Method for producing a polymer composition having excellent processability

Abstract

A method for preparing an alpha composition, the alpha composition comprising a first ethylene / α-olefin / interpolymer portion and a second ethylene / α-olefin / interpolymer portion; the method comprising polymerizing a reaction mixture in one reactor, the reaction mixture comprising ethylene and an α-olefin, a biphenol metal complex selected from Structure 1 as described herein and a biphenol metal complex selected from Structure 2 as described herein; and an alpha composition prepared therefrom.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Application No. 62 / 953,707, filed on December 26, 2019, which is incorporated herein by reference in its entirety. Background Art

[0003] Improved elastomer processability is one of the key needs of end-use manufacturers for various elastomeric products, such as automotive components, photovoltaic modules, wire and cable assemblies, and footwear components. There is a need for new elastomeric resins with improved processability, as indicated by excellent shear thinning phenomena. Such resins should be polymerized in a cost-effective and high efficiency process.

[0004] US Publication 2011 / 0290317 discloses the preparation and electronic applications of bimodal and multimodal polymers based on ethylene. These polymers are prepared in two reactors, increasing the complexity and capital cost of the overall polymerization process. International Publication WO2018 / 022588 discloses the polymerization of multimodal elastomers, mainly synthesized in the presence of biphenol catalyst and constrained geometry catalyst (CGC). A comparative example (Comp. C), which uses two biphenol catalysts, has a lower overall catalyst efficiency of 1.4×10 per gram of total catalyst metal. 6 Other ethylene-based in-situ, bimodal polymers and post-reactor blends are disclosed in the following references: WO2001 / 014434 (polymerization using a hybrid constrained geometry catalyst system), WO2002 / 074817 (polymerization using a hybrid constrained geometry catalyst system), US20160115264 (metallocene-catalyzed polymers), US5849823 (blends of linear or substantially linear homogeneously branched ethylene / α-olefin interpolymers), US6451894 (blends comprising crystalline or semi-crystalline polyolefins or copolymers of ethylene and C3 to C10 olefins, and multimodal elastomers of sequentially polymerized ethylene-α-olefin monomers; see also US6610408). However, the cited techniques do not result in elastomeric resins having excellent shear thinning phenomena and which can be polymerized in a cost-effective, high-efficiency process. These needs have been met by the following invention. Summary of the invention

[0005] A method for preparing an alpha composition comprising a first ethylene / α-olefin / interpolymer portion and a second ethylene / α-olefin / interpolymer portion; the method comprising polymerizing a reaction mixture in one reactor, the reaction mixture comprising ethylene, an α-olefin, a metal complex selected from the following a) and a metal complex selected from the following b):

[0006] a) a biphenol metal complex selected from the following structure 1:

[0007]

[0008] Structure 1, wherein:

[0009] M is a metal selected from zirconium (Zr) or hafnium (Hf), the metal being in a formal oxidation state of +2, +3 or +4;

[0010] n is 0, 1 or 2;

[0011] When n is 1, X is a monodentate ligand or a bidentate ligand;

[0012] When n is 2, each X is an independently selected monodentate ligand;

[0013] The metal complex is generally charge neutral;

[0014] -Z 1 -and-Z 2 -, each of which is independently selected from -O-, -S-, -N(R N )-or–P(R P )-;

[0015] R 1 and R 8 Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (I), a group having the formula (II) and a group having the formula (III):

[0016]

[0017] Where R 31–35 , R 41–48 and R 51–59Each of which is independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2, -N=CHR C 、-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)-, halogen or –H;

[0018] R 2–7 , R 9–16 Each of which is independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2, -N=CHR C 、-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)-, halogen or -H;

[0019] L is (C1-C 40 )alkylene or (C1-C 40 )heteroalkylene, wherein the (C1-C 40 ) alkylene has a portion of a linker backbone including 1 to 10 carbon atoms, connecting two Z groups in structure 1 (L is bonded to the two Z groups); or the (C1-C 40) heteroalkylene has a linker backbone portion comprising 1 to 10 atoms, connecting two Z groups in structure 1, wherein the (C1-C 40 Each of the 1 to 10 atoms of the 1 to 10 carbon atoms of the linker backbone of the heteroalkylene group is independently a carbon atom or a heteroatom group, wherein 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 ), where independently, each R C is (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl; and

[0020] Each R in structure 1 P , R N and the rest of R C Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H;

[0021] b) a biphenol metal complex selected from structure 2:

[0022]

[0023] Structure 2, where:

[0024] M is Zr or Hf, the metal being in a formal oxidation state of +2, +3 or +4;

[0025] n is 0, 1 or 2;

[0026] When n is 1, X is a monodentate ligand or a bidentate ligand;

[0027] When n is 2, each X is an independently selected monodentate ligand;

[0028] The metal complex is generally charge neutral;

[0029] -Z 1 -and-Z 2 -, each of which is independently selected from -O-, -S-, -N(R N )-or–P(R P )-;

[0030] R 1 and R 8 Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(RC )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (I), a group having the formula (II) and a group having the formula (III):

[0031]

[0032] Where R 31–35 , R 41–48 and R 51–59 Each of which is independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2, -N=CHR C 、-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)-, halogen or –H;

[0033] R 2–7 , R 9–16 Each of which is independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2, -N=CHRC 、-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)-, halogen or –H;

[0034] Y is -(CH2) n -, wherein n = 0 to 2; -CR a R b -, where R a and R b Each independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl or -H; -Ge(R D )2- or -Si(R D )2-, where each R D Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )- and (R N )2NC(O)-; and

[0035] Each R in structure 2 C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H;

[0036] Provided that for either Structure 1 or Structure 2, when R1 and R8 are each a group having formula (II), R 12 and R 13 Not all of them can be halogen groups, where R 43 =R 46 =t-Bu, and R 41-42 =R 44-45 =R 47-48 = -H; and

[0037] The prerequisite is that when structure 1 and structure 2 have the same R group, Z group, X group and Z 1 With Z 2 When the connecting group between them is , these structures do not have the same metal (M) such that for one structure M is Hf, then for the other structure M is Zr.

[0038] A composition comprising an alpha composition comprising a first ethylene / alpha-olefin interpolymer portion and a second ethylene / alpha-olefin interpolymer portion, and

[0039] The alpha composition comprises the following characteristics:

[0040] i) Mz / Mn ≥ 8.0,

[0041] ii) a density of 0.855 to 0.890 g / cc,

[0042] iii) V100 (190°C) ≤ 600 Pa·s, and

[0043] iv)V0.1(190℃)≥4,000Pa·s. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 The SAOS curves (190°C) of the α compositions of the present invention (POE A, POE B, POE C, POE F) and two commercial resins (ENGAGE 8457 polyolefin elastomer and ATEVA 2810A) are shown. The curves at "0.1 rad / s" are from top to bottom: POE F, POE C, POE B, POE A, ENGAGE 8457 and ATEVA 2810A. DETAILED DESCRIPTION

[0045] Ethylene / α-olefin multimodal interpolymers with excellent processability have been found. These compositions exhibit low viscosity at high shear and high viscosity at low shear to improve processability; for example, low injection pressure during high shear rate injection molding or low shear heating during high shear rate mixing, and high resistance to sag on extruded parts at low shear rates. It has also been found that such interpolymers can be produced in a single reactor using a multi-catalyst system (e.g., a dual catalyst system) at high temperature (≥150° C.) and high efficiency. For example, under the same reactor conditions, the first catalyst produces a high molecular weight (HMW) interpolymer portion, and the second catalyst produces a low molecular weight (LMW) interpolymer portion.

[0046] As described above, a method for preparing an alpha composition comprising a first ethylene / α-olefin / interpolymer fraction and a second ethylene / α-olefin / interpolymer fraction is provided; the method comprising polymerizing a reaction mixture in one reactor, the reaction mixture comprising ethylene, an α-olefin, a metal complex selected from the following a) and a metal complex selected from the following b):

[0047] a) a biphenol metal complex selected from Structure 1, as described above (see Summary of the Invention (SOI)); and

[0048] b) A biphenol metal complex selected from structure 2, as described above (see SOI).

[0049] The inventive method may comprise a combination of two or more embodiments as described herein. Each biphenol metal complex may independently comprise a combination of two or more embodiments as described herein. As used herein, R1=R 1 , R2=R 2 , R3=R 3 , and so on. In addition, the symbol R a(1) -R a(n) , where "a(1) to a(n)" represent consecutive numbers, referring to R a (1) , R a(2) , R a(3) , …, R a(n) For example, R 31 -R 35 Refers to R 31 , R 32 , R 33 , R 34 , R 35 ; and R 51 -R 59 Refers to R 51 , R 52 , R 53 , R 54 , R 55 , R56 , R 57 , R 58 , R 59 In each of Formulas (I)-(III), the wavy line indicates the corresponding formula (R 1 or R 8 The connection (bond) between the phenol group and the rest of the biphenol metal complex.

[0050] The term "independently selected" is used herein to refer to R groups (such as R 1 , R 2 , R 3 , R 4 , and R 5 ) can be the same or different (e.g., R 1 , R 2 , R 3 , R 4 and R 5 can be substituted alkyl, or R 1 and R 2 It may be a substituted alkyl group and R 3 can be aryl, etc.). The use of the singular encompasses the use of the plural, and vice versa (e.g., a hexane solvent encompasses a plurality of hexanes). A named R group will generally have a structure that is recognized in the art to correspond to the R group having the name. These definitions are intended to supplement and illustrate, but not to exclude, definitions known to those skilled in the art. When used to describe certain chemical groups containing carbon atoms, a group having the form "(C x -C y )" means that the chemical group has from x to y carbon atoms, including x and y. For example, (C1-C 40 ) The alkyl group is an alkyl group having 1 to 40 carbon atoms.

