PROCESS TO FORM AN OLEFIN-BASED POLYMER

专利摘要:
process for polymerizing olefins. the invention provides a process for forming an olefin-based polymer, said process comprising polymerizing at least one olefin in the presence of at least one catalyst system comprising the reaction product of the following: a) at least one cocatalyst; and b) a procatalyst comprising a metal-ligand complex of formula (i), as described herein: (formula i).
公开号:BR112016029439B1
申请号:R112016029439-4
申请日:2015-06-29
公开日:2022-01-04
发明作者:Philip P. Fontaine；Jerzy Klosin；Endre Szuromi；Carl N. Iverson；Zach T. Rickaway；Andrew J. Young；Susan G. Brown；Ruth Figueroa；Mehmet Demirors；Mridula Kapur
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

BACKGROUND
[001] Olefin-based polymers such as ethylene-based polymers and/or propylene-based polymers are produced through various polymerization processes. Ethylene-based polymers such as polyethylene are known for use in the manufacture of a wide variety of articles. The polyethylene polymerization process can be varied and in myriad ways to produce a wide variety of resulting polyethylene resins having different physical properties that make the various resins suitable for use in different applications. It is generally known that ethylene-based polymers can be produced in solution-phase loop reactors, in which the ethylene monomer and, optionally, one or more alpha-olefin comonomers, typically having from 3 to 10 carbon atoms , are circulated in the presence of one or more catalyst systems, under pressure, around a reactor in a closed circuit, by a circulation pump. The ethylene monomers and, optionally, one or more comonomers, are present in a liquid diluent, such as an alkane or isoalkane. Hydrogen can also be added to the reactor. Catalyst systems for producing ethylene-based polymers can typically comprise a chromium-based catalyst system, a Ziegler Natta catalyst system, and/or a molecular catalyst system (whether metallocene or non-metallocene). However, there is still a need for a polymerization process, exhibiting high reactivity towards hydrogen, and the ability to produce olefin-based polymers under optimal polymerization conditions. These needs have been met by the invention below. SUMMARY OF THE INVENTION
[002] The present invention provides a process for forming an olefin-based polymer, said process comprising polymerizing at least one olefin, in the presence of at least one catalyst system comprising the reaction product of the following (I): A) at least one cocatalyst, and B) a procatalyst comprising a metal-alloy complex of Formula (I):
(Formula I), wherein: M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; en is an integer from 0 to 3, and where when n is 0, X is absent; and each X, independently, is a (C1-C40)hydrocarbyl, a (C1-C40)heterohydrocarbyl, or a halide, and wherein each X, independently, is a monodentate linker that is neutral, monoanionic, or dianionic; or wherein two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and wherein X and n are chosen such that the metal-ligand complex of Formula (I) is generally neutral; and Each Z independently is an oxygen atom, a sulfur atom, -N[(C1-C40)hydrocarbyl]-, or -P[(C1-C40)hydrocarbyl]-; and L is a substituted or unsubstituted (C1-C40)hydrocarbylene, or a substituted or unsubstituted (C1-C40)heterohydrocarbylene, and wherein for L, the (C1-C40)hydrocarbylene has a moiety comprising a chain main linker having 1 carbon to 10 carbon atoms linking R21 and R22 in Formula (I) (to which L is attached), or wherein for L, the (C1-C40)heterohydrocarbylene has a moiety comprising a 1 atom to 10 atom linker backbone linking R21 and R22 in Formula (I), wherein each of 1 to 10 atoms of the 1 atom to 10 atom linker backbone of the (C1-C40)heterohydrocarbylene, independently , is one of the following: i) a carbon atom, ii) a heteroatom, wherein each heteroatom independently is O or S, or iii) a substituent selected from -S(O)-,-S(O)2 -,-Si(RC)2-,-Ge(RC)2-,-P(RC)-, or -N(RC)-, and wherein each RC is independently a substituted or unsubstituted (C1- C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30) heterohydrocarbyl; and R21 and R22 are each independently C or Si; and R1 to R20 are each independently selected from the group consisting of: a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, -Si(RC) 