(O)-, halogen or -H, R ２～７ and R ９～１６ each independently is selected from (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -N=CHR Ｃ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ )-, (R Ｃ ) ２ NC(O)-, halogen, or -H, Y is -(CH ２ ) ｎ -(where n = 0 to 2), -CR ａ R ｂ -(where R ａ and R ｂ are each independently (C １ to C ４０ ) hydrocarbyl, (C １ to C ４０ ) heterohydrocarbyl, or -H), -Ge(R Ｄ ) ２ - or -Si(R Ｄ ) ２ (where each R Ｄ is independently -H, (C １ to C ４０ ) hydrocarbyl, (C １ to C ４０ ) heterohydrocarbyl, -Si(R Ｃ ) ３ , -Ge(R Ｃ ) ３ , -P(R Ｐ ) ２ , -N(R Ｎ ) ２ , -OR Ｃ , -SR Ｃ , -NO ２ , -CN, -CF ３ , R Ｃ S(O)-, R Ｃ S(O) ２ -, (R Ｃ ) ２ C=N-, R Ｃ C(O)O-, R Ｃ OC(O)-, R Ｃ C(O)N(R Ｎ )-, and (R Ｎ ) ２ NC(O)- selected from the group consisting of), and is any one of Each R in structure 2 Ｃ R Ｐ and R Ｎ are independently (C １ to C ３０ ) hydrocarbyl, (C １ to C ３０ ) heterohydrocarbyl, or -H), However, for one of Structure 1 or Structure 2, R １２ and R １３ cannot both be halo, and R1 and R8 are each radicals having the formula (II), where R ４３ = R ４６ = t-Bu, and R ４１～４２ = R ４４～４５ = R ４７～４８ = -H. However, Structures 1 and 2 do not have the same metal (M) when they have the same R group, Z group, X group(s), and linker group between Z １ and Z ２ Therefore, if M is Hf for one structure, M is Zr for the other structure Structure 2 is selected from the following Structure 2a or 2b: 【Chemical Formula 5】 a process.

2. Regarding Structure 1, R １ and R ８ are the same and are selected from the group consisting of a radical having formula (I), a radical having formula (II), and a radical having formula (III), the process according to claim 1.

3. For Structure 1, L is i) -CH ２ Si(R ａ )(R ｂ )CH ２ - or -CH ２ Ge(R ａ )(R ｂ )CH ２ -(wherein R ａ and R ｂ are each independently (C １ ~C ３０ ) hydrocarbyl or (C １ ~C ３０ ) heterohydrocarbyl), ii) 1,3-dimethylpropane-1,3-diyl, iii) bis(methylene)cyclohexane-1,2-diyl, iv) propane-1,3-diyl, or v) butane-1,4-diyl The process according to claim 1 or 2, selected from.

4. Structure 1 is selected from the following Structures 1a to 1c: ​ The process according to any one of claims 1 to 3, selected from.

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