[0051] The term "substituent" refers to a substituent (R s ) replaces a hydrogen atom (-H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound. The symbol "R S " refers to a heteroatom or a chemical group including 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 ) instead.

[0052] The term "-H" means a hydrogen or a hydrogen group covalently bonded to another atom. "Hydrogen," H, and "-H" are interchangeable and have the same meaning unless expressly specified otherwise.

[0053] The term “(C1–C 40)hydrocarbyl" means a hydrocarbon group having 1 to 40 carbon atoms, and the term "(C1-C 40 )alkylene group" means a hydrocarbon diradical having 1 to 40 carbon atoms, wherein each hydrocarbon group and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic; 3 or more carbon atoms) or acyclic, and is unsubstituted or substituted with one or more R S replace.

[0054] In the present disclosure, (C1-C 40 The hydrocarbon group may be 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-C 20 )aryl-(C1-C 20 In some embodiments, the aforementioned (C1-C 40 ) each of which has up to 20 carbon atoms (i.e., (C1-C 20 )alkyl), and in other embodiments, has up to 12 carbon atoms.

[0055] The term "(C1-C 40 )alkyl" and "(C1-C 30 ) alkyl refers to a saturated straight or branched hydrocarbon group of 1 to 40 carbon atoms or 1 to 30 carbon atoms, which is unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C1–C 40 Examples of alkyl groups 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. Substituted (C1–C 40 Examples of alkyl groups are substituted (C1-C 20 )alkyl, substituted (C1–C 10 )alkyl and trifluoromethyl.

[0056] The term "(C6-C 40 ) aryl refers to an unsubstituted or substituted (with one or more R SUnsubstituted (C6-C 6-substituted) monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms, and the monocyclic, bicyclic or tricyclic groups include 1, 2 or 3 rings, respectively; wherein 1 ring is aromatic, and 2 or 3 rings are independently fused or non-fused, and at least one of the 2 or 3 rings is aromatic. 40 Examples of aryl groups are unsubstituted (C6-C 20 )Aryl; Unsubstituted (C6–C 18 )aryl; 2-(C1-C5)alkyl-phenyl; 2,4-bis(C1–C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6–C 40 Examples of aryl groups are substituted (C1-C 20 ) aryl; substituted (C6-C 18 ) aryl; polyfluorophenyl and pentafluorophenyl.

[0057] The term “(C3–C 40 )Cycloalkyl refers to a cycloalkyl having 3 to 40 carbon atoms which is unsubstituted or substituted with one or more R S Other cycloalkyl groups (e.g., (C x –C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C3-C 40 Examples of cycloalkyl groups are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3–C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Substituted (C3–C 40 Examples of cycloalkyl groups are substituted (C3-C 20 )cycloalkyl, substituted (C3–C 10 )cycloalkyl and 1-fluorocyclohexyl.

[0058] (C1–C 40 Examples of alkylene groups include unsubstituted or substituted (C6-C 40 )arylene, (C3–C 40 )cycloalkylene and (C1–C 40 ) alkylene (e.g., (C1–C 20) alkylene). In some embodiments, the diradicals are located on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are separated by one, two, or more than two intervening carbon atoms (e.g., respective 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include α,ω-diradicals. α,ω-diradicals are diradicals with the largest carbon backbone spacing between the radical carbons. (C2–C 20 Some examples of alkylene α,ω-diyl radicals include ethane-1,2-diyl (ie, -CH2CH2), propane-1,3-diyl (ie, -CH2CH2CH2-), 2-methylpropane-1,3-diyl (ie, -CH2CH(CH3)CH2-). (C6–C 40 )Some examples of arylene α,ω-diyl include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0059] The term “(C1–C 40 ")Alkylene" means a saturated straight or branched chain diradical (i.e., the radical is not on a ring atom) of 1 to 40 carbon atoms, which is unsubstituted or substituted with one or more R S Substituted. Substituted (C1–C 40 Examples of alkylene groups are unsubstituted (C1-C 20 )alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*(H)(CH3), and -(CH2)4C*(H)(CH3), wherein "C*" indicates a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C1-C 40 Examples of alkylene groups are substituted (C1-C 20 )alkylene and -CF2-, -C(O)-. The term "(C3–C 40 "Cycloalkylene" means a cyclic diradical (i.e., the radical is on a ring atom) of 3 to 40 carbon atoms, which is unsubstituted or substituted with one or more R S replace.

[0060] 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–, where each R C and each R P are independently unsubstituted (C1-C 30 )alkyl or -H, and each R N is unsubstituted (C1-C 30 ) hydrocarbon group.

[0061] The term "heterohydrocarbon" refers to a molecule or molecular backbone in which one or more carbon atoms are replaced by a heteroatom. 40 ) heteroalkyl" means a heteroalkyl group of 1 to 40 carbon atoms, and the term "(C1-C 40 The term "heteroalkylene" means a heteroalkyl diradical of 1 to 40 carbon atoms, each of which has one or more heteroatoms. The radical of the heteroalkyl group is located on a carbon atom or a heteroatom, and the diradical of the heteroalkyl group can be located on: (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) both carbon atoms and heteroatoms. Each (C1-C 40 ) heteroalkyl and (C1–C 40 ) The heteroalkylene group may be unsubstituted or substituted with (one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0062] (C1–C 40 )Heteroalkyl may be unsubstituted or substituted. (C1–C 40 Non-limiting examples of heteroalkyl groups include: (C1-C 40 ) heteroalkyl, (C1–C 40 )alkyl-O-, (C1–C 40 )alkyl-S-, (C1–C 40 )alkyl-S(O)-, (C1–C 40 )alkyl-S(O)2-, (C1-C 40 )alkyl-Si(R C )2-、(C l –C 40 )alkyl-N(R N )-、(C–C 40 )alkyl-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.

[0063] The term “(C1–C 40 ) heteroaryl" means an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups, and the monocyclic, bicyclic or tricyclic groups include 1, 2 or 3 rings respectively; wherein 2 or 3 rings are independently fused or non-fused, and at least one of the 2 or 3 rings is heteroaromatic. Other heteroaryl groups (for example, usually (C x –C y ) heteroaryl, such as (C1–C 12 ) heteroaryl) is defined in a similar manner as having x to y carbon atoms (e.g., 1 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one R Ssubstituted. The monocyclic heteroaromatic hydrocarbon group 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 heteroaromatic hydrocarbon groups are pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thien-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, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups are pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6-ring systems or 6,6-ring systems. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6,5-ring systems; 5,6,6-ring systems; 6,5,6-ring systems; or 6,6,6-ring systems. Examples of fused 5,6,5-ring systems are 1,7-dihydropyrrolo[3,2-f]indol-1-yl. Examples of fused 5,6,6-ring systems are 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.

[0064] The aforementioned heteroalkyl group may be a group comprising (C1-C 40 ) carbon atoms or less and one or more heteroatoms. Similarly, heteroalkylene can be a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatom group can 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. Heteroalkyl and heteroalkylene are unsubstituted or substituted with one or more R S replace.

[0065] Unsubstituted (C2–C 40Examples of heterocycloalkyl groups are unsubstituted (C2-C 20 )-heterocycloalkyl, unsubstituted (C2–C 10 )heterocycloalkyl, aziridine-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroaziridine-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

[0066] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halogen ion" refers to the anionic form of a halogen atom: fluorine (F - ), chlorine (Cl - ), bromine (Br - ) or iodine (I - ).

[0067] The term "procatalyst" 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 procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0068] In some embodiments, the catalyst system comprising the metal-ligand complex of Structure 1 and Structure 2 is each catalytically active by any technique known in the art for activating a metal-based catalyst for olefin polymerization. For example, the metal-ligand complex of Structure 1 and Structure 2 can be catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Activating cocatalysts suitable for use herein include alkylaluminums; polymeric or oligomeric aluminoxanes (also referred to as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts 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 aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0069] The Lewis acid activator (cocatalyst) comprises a catalyst having 1 to 3 (C1-C 20 ) hydrocarbyl substituent. In one embodiment, the Group 13 metal compound is tri((C1-C 20 ) alkyl) substituted aluminum or tri((C1–C 20In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)substituted aluminum, a tri(hydrocarbyl)-boron compound, a tri(C1-C 10 )alkyl)aluminum, tri((C6–C 18 ) aryl) boron compounds and halogenated (including perhalogenated) derivatives thereof. In other embodiments, the Group 13 metal compound is tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tetra((C1-C 20 ) alkyl borate (e.g., trityl tetrafluoroborate) or tris((C1–C 20 )alkyl)ammonium tetra((C1–C 20 ) alkyl) borate (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a nitrogen cation that is ((C1-C 20 )alkyl)4N + 、((C1-C 20 )alkyl)3N(H) + , ((C1–C 20 )alkyl)2N(H)2 + , (C1–C 20 )Hydrocarbon N(H)3 + or N(H)4 + , where there are two or more (C1–C 20 ) hydrocarbon groups, they may be the same or different.

[0070] The combination of a non-polymeric, non-coordinating, ion-forming compound and a polymeric or oligomeric aluminoxane comprises a polymeric or oligomeric aluminoxane (also known as aluminoxane) and a halogenated tetraborate compound, particularly bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)boric acid (1 - The molar ratio of (metal-ligand complex):((bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)boronic acid (1-)amine):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tetra(pentafluorophenyl-borate):(aluminoxane)] 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 aluminoxanes and combinations of a single neutral Lewis acid (especially tris(pentafluorophenyl)borane) with polymeric or oligomeric aluminoxanes.

[0071] The catalyst system including the metal-ligand complex of Structure 1 and Structure 2 can be activated to form an active catalyst composition by combining with one or more cocatalysts, such as a cation forming cocatalyst, a strong Lewis acid, or a combination thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methyl aluminoxane) and inert, compatible, non-coordinating ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl) methyl tetrakis(pentafluorophenyl) borate (1 - )amines and combinations thereof.