3, -Ge(RC)3, -P(RC)2, -N(RC)2, -ORC, -SRC, -NO2, -CN, -CF3, -S(O)RC, -S(O) 2RC, -N=C(RC)2, -OC(O)RC, -C(O)ORC, -N(R)C(O)RC, -C(O)N(RC)2, an atom of halogen, and a hydrogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; and wherein, when R17 is a hydrogen atom, then R18 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- SCCCC CC i(R)3, -Ge(R)3,-P(R)2,-N(R)2,-OR,-SR,-NO2,-CN,-CF3,-SC CC CCC (O)R,-S(O) 2R,-N=C(R)2,-OC(O)R,-C(O)OR,-N(R)C(O)R,-C(O)N(RC)2, an atom of halogen, or a hydrogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; or wherein, when R18 is a hydrogen atom, then R17 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- SCCCC CC i(R)3, -Ge(R)3,-P(R)2,-N(R)2,-OR,-SR,-NO2,-CN,-CF3,-SC CC CCC (O)R,-S(O) 2R,-N=C(R)2,-OC(O)R,-C(O)OR,-N(R)C(O)R,-C(O)N(RC)2, an atom of halogen, or a hydrogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; and/or wherein, when R19 is a hydrogen atom, then R20 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- SCCCC CC i(R) 3,-Ge(R)3,-P(R)2,-N(R)2,-OR,-SR,-NO2,-CN,-CF3,-SC CC CCC (O)R,-S( O)2R,-N=C(R)2,-OC(O)R,-C(O)OR,-N(R)C(O)R,-C(O)N(RC)2, a halogen atom, or a hydrogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; or wherein, when R20 is a hydrogen atom, then R19 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- SC CCC CC i(R)3 ,-Ge(R)3,-P(R)2,-N(R)2,-OR,-SR,-NO2,-CN,-CF3,-SC CC CCC (O)R,-S(O )2R,-N=C(R)2,-OC(O)R,-C(O)OR,-N(R)C(O)R,-C(O)N(RC)2, one atom of halogen, or a hydrogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; and wherein for Formula I, two or more of R1 to R22, optionally, may form one or more ring structures, and wherein each ring structure has from 3 to 50 ring atoms, excluding any hydrogen atoms; and wherein, for Formula I, one or more hydrogen atoms may be optionally substituted with one or more deuterium atoms. DETAILED DESCRIPTION OF THE INVENTION
[003] The present invention provides a process for forming an olefin-based polymer, said process comprising polymerizing at least one olefin, additionally ethylene or propylene and additionally ethylene, in the presence of at least one catalyst system comprising the product of reaction of the following: A) at least one cocatalyst, and B) a procatalyst comprising a metal-ligand complex of Formula (I):
(Formula I). wherein Formula I is described above.
[004] An inventive process may comprise a combination of two or more modalities as described above:
[005] The procatalyst may comprise a combination of two or more modalities as described herein.
[006] As used here, R1 = R1, R2 = R2, R3 = R3, and so on. As is known in the art, O is oxygen, S is sulfur, Si is silicon, and so on.
[007] In one embodiment, for Formula I, when R17 is a hydrogen atom, then R18 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- Si(RC)3,-Ge(RC)3,-P(RC)2,-NC CC CCC (R)2,-OR,-SR,-NO2,-CN,-CF3,-S(O)R ,-S(O)2R,-N=C(R)2,-OC(O)RC,-C(O)ORC,-N(R)C(O)RC,-C(O)N(RC )2, or a halogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; or
[008] wherein, when R18 is a hydrogen atom, then R17 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- SCCCC CC i(R) 3,-Ge(R)3,-P(R)2,-N(R)2,-OR,-SR,-NO2,-CN,-CF3,-SC CC CCC (O)R,-S( O)2R, -N=C(R)2, -OC(O)R, -C(O)OR, -N(R)C(O)R, -C(O)N(RC)2, or a halogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; and/or
[009] wherein, when R19 is a hydrogen atom, then R20 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- SC CCC CC i(R )3,-Ge(R)3,-P(R)2,-N(R)2,-OR,-SR,-NO2,-CN,-CF3,-SC CC CCC (O)R,-S (O)2R,-N=C(R)2,-OC(O)R,-C(O)OR,-N(R)C(O)R,-C(O)N(RC)2, or a halogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl; or
[0010] wherein, when R20 is a hydrogen atom, then R19 is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl,- SC CCC CC i(R )3,-Ge(R)3,-P(R)2,-N(R)2,-OR,-SR,-NO2,-CN,-CF3,-SC CC CCC (O)R,-S (O)2R,-N=C(R)2,-OC(O)R,-C(O)OR,-N(R)C(O)R,-C(O)N(RC)2, or a halogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl.
[0011] In one embodiment, the polymerization is solution polymerization. As used herein, the term "solution polymerization" refers to a polymerization process in which the polymer formed is soluble in the reaction medium (e.g., a hydrocarbon-based solvent such as ISOPAR E). The solubility of the polymer will mainly depend on the polymerization temperature and the polymer concentration.