[0072] In some embodiments, one or more of the aforementioned activating co-catalysts 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 moles of the metal-ligand complex of one or more structures 1 and 2 to the total moles of the one or more activating co-catalysts is at least 1:500, or 1:300, or 1:100, or 1:50, or 1:10, or 1:5. When aluminoxane is used alone as an activating co-catalyst, the moles of aluminoxane used are preferably at least 10 times the total moles of the metal-ligand complex of structures 1 and 2.

[0073] It should be understood that the catalyst system of the present disclosure can be embodied in different forms and should not be construed as being limited to the specific embodiments set forth in the present disclosure. On the contrary, the embodiments are provided so that the present disclosure will be thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art. Specific embodiments of the catalyst system will now be described.

[0074] In one embodiment or a combination of two or more embodiments described herein, for Structure 2, Y is -(CH2) n -, wherein n=0 to 2, further n=1 or 2, further n=1; -CR a R b -, where R a and R b Each independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl or -H; -Ge(R D )2- or -Si(R D )2-, where each R D Independently selected from the group consisting of: -H, (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl.

[0075] In one embodiment or a combination of two or more embodiments described herein, for structure 1, -Z1 -and-Z 2 Each of - is -O-.

[0076] In one embodiment or a combination of two or more embodiments described herein, for Structure 2, -Z 1 -and-Z 2 Each of - is -O-.

[0077] In one embodiment or a combination of two or more embodiments described herein, for Structure 1, R 1 and R 8 are the same and are selected from the group consisting of a group having formula (I), a group having formula (II) and a group having formula (III).

[0078] In one embodiment or a combination of two or more embodiments described herein, for Structure 2, R 1 and R 8 are the same and are selected from the group consisting of a group having formula (I), a group having formula (II) and a group having formula (III).

[0079] In one embodiment or a combination of two or more embodiments described herein, for Structure 1, R 1 or R 8 At least one of the groups is selected from a group having formula (II) or a group having formula (I).

[0080] In one embodiment or a combination of two or more embodiments described herein, for Structure 2, R 1 or R 8 At least one of them is selected from the group having formula (II).

[0081] In one embodiment or a combination of two or more embodiments each described herein, for Structure 1, L is selected from the following:

[0082] i)-CH2Si(R a )(R b )CH2- or -CH2Ge(R a )(R b )CH2-, where R a and R b Each independently is (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl;

[0083] ii) 1,3-dimethylpropane-1,3-diyl;

[0084] iii) bis(methylene)cyclohexane-1,2-diyl;

[0085] iv) propan-1,4-diyl; or

[0086] v) butane-1,4-diyl.

[0087] In one embodiment or a combination of two or more embodiments described herein,

[0088] For Structure 2, Y is selected from the following:

[0089] i)-SiR c R d -or-GeR c R d -, where R c and R d Each independently is (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl;

[0090] ii)-(CH2) n -, wherein n=0 to 2, further n=1 or 2, further n=1; or

[0091] iii)-CR a R b -, where R a and R b Each independently is (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0092] In one embodiment or a combination of two or more embodiments individually described herein, for Structure 1, R2=R4=R5=R7=R9=R11=R12=R13=R14=R16=H.

[0093] In one embodiment or a combination of two or more embodiments individually described herein, for Structure 2, R2=R4=R5=R7=R9=R11=R12=R13=R14=R16=H.

[0094] In one embodiment or a combination of two or more embodiments described herein, Structure 1 is selected from the following Structures 1a to 1c:

[0095]

[0096] In one embodiment or a combination of two or more embodiments described herein, Structure 2 is selected from the following Structure 2a or Structure 2b:

[0097]

[0098] In one embodiment or a combination of two or more embodiments described herein, the process has an overall catalyst efficiency of ≥2.8×10 6 , ≥3.0×10 6 , or ≥3.2×10 6 , or ≥3.4×10 6 , or ≥3.6×10 6 [(g alpha composition) / (g total catalyst metal)].

[0099] In one embodiment or a combination of two or more embodiments described herein, the method is 0.855 to 0.890 g / cc, or 0.860 to 0.890 g / cc, or 0.865 to 0.890 g / cc, or 0.865 to 0.885 g / cc (1 cc = 1 cm 3 The total catalyst efficiency at the α composition density of ≥2.8×10 6 , ≥3.0×10 6 , or ≥3.2×10 6 , or ≥3.4×10 6 , or ≥3.6×10 6 [(g alpha composition) / (g total catalyst metal)].

[0100] In one embodiment or a combination of two or more embodiments described herein, the mass flow ratio of (hydrogen reactor feed) to (ethylene reactor feed) is ≤ 6.00×10 -4g / g, or ≤5.50×10 -4g / g, or ≤5.00×10 -4g / g, or ≤4.50×10 -4g / g.

[0101] In one embodiment or a combination of two or more embodiments individually described herein, the process is operated at a reactor temperature of ≥ 150°C, or ≥ 155°C, or ≥ 160°C, or ≥ 165°C.

[0102] Also provided is a composition comprising an alpha composition comprising a first ethylene / α-olefin interpolymer portion and a second ethylene / α-olefin interpolymer portion, and wherein the alpha composition comprises the following characteristics:

[0103] i) Mz / Mn ≥ 8.0,

[0104] ii) a density of 0.855 to 0.890 g / cc,

[0105] iii) V100 (190°C) ≤ 600 Pa·s, and

[0106] iv)V0.1(190℃)≥4,000Pa·s.

[0107] The present invention also provides a cross-linked composition formed from the composition of any one embodiment or a combination of two or more embodiments 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 described herein.

[0108] An inventive composition may comprise a combination of two or more embodiments as described herein.a Compositions may comprise a combination of two or more embodiments as described herein.

[0109] The α composition comprises at least two ethylene / α-olefin interpolymer parts that differ in one or more polymer characteristics. Each ethylene / α-olefin interpolymer part independently comprises ethylene and α-olefin in polymerized form, and optionally may comprise a polyene, and further a non-conjugated polyene. The α-olefin may be an aliphatic or aromatic compound. The α-olefin is preferably C3-C 20 Aliphatic compounds, preferably C3-C 16 Aliphatic compounds, and more preferably C3-C 10 Aliphatic compounds. Preferred C3-C 10 Aliphatic α-olefins include propylene, 1-butene, 1-hexene, 1-octene and 1-decene, and more preferably 1-octene. Suitable examples of non-conjugated polyenes include linear acyclic dienes such as 1,4-hexadiene and 1,5-heptadiene; branched 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 dihydromyrcene. Monocyclic alicyclic dienes, such as 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; polycyclic alicyclic fused and bridged cyclic dienes, such as tetrahydroindene, methyltetrahydroindene; alkenyl, alkylene, cycloalkenyl and cycloalkylene 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-cyclohexylene-2-norbornene. The polyene is preferably a non-conjugated diene selected from ENB, VNB and dicyclopentadiene, and is preferably ENB.

[0110] In one embodiment or a combination of two or more embodiments described herein, the composition of the invention further comprises a thermoplastic polymer that is independently different from each of the first and second interpolymer parts in one or more characteristics, such as monomer type 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 multi-block 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), ethylene-based homogeneously branched linear polymers, and ethylene-based homogeneously branched substantially linear polymers (i.e., homogeneously branched long-chain branched ethylene polymers). Examples of propylene-based polymers include polypropylene homopolymers and propylene / ethylene copolymers.

[0111] definition

[0112] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0113] As used herein, the term "composition" encompasses a mixture of materials comprising the composition, as well as 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.

[0114] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer encompasses the term homopolymer (used to refer to polymers prepared from only one type of monomer, it being understood 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. The polymer is stable at very low amounts ("ppm" amounts) of one or more stabilizers.

[0115] As used herein, the term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. The term interpolymer thus includes the term copolymer (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0116] As used herein, the term "propylene-based polymer" refers to a polymer that, in polymerized form, comprises a majority weight percent propylene (based on the weight of the polymer) and, optionally, may include one or more comonomers.

[0117] As used herein, the term "ethylene-based polymer" refers to a polymer that, in polymerized form, comprises 50 wt% or a majority weight percent ethylene (based on the weight of the polymer), and optionally may include one or more comonomers.

[0118] As used herein, the term "ethylene / α-olefin interpolymer" refers to a random interpolymer comprising ethylene and α-olefin in polymerized form. In one embodiment, the "ethylene / α-olefin interpolymer" comprises 50 wt% or a majority weight percentage of ethylene (based on the weight of the interpolymer) in polymerized form.

[0119] As used herein, the term "ethylene / α-olefin / non-conjugated polyene interpolymer" refers to a random interpolymer that includes ethylene, α-olefin, and non-conjugated polyene (e.g., non-conjugated diene) in polymerized form. In one embodiment, the "ethylene / α-olefin / non-conjugated polyene interpolymer" includes 50 wt% or a majority weight percent ethylene (based on the weight of the interpolymer) in polymerized form.

[0120] As used herein, the term "ethylene / α-olefin copolymer" refers to a random copolymer comprising, in polymerized form, 50 wt% or majority weight percent ethylene monomer (based on the weight of the copolymer) and α-olefin as the only two monomer types.

[0121] 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.

[0122] 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.

[0123] As used herein, the term "reaction mixture" refers to a mixture comprising one or more monomer types and at least one metal complex. Typically, the reaction mixture also comprises a solvent, one or more co-catalysts and hydrogen (H2).

[0124] As used herein, the term "total catalyst efficiency (units of 10^6 g polymer composition / g total catalyst metal)" with reference to a polymerization process refers to the production rate (e.g., lb / hr) of the polymer composition formed during a polymerization process (or polymerization run) divided by the total feed rate (e.g., lb / hr) of the catalyst metal (e.g., metal from one or more metal complexes) used during the same polymerization process (or polymerization run). Typically, polymerization is a steady-state process.

[0125] 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 the components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes from the scope of any subsequently recited component, step, or procedure, except those that are not essential to operability. The term "consisting of excludes any component, step, or procedure not specifically recited or listed.

[0126] List of some composition features

[0127] A] A method for preparing an alpha composition comprising a first ethylene / α-olefin / interpolymer portion and a second ethylene / α-olefin / interpolymer portion; the method comprising polymerizing a reaction mixture in one reactor, the reaction mixture comprising ethylene, an α-olefin, a metal complex selected from the following a) and a metal complex selected from the following b):

[0128] a) a biphenol metal complex selected from the following structure 1, as described above in the Summary of the Invention (SOI):

[0129]

[0130] b) a biphenol metal complex selected from structure 2, as described above in SOI:

[0131]

[0132] B] According to the method of A] above, wherein for structure 1, -Z 1 -and-Z 2 Each of - is -O-.

[0133] C] According to the method of A] or B] above, wherein for structure 2, -Z 1 -and-Z 2 Each of - is -O-.

[0134] D] A method according to any one of A]-C] (A] to C]) above, wherein for structure 1, R 1 and R 8 At least one of is a group having formula (I), a group having formula (II), or a group having formula (III).

[0135] E] A method according to any one of A] to D] above, wherein for structure 2, R 1 and R 8 At least one of is a group having formula (I), a group having formula (II), or a group having formula (III).

[0136] F] A method according to any one of A] to D] above, wherein for structure 1, R 1 and R 8 are the same and are selected from the group consisting of a group having formula (I), a group having formula (II) and a group having formula (III).

[0137] G] A method according to any one of A] to F] above, wherein for structure 2, R 1 and R 8 are the same and are selected from the group consisting of a group having formula (I), a group having formula (II) and a group having formula (III).

[0138] H] A method according to any one of A] to G] above, wherein for structure 1, R 1 and R 8 At least one of the following is selected from a group having formula (I) or a group having formula (II), and further R 1 or R 8 are selected from the group having the formula (II) or the group having the formula (I).

[0139] I] A method according to any one of A] to H] above, wherein for structure 2, R 1 and R 8 At least one of the following is selected from a group having formula (I) or a group having formula (II), and further R 1 or R 8 are selected from the group having the formula (II) or the group having the formula (I).

[0140] J] A method according to any one of A] to I] above, wherein for structure 1, R 1 =R 8 = a group having the formula (II).

[0141] K] The method according to J] above, wherein for formula (II) of structure 1, R 43 =R 46 = unsubstituted alkyl or H, further unsubstituted (C1-C 10)alkyl or H, further is unsubstituted (C1-C8)alkyl or H, further is unsubstituted (C1-C6)alkyl or H, further is unsubstituted (C1-C4)alkyl or H, further is tert-butyl or H.

[0142] L] The method according to J] or K] above, wherein for formula (II), R 43 =R 46 = unsubstituted alkyl, further unsubstituted (C1-C 10 )alkyl, further is unsubstituted (C1-C8)alkyl, further is unsubstituted (C1-C6)alkyl, further is unsubstituted (C1-C4)alkyl, further is tert-butyl.

[0143] M] According to the method described in any one of J] to L] above, wherein for formula (II), R 41 =R 42 =R 44 =R 45 =R 47 =R 48 =H.

[0144] N] A method according to any one of A] to M] above, wherein for structure 2, R 1 =R 8 = a group having the formula (II).

[0145] O] The method according to N] above, wherein for formula (II) of structure 2, R 43 =R 46 = unsubstituted alkyl, further unsubstituted (C1-C 10 )alkyl, further is unsubstituted (C1-C8)alkyl, further is unsubstituted (C1-C6)alkyl, further is unsubstituted (C1-C4)alkyl, further is tert-butyl.

[0146] P] According to the method described in N] or O] above, wherein for formula (II), R 41 =R 42 =R 44 =R 45 =R 47 =R 48 =H.

[0147] Q] A method according to any one of A] to P] above, wherein for Structure 1, L is selected from the following:

[0148] i)-CH2Si(R a )(R b )CH2- or -CH2Ge(R a )(Rb )CH2-, where R a and R b Each independently is (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl;

[0149] ii) 1,3-dimethylpropane-1,3-diyl;

[0150] iii) bis(methylene)cyclohexane-1,2-diyl;

[0151] iv) propan-1,3-diyl; or

[0152] iv) butane-1,4-diyl.

[0153] R] A method according to any one of A] to Q] above, wherein for Structure 1, L is selected from the following:

[0154] i)-CH2Si(R a )(R b )CH2-, where R a and R b are each independently unsubstituted (C1-C 10 )alkyl, further unsubstituted (C1-C8)alkyl, further unsubstituted (C1-C6)alkyl, further unsubstituted (C1-C4)alkyl, further unsubstituted (C1-C3)alkyl;

[0155] ii) 1,3-dimethylpropane-1,3-diyl; or

[0156] iii) Bis(methylene)cyclohexane-1,2-diyl.

[0157] S] A method according to any one of A] to R] above, wherein for Structure 2, Y is selected from the following:

[0158] i)-SiR c R d -or-GeR c R d -, where R c and R d Each independently is (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl;

[0159] ii)-(CH2) n -, wherein n=0 to 2, further n=1 or 2, further n=1; or

[0160] iii)-CR a Rb -, where R a and R b Each independently is (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0161] T] A method according to any one of A] to S] above, wherein for Structure 2, Y is selected from the following:

[0162] i)-SiR c R d -or-GeR c R d -, where R c and R d are each independently unsubstituted (C1-C 10 )alkyl, further unsubstituted (C1-C8)alkyl, further unsubstituted (C1-C6)alkyl, further unsubstituted (C1-C4)alkyl, further unsubstituted (C1-C3)alkyl;

[0163] ii)-(CH2) n -, wherein n=0 to 2, further n=1 or 2, further n=1; or

[0164] iii)-CR a R b -, where R a and R b are each independently H or unsubstituted (C1-C 10 )alkyl, further H or unsubstituted (C1-C8)alkyl, further H or unsubstituted (C1-C6)alkyl, further H or unsubstituted (C1-C4)alkyl.

[0165] U] A method according to any one of A] to T] above, wherein for Structure 2, Y is selected from the following:

[0166] ii)-(CH2) n -, wherein n=0 to 2, further n=1 or 2, further n=1; or

[0167] iii)-CR a R b -, where R a and R b are each independently H or unsubstituted (C1-C 10 )alkyl, further H or unsubstituted (C1-C8)alkyl, further H or unsubstituted (C1-C6)alkyl, further H or unsubstituted (C1-C4)alkyl.

[0168] V] A method according to any one of A] to U] above, wherein for structure 1, n=2, and each X is the same and is an unsubstituted alkyl group.

[0169] W] The method according to V] above, wherein each X is an unsubstituted (C1-C3) alkyl group, further an unsubstituted (C1-C2) alkyl group, further a methyl group.

[0170] X] A method according to any one of A] to W] above, wherein for Structure 1, R10 = R15.

[0171] Y] A method according to any one of A] to X] above, wherein for structure 1, R10=R15=H or halogen, and further H or F.

[0172] Z] A method according to any one of A] to Y] above, wherein for structure 1, R10=R15=halogen, and further is F.

[0173] AA] A method according to any one of A] to Z] above, wherein for Structure 1, R3 = R6.

[0174] BB] A method according to any one of A] to AA] above, wherein for structure 1, R3 = R6 = unsubstituted alkyl.

[0175] CC] A method according to any one of A] to BB] above, wherein for structure 1, R3 = R6 = unsubstituted (C1-C 12 ) alkyl, further unsubstituted (C1-C 10 )alkyl, further is unsubstituted (C1-C8)alkyl, further is methyl or unsubstituted C8 alkyl.

[0176] DD] A method according to any one of A] to CC] above, wherein for Structure 1, R2=R4=R5=R7=R9=R11=R12=R13=R14=R16=H.

[0177] EE] A method according to any one of A] to DD] above, wherein for structure 2, n=2, and each X is the same and is an unsubstituted alkyl group.

[0178] FF] The method according to EE] above, wherein each X is an unsubstituted (C1-C3) alkyl group, further an unsubstituted (C1-C2) alkyl group, further a methyl group.

[0179] GG] A method according to any one of A] to FF] above, wherein for Structure 2, R10 = R15.

[0180] HH] A method according to any one of A] to GG] above, wherein for structure 2, R10=R15=halogen, and further is F.

[0181] II] A method according to any one of A] to HH] above, wherein for Structure 2, R3 = R6.

[0182] JJ] A method according to any one of A] to II] above, wherein for structure 2, R3 = R6 = unsubstituted alkyl.

[0183] KK] A method according to any one of A] to JJ] above, wherein for Structure 2, R3 = R6 = unsubstituted (C1-C 12 ) alkyl, further unsubstituted (C1-C 10 )alkyl, further is unsubstituted (C2-C8)alkyl, further is unsubstituted (C4-C8)alkyl, further is unsubstituted C8 alkyl.

[0184] LL] A method according to any one of A] to KK] above, wherein for Structure 2, R2=R4=R5=R7=R9=R11=R12=R13=R14=R16=H.

[0185] MM] A method according to any one of A] to LL] above, wherein for Structure 2, metal M = Zr.

[0186] NN] A method according to any one of A]-MM] above, wherein Structure 1 is selected from the following structures (1a)-(1c), each of which is described in the above Detailed Description (DDI).

[0187] OO] The method according to NN] above, wherein Structure 1 is Structure (1a) as described in DDI above.

[0188] PP] The method according to any one of A] to OO] above, wherein Structure 2 is selected from the following structures (2a) or (2b) each described in DDI above.

[0189] QQ] According to the method described above PP], wherein Structure 2 is Structure (2b) as described above in DDI.

[0190] RR] The method according to A]-QQ] above, wherein the total catalyst efficiency of the method at a reactor temperature of ≥150°C, or ≥155°C, or ≥160°C, or ≥165°C is ≥2.8×10 6 , or ≥3.0×10 6 , or ≥3.2×10 6 , or ≥3.4×106 , or ≥3.6×10 6 [(g alpha composition) / (g total catalyst metal)].

[0191] SS] The method according to A]-RR] above, wherein the method is 0.855 to 0.890 g / cc, or 0.860 to 0.890 g / cc, or 0.865 to 0.890 g / cc, or 0.865 to 0.885 g / cc (1 cc = 1 cm 3 The total catalyst efficiency at the α composition density of ≥2.8×10 6 , or ≥3.0×10 6 , or ≥3.2×10 6 , or ≥3.4×10 6 , or ≥3.6×10 6 [(g alpha composition) / (g total catalyst metal)].

[0192] TT] A process according to A] - SS] above, wherein the process is operated at a reactor temperature of ≥ 150°C, or ≥ 155°C, or ≥ 160°C, or ≥ 165°C.

[0193] UU] A process according to any one of A] to TT] (A] to TT]) above, wherein the mass flow ratio of (hydrogen reactor feed) to (ethylene reactor feed) is ≥ 0.01×10 -4g / g, or ≥0.05×10 -4g / g, or ≥0.10×10 -4g / g, or ≥0.20×10 -4g / g, or ≥0.40×10 -4g / g, or ≥0.60×10 -4g / g, or ≥0.70×10 -4g / g.

[0194] VV] A process according to any one of A] to UU] above, wherein the mass flow ratio of (hydrogen reactor feed) to (ethylene reactor feed) is ≤ 6.00 × 10 -4g / g, or ≤5.50×10 -4g / g, or ≤5.00×10 -4g / g, or ≤4.50×10 -4g / g.

[0195] WW] The process according to any one of A] to VV] above, wherein the reactor is selected from a continuous stirred tank reactor, a loop reactor or a plug flow reactor (or a tubular reactor), further selected from a continuous stirred tank reactor or a loop reactor, and further selected from a continuous stirred tank reactor.

[0196] XX] The method according to any one of A] to WW] above, wherein the reaction mixture further comprises a solvent.

[0197] YY] A process according to any one of A] to XX] above, wherein the reaction mixture further comprises one or more co-catalysts.

[0198] ZZ] A method according to any one of A] to YY] above, wherein the reaction mixture further comprises hydrogen (H2).

[0199] A3] A method according to any one of A] to ZZ] above, wherein the method is a solution polymerization method.

[0200] B3] A composition comprising the α composition formed by the method described in any one of A] to A3] above.

[0201] C3] A composition according to B3] above, wherein the α composition comprises the following characteristics:

[0202] i) Mz / Mn ≥ 8.0,

[0203] ii) a density of 0.855 to 0.890 g / cc,

[0204] iii) V100 (190°C) ≤ 600 Pa·s, and

[0205] iv)V0.1(190℃)≥4,000Pa·s.

[0206] D3] A composition comprising an alpha composition comprising a first ethylene / α-olefin interpolymer portion and a second ethylene / α-olefin interpolymer portion, and wherein the alpha composition comprises the following characteristics:

[0207] i) Mz / Mn ≥ 8.0,

[0208] ii) a density of 0.855 to 0.890 g / cc,

[0209] iii) V100 (190°C) ≤ 600 Pa·s, and

[0210] iv)V0.1(190℃)≥4,000Pa·s.

[0211] E3] A composition according to any one of B3] to D3] above, wherein the Mz / Mn of the α composition is ≥8.2, or ≥8.4, or ≥8.6, or ≥8.8, or ≥9.0, or ≥10.0, or ≥12.0, or ≥14.0, or ≥16.0.

[0212] F3] A composition according to any one of B3] to E3] above, wherein the Mz / Mn of the α composition is ≤60.0, or ≤55.0, or ≤50.0, or ≤40.0.

[0213] G3] A composition according to any one of B3] to F3] above, wherein the density of the α composition is ≥0.856 g / cc, or ≥0.857 g / cc, or ≥0.858 g / cc, or ≥0.859 g / cc, or ≥0.860 g / cc, or ≥0.861 g / cc, or ≥0.862 g / cc, or ≥0.863 g / cc, or ≥0.864 g / cc, or ≥0.865 g / cc, or ≥0.866 g / cc.

[0214] H3] A composition according to any one of B3] to G3] above, wherein the density of the α composition is ≤0.889 g / cc, or ≤0.888 g / cc, or ≤0.887 g / cc, or ≤0.886 g / cc, or ≤0.885 g / cc, or ≤0.884 g / cc, or ≤0.883 g / cc, or ≤0.882 g / cc (1 cc = 1 cm 3 ).

[0215] I3] A composition according to any one of B3] to H3] above, wherein the V100 (100 rad / s, 190°C) of the α composition is ≥100 Pa·s, or ≥120 Pa·s, or ≥140 Pa·s, or ≥160 Pa·s, or ≥180 Pa·s, or ≥200 Pa·s, or ≥220 Pa·s.

[0216] J3] A composition according to any one of B3] to I3] above, wherein the V100 (100 rad / s, 190°C) of the α composition is ≤580 Pa·s, or ≤570 Pa·s, or ≤560 Pa·s, or ≤550 Pa·s, or ≤540 Pa·s, or ≤530 Pa·s, or ≤520 Pa·s.

[0217] K3] A composition according to any one of B3] to J3] above, wherein V0.1 (0.1 rad / s, 190°C) of the α composition is ≥4,100 Pa·s, or ≥4,200 Pa·s, or ≥4,300 Pa·s, or ≥4,400 Pa·s.

[0218] L3] A composition according to any one of B3] to K3] above, wherein the V0.1 (0.1 rad / s, 190°C) of the α composition is ≤28,000 Pa·s, or ≤26,000 Pa·s, or ≤24,000 Pa·s, or ≤22,000 Pa·s, or ≤20,000 Pa·s, or ≤18,000 Pa·s.

[0219] M3] A composition according to any one of B3] to L3] above, wherein the rheological ratio (V0.1 / V100, 190°C) of the α composition is ≥7.00, or ≥7.50, or ≥8.00, or ≥8.50.

[0220] N3] A composition according to any one of B3] to M3] above, wherein the rheological ratio (V0.1 / V100, 190°C) of the α composition is ≤64.0, or ≤62.0, or ≤60.0, or ≤58.0, or ≤56.0.

[0221] O3] A composition according to any one of B3] to N3] above, wherein the melt index (I2) of the α composition is ≥0.5 g / 10 min, ≥1.0 g / 10 min, or ≥1.1 g / 10 min, or ≥1.2 g / 10 min, or ≥1.3 g / 10 min, or ≥1.4 g / 10 min, or ≥1.5 g / 10 min.

[0222] P3] A composition according to any one of B3] to O3] above, wherein the melt index (I2) of the α composition is ≤50 g / 10 min, or ≤40 g / 10 min, or ≤30 g / 10 min, or ≤25 g / 10 min, or ≤20 g / 10 min, or ≤18 g / 10 min, or ≤16 g / 10 min, or ≤14 g / 10 min, or ≤12 g / 10 min, or ≤10 g / 10 min, or ≤8.0 g / 10 min.

[0223] Q3] A composition according to any one of B3] to P3] above, wherein the I10 / I2 of the α composition is ≥6.0, or ≥6.5, or ≥7.0, or ≥7.5, or ≥8.0, or ≥8.5, or ≥9.0, or ≥9.5, or ≥10.0, or ≥10.5, or ≥11.0, or ≥11.5, or ≥12.0, or ≥12.5, or ≥13.0.

[0224] R3] A composition according to any one of B3] to Q3] above, wherein the I10 / I2 of the α composition is ≤40.0, or ≤35.0, or ≤32.0, or ≤30.0, or ≤28.0, or ≤26.0, or ≤24.0.

[0225] S3] A composition according to any one of B3] to R3] above, wherein the number average molecular weight Mn of the α composition is ≥10,000 g / mol, or ≥12,000 g / mol, or ≥14,000 g / mol.

[0226] T3] A composition according to any one of B3] to S3] above, wherein the number average molecular weight Mn of the α composition is ≤50,000 g / mol, or ≤45,000 g / mol, or ≤40,000 g / mol, or ≤36,000 g / mol, or ≤34,000 g / mol, or ≤32,000 g / mol, or ≤30,000 g / mol.

[0227] U3] A composition according to any one of B3] to T3] above, wherein the weight average molecular weight Mw of the α composition is ≥60,000 g / mol, or ≥65,000 g / mol, or ≥70,000 g / mol, or ≥75,000 g / mol, or ≥80,000 g / mol, or ≥85,000 g / mol.

[0228] V3] A composition according to any one of B3] to U3] above, wherein the weight average molecular weight Mw of the α composition is ≤150,000 g / mol, or ≤145,000 g / mol, or ≤140,000 g / mol, or ≤135,000 g / mol, or ≤130,000 g / mol, or ≤125,000 g / mol, or ≤120,000 g / mol.

[0229] W3] A composition according to any one of B3] to V3] above, wherein the z-average molecular weight Mz of the α composition is ≥190,000 g / mol, or ≥200,000 g / mol, or ≥205,000 g / mol, or ≥210,000 g / mol, or ≥215,000 g / mol, or ≥220,000 g / mol, or ≥225,000 g / mol, or ≥230,000 g / mol, or ≥235,000 g / mol, or ≥240,000 g / mol, or ≥245,000 g / mol.

[0230] X3] A composition according to any one of B3] to W3] above, wherein the z-average molecular weight Mz of the α composition is ≤600,000 g / mol, or ≤580,000 g / mol, or ≤560,000 g / mol, or ≤540,000 g / mol, or ≤520,000 g / mol, or ≤500,000 g / mol, or ≤490,000 g / mol.

[0231] Y3] A composition according to any one of B3] to X3] above, wherein the molecular weight distribution MWD (=Mw / Mn) of the α composition is ≥3.00, or ≥3.05, or ≥3.10, or ≥3.15, or ≥3.20, or ≥3.25, or ≥3.50, or ≥4.00, or ≥4.20, or ≥4.40.

[0232] Z3] A composition according to any one of B3] to Y3] above, wherein the molecular weight distribution MWD (=Mw / Mn) of the α composition is ≤10.0, or ≤9.00, or ≤8.00, or ≤7.50, or ≤7.00, or ≤6.80, or ≤6.60, or ≤6.50, or ≤6.40, or ≤6.30.

[0233] A4] A composition according to any one of B3] to Z3] above, wherein the melting temperature (Tm, DSC) of the α composition is ≥30°C, or ≥35°C, or ≥40°C, or ≥45°C, or ≥50°C, or ≥51°C, or ≥52°C, or ≥53°C.

[0234] B4] A composition according to any one of B3] to A4] above, wherein the melting temperature (Tm, DSC) of the α composition is ≤100°C, or ≤95°C, or ≤90°C, or ≤85°C, or ≤80°C, or ≤78°C, or ≤76°C, or ≤75°C.

[0235] C4] A composition according to any one of B3] to B4] above, wherein the glass transition temperature (Tg, DSC) of the α composition is ≥-68°C, or ≥-66°C, or -64°C, or ≥-62°C, or ≥-60°C.

[0236] D4] A composition according to any one of B3] to C4] above, wherein the glass transition temperature (Tg, DSC) of the α composition is ≤-42°C, or ≤-44°C, or ≤-46°C, or ≤-48°C.

[0237] E4] A composition according to any one of B3] to D4] above, wherein the crystallization temperature (Tc, DSC) of the α composition is ≥14°C, or ≥16°C, or ≥18°C, or ≥20°C, or ≥22°C.

[0238] F4] A composition according to any one of B3] to E4] above, wherein the crystallization temperature (Tc, DSC) of the α composition is ≤80°C, or ≤78°C, or ≤76°C, or ≤74°C, or ≤72°C, or ≤70°C, or ≤68°C, or ≤66°C.

[0239] G4] A composition according to any one of B3] to F4] above, wherein the α composition has a crystallinity % of ≥14%, or ≥16%, or ≥18%, or ≥20%.

[0240] H4] A composition according to any one of B3] to G4] above, wherein the α composition has a crystallinity % of ≤40%, or ≤35%, or ≤30%, or ≤28%.

[0241] I4] A composition according to any one of B3] to H4] above, wherein the first ethylene / α-olefin interpolymer portion differs from the second ethylene / α-olefin interpolymer portion in one or more polymer properties, and further differs in one or more properties selected from density, I2, I10 / I2, Mn, Mw, Mz, MWD or any combination thereof, and further differs in one or more properties selected from Mn, Mw, Mz, MWD or any combination thereof.

[0242] J4] A composition according to any one of B3] to I4] above, wherein the α composition comprises 50 wt% or a majority weight percentage of polymerized ethylene based on the weight of the α composition.

[0243] K4] A composition according to any one of B3] to J4] above, wherein the α composition comprises ≥98.0wt%, or ≥98.5wt%, or ≥99.0wt%, or ≥99.5wt%, or ≥99.8wt%, or ≥99.9wt% of the sum of the first ethylene / α-olefin interpolymer portion and the second ethylene / α-olefin interpolymer portion, based on the weight of the α composition.

[0244] L4] A composition according to any one of B3] to K4] above, wherein the alpha composition comprises ≤100.0 wt% of the sum of the first ethylene / alpha-olefin interpolymer portion and the second ethylene / alpha-olefin interpolymer portion, based on the weight of the alpha composition.

[0245] M4] A composition according to any one of B3] to L4] above, wherein for the first ethylene / α-olefin interpolymer portion, the α-olefin is C3-C 20 α-olefins, further C3-C 10 α-Olefins.

[0246] N4] A composition according to any one of B3] to M4] above, wherein for the first ethylene / α-olefin interpolymer portion, the α-olefin is selected from propylene, 1-butene, 1-pentene, 1-hexene or 1-octene, and is further selected from propylene, 1-butene or 1-octene, and is further selected from 1-butene or 1-octene, and is further selected from 1-octene.

[0247] O4] A composition according to any one of B3] to N4] above, wherein the first ethylene / α-olefin interpolymer portion is an ethylene / α-olefin copolymer.

[0248] P4] A composition according to any one of B3] to O4] above, wherein the first ethylene / α-olefin interpolymer portion is selected from the following: ethylene / propylene copolymers, ethylene / butene copolymers or ethylene / octene copolymers, and is further selected from ethylene / butene copolymers or ethylene / octene copolymers, and is further selected from ethylene / octene copolymers.

[0249] Q4] A composition according to any one of B3] to P4] above, wherein for the second ethylene / α-olefin interpolymer portion, the α-olefin is C3-C 20 α-olefins, further C3-C 10 α-Olefins.

[0250] R4] A composition according to any one of B3] to Q4] above, wherein for the second ethylene / α-olefin interpolymer portion, the α-olefin is selected from propylene, 1-butene, 1-pentene, 1-hexene or 1-octene, and is further selected from propylene, 1-butene or 1-octene, and is further selected from 1-butene or 1-octene, and is further selected from 1-octene.

[0251] S4] A composition according to any one of B3] to R4] above, wherein the second ethylene / α-olefin interpolymer portion is an ethylene / α-olefin copolymer.

[0252] T4] A composition according to any one of B3] to S4] above, wherein the second ethylene / α-olefin interpolymer portion is selected from the following: ethylene / propylene copolymers, ethylene / butene copolymers or ethylene / octene copolymers, and is further selected from ethylene / butene copolymers or ethylene / octene copolymers, and is further selected from ethylene / octene copolymers.

[0253] U4] A composition according to any one of B3] to T4] above, wherein the composition comprises ≥50.0wt%, or ≥55.0wt%, or ≥60.0wt%, or ≥65.0wt%, or ≥70.0wt%, or ≥75.0wt%, or ≥80.0wt%, or ≥85.0wt%, or ≥90.0wt% of the α composition, based on the weight of the composition.

[0254] V4] A composition according to any one of B3] to U4] above, wherein the composition comprises ≥95.0wt%, or ≥95.5wt%, or ≥96.0wt%, or ≥96.5wt%, or ≥97.0wt%, or ≥97.5wt%, or ≥98.0wt%, or ≥98.5wt% of the α composition, based on the weight of the composition.

[0255] W4] A composition according to any one of B3] to V4] above, wherein the composition comprises ≤99.8wt%, ≤99.6wt%, or ≤99.4wt%, or ≤99.2wt%, or ≤99.0wt%, or ≤98.8wt% of the α composition, based on the weight of the composition.

[0256] X4] A composition according to any one of UU] to W4] above, wherein the composition further comprises at least one additive selected from UV stabilizers, antioxidants or combinations thereof.

[0257] Y4] A composition according to any one of B3] to X4] above, wherein the weight ratio of the first ethylene / α-olefin interpolymer portion to the second ethylene / α-olefin interpolymer portion is ≥0.20, or ≥0.22, or ≥0.24, or ≥0.26, or ≥0.28, or ≥0.30, or ≥0.32, or ≥0.34, or ≥0.36, or ≥0.38, or ≥0.39, or ≥0.40, or ≥0.42, or ≥0.44, or ≥0.46, or ≥0.48.

[0258] Z4] A composition according to any one of B3] to Y4] above, wherein the weight ratio of the first ethylene / α-olefin interpolymer portion to the second ethylene / α-olefin interpolymer portion is ≤2.00, or ≤1.80, or ≤1.50, or ≤1.40, or ≤1.30, or ≤1.25, or ≤1.20, or ≤1.15, or ≤1.10.

[0259] A5] A composition according to any one of B3] to Z4] above, wherein the number average molecular weight Mn of the first ethylene / α-olefin interpolymer portion is ≥40,000 g / mol, or ≥42,000 g / mol, or ≥44,000 g / mol, or ≥46,000 g / mol, or ≥48,000 g / mol, or ≥50,000 g / mol 52,000 g / mol, or ≥54,000 g / mol, or ≥56,000 g / mol, or ≥58,000 g / mol.

[0260] B5] A composition according to any one of B3] to A5] above, wherein the number average molecular weight Mn of the first ethylene / α-olefin interpolymer portion is ≤150,000 g / mol, or ≤145,000 g / mol, or ≤140,000 g / mol, or ≤135,000 g / mol, or ≤130,000 g / mol.

[0261] C5] A composition according to any one of B3] to B5] above, wherein the number average molecular weight Mn of the second ethylene / α-olefin interpolymer portion is ≥6,000 g / mol, or ≥7,000 g / mol, or ≥8,000 g / mol, or ≥9,000 g / mol, or ≥10,000 g / mol, or ≥11,000 g / mol.

[0262] D5] A composition according to any one of B3] to C5] above, wherein the number average molecular weight Mn of the second ethylene / α-olefin interpolymer portion is ≤35,000 g / mol, or ≤30,000 g / mol, or ≤28,000 g / mol, or ≤26,000 g / mol, or ≤24,000 g / mol.

[0263] E5] A composition according to any one of B3] to D5] above, wherein the ratio [Mn( 第一乙烯 / α-烯烃互聚物部分 ) / Mn( 第二乙烯 / α-烯烃互聚物部分 )] is ≥2.0, or ≥2.2, or ≥2.4, or ≥2.6, or ≥2.8, or ≥3.0, or ≥3.2, or ≥3.4.

[0264] F5] A composition according to any one of B3] to E5] above, wherein the ratio [Mn( 第一乙烯 / α-烯烃互聚物部分 ) / Mn( 第二乙烯 / α-烯烃互聚物部分 )] is ≤12.0, or ≤11.5, or ≤11.0, or ≤10.8, or ≤10.6, or ≤10.4, or ≤10.2, or ≤10.0.

[0265] G5] A cross-linked composition, which is formed from the composition according to any one of B3] to F5] above.

[0266] H5] An article comprising at least one component formed from the composition according to any one of B3] to G5] above.

[0267] I5] The article according to H5] above, wherein the article is a film, and further an extruded film.

[0268] J5] The article according to H5] above, wherein the article is a solar cell module.

[0269] K5] A method according to any one of A] to A3] above, wherein for structure 2, Y is -(CH2) n -, wherein n=0 to 2, further n=1 or 2, further n=1; -CR a R b -, where R a and R b Each independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl or -H; -Ge(R D )2- or -Si(R D )2-, where each R D Independently selected from the group consisting of: -H, (C1-C 40 ) alkyl and (C1-C 40 ) heteroalkyl.

[0270] Test Method

[0271] Small Amplitude Oscillatory Shear (SAOS)

[0272] The rheological properties of each composition were analyzed by SAOS (or DMS) using an ARES-G2 rheometer equipped with a "25 mm diameter" stainless steel parallel plate under nitrogen purge. Constant temperature dynamic frequency sweeps were performed at 190° C. in the range of 0.1 to 100 rad / s or 500 rad / s. The data at 190° C. were used to evaluate the processability of the composition.

[0273] A sample of approximately "25 mm diameter x 3.3 mm thick" was cut from a compression molded disc (see below). The sample was placed on the lower plate and allowed to melt for five minutes. The disc was then closed to a gap of "2.0 mm" and the sample was trimmed to a diameter of "25 mm". The sample was allowed to reach thermal equilibrium for five minutes before starting the test. The complex viscosity is measured at a constant strain amplitude (e.g., 10%) that is well within the linear viscoelastic range. The stress response is analyzed based on amplitude and phase, from which the storage modulus (G'), loss modulus (G"), dynamic viscosity η* and tanδ can be calculated. Each compression molded disc was formed in ambient atmosphere at 180°C and 10MPa molding pressure for five minutes, and then quenched between cold press plates (15-20°C) for two minutes. Record the viscosity (V0.1, V1.0, V100, each at 190°C).

[0274] Gel Permeation Chromatography

[0275] The chromatographic system consists of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment is set at 160°C and the column compartment is set at 150°C. The columns are four Agilent "Mixed A" 30cm 20 micron linear mixed bed columns. The chromatographic solvent is 1,2,4-trichlorobenzene containing 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0276] The GPC column set was calibrated with 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 molecular weights and arranged in six "cocktail" mixtures with at least ten times intervals between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, "0.025 grams of polystyrene standards were prepared in 50 milliliters of solvent," and for molecular weights less than 1,000,000, "0.05 grams of polystyrene standards were prepared in 50 milliliters of solvent." The polystyrene standards were dissolved at 80 degrees Celsius with gentle stirring for 30 minutes. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0277] M 聚乙烯 =A×(M 聚苯乙烯 ) B (EQ1), where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0278] A fifth order polynomial was used to fit the calibration points to the corresponding polyethylene equivalents.A small adjustment to A (from about 0.375 to 0.445) was made to correct for column resolution and band broadening effects such that a linear homopolymer polyethylene standard was obtained at 120,000 Mw.

[0279] Total plate counts for the GPC column set were performed using decane (prepared as 0.04 g in 50 ml TCB and dissolved for 20 minutes under slow stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured at 200 microliter injections according to the following equations:

[0280] Where RV is the retention volume in milliliters, peak width is in milliliters, peakmax is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the peakmax.

[0281] Where RV is the retention volume in milliliters, and peak width is in milliliters, peakmax is the maximum peak position, tenth height is 1 / 10 the height of the maximum peak, and where postpeak refers to the tail of the peak at a later retention volume than the maximum peak, and where prepeak refers to the front of the peak at an earlier retention volume than the maximum peak. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0282] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set at 2 mg / ml and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen by the PolymerChar high temperature autosampler. The samples were dissolved at 160°C for two hours under "low speed" shaking.

[0283] Based on the GPC results, the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer was used, according to Equations 4-6, using the PolymerChar GPCOne TM The software was used to calculate the Mn using the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation of. Equation 4-6 is as follows:

[0284] and

[0285]

[0286] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (nominal)) of each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the RV of the decane peak in the narrow standard calibration (RV (FM calibrated)). It was then assumed that any change in the time of the decane marker peak was related to a linear change in the flow rate (flow rate (effective)) of the entire run. In order to facilitate the highest accuracy of the RV measurement of the flow marker peak, the peak of the flow marker concentration chromatogram was fitted to a quadratic equation using a least squares fitting procedure. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated by equation 7: flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (EQ7).

[0287] By PolymerChar GPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.7% of the nominal flow rate.

[0288] GPC deconvolution

[0289] The GPC data is deconvoluted to give the most likely fit values ​​for the 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). In order to allow for changes in the basic distribution, due to the incorporation of small fluctuations in macromonomers and reactor conditions (i.e., temperature, concentration), the basis functions are modified to incorporate normal distribution terms. This term allows the basis functions of each component to be "smeared" to varying degrees along the molecular weight axis. The advantage is that in the limit (low LCB, perfect concentration and temperature control), the basis function will become a simple, most likely Flory distribution.

[0290] Three components (j=1, 2, 3) are derived, where the third component (j=3) is an adjustable error term. The GPC data must be normalized and properly converted to a "weight fraction versus Log10 molecular weight" vector. In other words, each deconvoluted potential curve should consist of a height vector h i composition, where the height is reported in known intervals of "Log10 molecular weight", the h i The values ​​have been appropriately converted from the elution volume domain to the "Log10 molecular weight" domain, and h iThe values ​​are normalized. In addition, these data should be available for use with the Microsoft EXCEL application. Several assumptions are made in the deconvolution. Each component j consists of the most likely Flory distribution, which has been extended by a normal or Gaussian function with parameter σ j The convolution is performed. The three basis functions obtained are used for Chi-square, X 2 In the GPC data vector h i A minimization routine for locating the parameters of the most optimal fit to n points.

[0291]

[0292] Use the EXCEL function "NORMDIST(x, mean, standard deviation, cumulative value)" to calculate the variable CumND j,k , where the parameters are set as follows: x = μ j +(k-10)*σ j / 3; average value = μ j ; Standard deviation = σ j ; Cumulative value = TRUE. Table A below summarizes these variables and their definitions. The EXCEL software application SOLVER is sufficient to accomplish this task. Constraints are added to SOLVER to ensure proper minimization.

[0293] Table A: Variable definitions

[0294] Variable Name definition <![CDATA[λ j,k ]]> The reciprocal of the number average molecular weight of the most likely (Flory) distribution of component j (normal distribution slice k) <![CDATA[σ j ]]> Sigma (square root of variance) of the normal (Gaussian) spread function of component j. <![CDATA[w j ]]> Weight fraction of component j K <![CDATA[Normalization term (1.0 / Log e 10)]]> <![CDATA[M i ]]> Molecular weight of elution volume slice i <![CDATA[h i ]]> <![CDATA[log at slice i 10 (molecular weight) height of the graph]]> n Number of slices in log molecular weight plot i Logarithmic molecular weight slice index (1 to n) j Component index (1 to 3) k Normal distribution slice index <![CDATA[Δlog 10 M]]> <![CDATA[Height relative to log 10 log in Figure M 10 M i and log 10 M i-1 Average difference between]]>

[0295] The eight parameters derived from the chi-square minimization are μ1, μ2, μ3, σ1, σ2, σ3, w1, and w2. The term w3 is then derived from w1 and w2 because the sum of the three components must equal "1". Table B summarizes the SOLVER constraints used in the EXCEL program.

[0296] Table B: Summary of constraints

[0297] describe constraint Maximum value of fraction 1 <![CDATA[w1 < 0.95 (user adjustable)]]> Lower bound of expansion function <![CDATA[σ1,σ2,σ3>0.001 (must be positive)]]> Upper limit of extension function <![CDATA[σ1, σ2, σ3 < 0.2 (user adjustable)]]> Normalized score <![CDATA[w1+w2+w3=1.0]]>

[0298] Other constraints that should be understood include the following restrictions: only μ j > 0, but if SOLVER is properly initialized, then this constraint does not need to be entered because the SOLVER routine will not convert any μ j moves to a value less than about 0.005. In addition, w j All should be interpreted as positive. This constraint can be handled outside of SOLVER. jUnderstood to be generated by selecting two points along the interval 0.0 < P1 < P2 < 1.0; where w1 = P1, w2 = P2 - P1 and w3 = 1.0 - P2; then the constraints on P1 and P2 are equivalent to the above w j The required constraints. Table C is an overview of the SOLVER settings under the Options tab.

[0299] Table C: Solver settings

[0300] mark Value or selection mark Value or selection Maximum time (seconds) 1000 Estimated value Tangent Iteration 100 Derivative Forward Accuracy 0.000001 search Newton tolerance(%) 5 All other options Not selected convergence 0.001

[0301] Initial estimates of the values of μ1, μ2, w1, and w2 can be obtained by assuming two ideal Flory components that give the observed weight-average molecular weight, number-average molecular weight, and z-average molecular weight for the observed GPC distribution.

[0302]

[0303]

[0304]

[0305] w1 + w2 = 1

[0306] Next, calculate the values of μ1, μ2, w1, and w2. These values should be carefully adjusted before inputting into the SOLVER for the minimization step to make the error term w3 small and satisfy the constraints in Table B. σ j The starting values of all are set to 0.05.

[0307] Differential Scanning Calorimetry (DSC)

[0308] Differential scanning calorimetry (DSC) is used to measure Tm, Tc, Tg and crystallinity in ethylene-based (PE) samples and propylene-based (PP) samples. Each sample (0.5 g) is compression molded into a film at 5000 psi, 190 ° C for two minutes. About 5 to 8 mg of the film sample is weighed and placed in a DSC pan. The lid is screwed on the pan to ensure a closed atmosphere. The sample pan is placed in a DSC unit and then heated to a temperature of 180 ° C for PE (for PP, heated to 230 ° C) at a rate of about 10 ° C / minute. The sample is kept at this temperature for three minutes. Then, the sample is cooled to -90 ° C (for PP, cooled to -60 ° C) at a rate of 10 ° C / minute for PE, and isothermally maintained at the temperature for three minutes. The sample is then heated at a rate of 10 ° C / minute until it is completely melted (second heating). Unless otherwise stated, the melting point (Tm) and glass transition temperature (Tg) of each polymer are determined from the second heating curve, and the crystallization temperature (Tc) is determined from the first cooling curve. The corresponding peak temperatures of Tm and Tc are recorded. The percentage of crystallinity can be calculated by dividing the heat of fusion (Hf) determined from the second heating curve by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this number by 100 (e.g., % crystallinity = (Hf / 292 J / g) × 100 (for PE)).

[0309] Melt index

[0310] The melt index I2 of ethylene-based polymers is measured according to ASTM D-1238 at 190°C / 2.16kg (melt index I5 is measured at 190°C / 5.0kg, melt index I10 is measured at 190°C / 10.0kg, and high load melt index I21 is measured at 190°C / 21.0kg). The melt flow rate (MFR) of propylene-based polymers is measured according to ASTM D-1238 at 230°C / 2.16kg.

[0311] Polymer Density Polymer density was measured according to ASTM D-792.

[0312] experiment

[0313] Catalysts, cocatalysts, polymer synthesis (alpha compositions) and properties

[0314] BPP catalysts and suitable cocatalysts are listed in Table 1. Each alpha composition was prepared in a one-gallon polymerization reactor that was full of liquid and operated under steady-state conditions. The catalyst and cocatalyst are listed above. Solvent, hydrogen, catalyst, and cocatalyst were fed into the reactor to produce the alpha composition according to the process conditions outlined in Tables 1A, 1B, and 1C. The solvent was ISOPAR E supplied by ExxonMobil Chemical Company. The reactor temperature was measured at or near the reactor outlet. Overall properties are shown in Tables 2-4, and the molecular weight properties of the interpolymer portion are shown in Table 5.

[0315] Table 1: Catalysts and co-catalysts

[0316]

[0317] Table 1A: Reactor Conditions

[0318]

[0319] Table 1B: Catalyst Feed Flow Rates and Efficiencies

[0320]

[0321] * "ppm" amounts based on weight of corresponding catalyst feed solution.

[0322] Table 1C: Cocatalyst Feed Flow Rates

[0323]

[0324] * "ppm" amount based on the weight of the co-catalyst feed solution. ** "ppm" amount of Al based on the weight of the co-catalyst feed solution.

[0325] Table 2: Melt index and GPC properties

[0326]

[0327] Table 3: DSC characteristics

[0328]

[0329] *% crystallinity = (Hf / 292 J / g) x 100.

[0330] Table 4: SAOS at 190°C

[0331] α Composition V0.1(Pa·s) V1.0(Pa·s) V100(Pa·s) V0.1 / V100 V1.0 / V100 POE A 4432 2799 510 8.69 5.49 POE B 11088 5181 428 25.9 12.1 POE C 15219 4779 286 53.2 16.7 POE D 4689 2394 230 20.4 10.4 POE E 943 862 228 4.14 3.78 POE F 17164 5795 389 44.1 14.9 Commercial polymers ATEVA 2810A* 2300 1960 437 5.26 4.49 ENGAGE 8457** 3202 2727 900 3.56 3.03

[0332] *ATEVA 2810A, ethylene vinyl acetate from Celanese: density 0.949 g / cc, I2 6 g / 10 min.

[0333] **ENGAGE 8457, polyolefin elastomer from The Dow Chemical Company, ethylene / 1-octene random copolymer: density 0.875 g / cc, I2 3 g / 10 min.

[0334] Table 5: GPC deconvolution

[0335]

[0336] Figure 1 The SAOS (190°C) curves of the α compositions of the present invention (POE A, POE B, POE C, POE F) and two commercial resins (ENGAGE 8457 polyolefin elastomer and ATEVA 2810A (EVA (benchmark resin)) are shown. Figure 1 As seen in Figure 1, the inventive alpha compositions exhibit lower viscosity at high shear rates (at V>10 rad / s) compared to ENGAGE 8457, thereby improving processability, and have higher viscosity at lower shear rates (at V<1 rad / s), thereby improving mechanical strength. Most of the inventive samples also exhibit comparable or better shear thinning than ATEVA 2810A, thereby achieving excellent processability, and all have higher "low shear viscosity". Each of the inventive compositions can be prepared in a cost-effective single reactor synthesis with excellent overall catalyst efficiency.

Claims

1. A method for preparing an alpha composition comprising a first ethylene / α-olefin / interpolymer portion and a second ethylene / α-olefin / interpolymer portion; the method comprising polymerizing a reaction mixture in one reactor, the reaction mixture comprising ethylene, an α-olefin, a metal complex selected from the following a) and a metal complex selected from the following b): a) a biphenol metal complex selected from the following structure 1: Structure 1, wherein: M is a metal selected from zirconium (Zr) or hafnium (Hf), the metal being in a formal oxidation state of +4; n is 2; Each X is an independently selected monodentate ligand; The metal complex is generally charge neutral; -Z 1 -and-Z 2 - is independently selected from -O- or -S-; R 1 and R 8 are independently a group having formula (II): Where R 41–48 Each of which is independently selected from C1-C 40 Hydrocarbyl or H; R 2–7 , R 9–16 Each of which is independently selected from C1-C 40 Hydrocarbyl, halogen or H; L is C1-C 40 Heteroalkylene, the C1-C 40 The heteroalkylene group is a heteroalkyl diradical having 1 to 40 carbon atoms, and each heteroalkyl has one or more heteroatoms, wherein the C1-C 40 The heteroalkylene group has a linker backbone portion including 1 to 10 atoms, connecting the two Z groups in Structure 1, wherein the C1-C 40 Each of the 1 to 10 atoms of the 1 to 10 carbon atoms of the heteroalkylene linker backbone is independently a carbon atom or a heteroatom group, wherein each heteroatom group is independently Si(R C )2 or Ge(R C )2, where independently, each R C C1-C 30 Hydrocarbon or C1-C 30 heteroalkyl; and b) a biphenol metal complex selected from structure 2: M is Zr, the metal being in a formal oxidation state of +4; n is 2; Each X is an independently selected monodentate ligand; The metal complex is generally charge neutral; -Z 1 -and-Z 2 - is independently selected from -O- or -S-; R 1 and R 8 are independently a group having formula (II): Where R 41–48 Each of which is independently selected from C1-C 40 Hydrocarbyl or H; R 2–7 , R 9–16 Each of which is independently selected from C1-C 40 Hydrocarbyl, halogen or H; Y is -(CH2) n -, wherein n = 0 to 2; -CR a R b -, where R a and R b Each independently is C1-C 40 Hydrocarbon, C1-C 40 heteroalkyl or H; and Provided that for either Structure 1 or Structure 2, when R1 and R8 are each a group having formula (II), R 12 and R 13 Not all of them can be halogen groups, where R 43 =R 46 = t-Bu, and R 41-42 =R 44-45 =R 47-48 =H; and The prerequisite is that when structure 1 and structure 2 have the same R group, Z group, X group and Z 1 With Z 2 When the connecting group between them is , these structures do not have the same metal M, so that for one structure M is Hf, then for the other structure M is Zr.

2. The method according to claim 1, wherein for structure 1, R 1 and R 8 for the same.

3. The method according to claim 1 or 2, wherein for structure 2, R 1 and R 8 for the same.

4. The method according to claim 1 or 2, wherein for structure 1, L is: i)-CH2Si(R a )(R b )CH2- or -CH2Ge(R a )(R b )CH2-, where R a and R b Each independently is C1-C 30 Hydrocarbon or C1-C 30 Heteroalkyl.

5. The method according to claim 1 or 2, wherein for Structure 2, Y is selected from the following: i)-(CH2) n -, wherein n=0 to 2; or ii)-CR a R b -, where R a and R b Each independently is C1-C 30 Hydrocarbon, C1-C 30 Heteroalkyl or H.

6. The method according to claim 1 or 2, wherein Structure 1 is selected from the following Structure 1a:

7. The method according to claim 1 or 2, wherein Structure 2 is selected from the following Structure 2a or Structure 2b:

8. The process according to claim 1 or 2, wherein the total catalyst efficiency of the process at a reactor temperature of ≥150°C is ≥2.8×10 6 Grams of alpha composition / gram of total catalyst metal.

9. The process of claim 1 or 2, wherein the process has an overall catalyst efficiency of ≥ 2.8×10 6 Grams of alpha composition / gram of total catalyst metal.

10. The method according to claim 1 or 2, wherein the mass flow ratio of the hydrogen reactor feed to the ethylene reactor feed is ≤6.00×10 -4 g / g.

11. The process according to claim 1 or 2, wherein the process is operated at a reactor temperature of ≥ 150°C.

12. The method according to claim 1 or 2, wherein the alpha composition comprises the following characteristics: i) Mz / Mn ≥ 8.0, ii) a density of 0.855 to 0.890 g / cc, iii) V100 ≤ 600 Pa·s at 190°C, and iv) V0.1 ≥ 4,000 Pa·s at 190°C.

13. The method of claim 12, wherein the alpha composition is cross-linked.

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