[0012] In one embodiment, the cocatalyst is selected from a borate, an aluminum alkyl, or an aluminoxane.
[0013] In one embodiment, the polymerization takes place at a temperature of from 25°C to 250°C, additionally from 50°C to 230°C, additionally from 100°C to 220°C, additionally from 150°C to 200°C Ç.
[0014] In one embodiment, polymerization occurs at a pressure of 10 psi to 2000 psi, additionally 100 psi to 500 psi.
[0015] In one embodiment, the polymerization occurs at a temperature greater than or equal to 140°C, additionally greater than or equal to 150°C, and the olefin-based polymer has a zero shear viscosity ratio of less than 2.0 and an I10/I2 less than 7.0, less than 6.0. In a further embodiment, the olefin-based polymer is an ethylene-based polymer, and additionally an ethylene/α-olefin copolymer. Suitable α-olefins include C3-C8 α-olefins.
[0016] In one embodiment, the olefin-based polymer is an ethylene-based polymer.
[0017] In one embodiment, the ethylene-based polymers have a density in the range of 0.855 to 0.973 g/cm3. All individual values and subranges from 0.855 to 0.973 g/cm3 are included and disclosed herein; for example, the density can be from a lower limit of 0.855, 0.880, 0.900, 0.910 or 0.920 g/cm 3 to an upper limit of 0.973, 0.965, 0.960, 0.955, 0.950, 0.945, 0.940, 0.935 or 0.930 g/cm 3 .
[0018] In one embodiment, an ethylene-based polymer has a melt index (I2) in the range of 0.1 to 200 g/10 minutes. All individual values and subranges from 0.1 to 200 g/10 minutes are included and disclosed herein; for example, the melt index (I2) may be a lower limit of 0.1, 0.2, 0.5, 1, 1.5, 2.0, 3.0, 5.0, 10, 15 , 20, 30, 40, 50, 60, 80, 90, 100 or 150 g/10 minutes, up to an upper limit of 5.0, 10, 15, 20, 30, 40, 50, 60, 80, 90, 100, 150 or 200 g/10 minutes.
[0019] Ethylene-based polymers include ethylene homopolymers and interpolymers and optionally one or more comonomers, such as α-olefins. α-olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers may preferably have 3 to 10 carbon atoms and more preferably 3 to 8 carbon atoms. Examples of α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-hexene and 1-octene; and preferably 1-hexene and 1-octene.
[0020] In one embodiment, the olefin-based polymer is a propylene-based polymer.
[0021] In one embodiment, for Formula I, each Z is an oxygen atom.
[0022] In one embodiment, for Formula I, R21 and R22 are each C(carbon).
[0023] In one embodiment, each X is independently a (C1-C40)hydrocarbyl, a (C1-C40)heterohydrocarbyl, or a halide. In an additional embodiment both X groups are the same.
[0024] In one embodiment, each X is independently a (C1-C40)hydrocarbyl, or a halide. In an additional embodiment both X's are the same.
[0025] In one embodiment, each X is independently a (C1-C40)hydrocarbyl. In an additional embodiment both X groups are the same.
[0026] In one embodiment, each X is independently a (C1-C3)alkyl, additionally ethyl or methyl, and additionally methyl. In an additional embodiment both X groups are the same.
[0027] In one embodiment, for Formula I, L is selected from the following: -CH2CH2CH2-, -CH2CH2- or -CH2-; and additionally -CH2CH2- or -CH2-, and additionally -CH2-.
[0028] In one embodiment, for Formula I, each (C1-C40)hydrocarbyl, and each (C1-C40)heterohydrocarbyl is not substituted.
[0029] In one embodiment, for Formula I, at least one (C1-C40)hydrocarbyl, and/or at least one (C1-C40)heterohydrocarbyl is independently substituted with at least one RS substituent, and in that each substituent RS is independently selected from the following: a halogen atom, a polyfluor substituent, a perfluoro substituent, F3C-, FCH2O-, F2HCO-, F3CO-, CC CCC C(R)3Si-, (R)3Ge, (R)O-, (R)S-, (R)S(O)-, (R)S(O)2-, (RC)2P-, (RC)2N-, (RC) )2C=N-, NC-, (RC)C(O)O-, (RC)OC(O)-, (RC)C(O)N(RC)-, or (RC)2NC(O)- and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl.
[0030] In one embodiment, for Formula I, two or more of R1 to R22 do not form one or more ring structures.
[0031] In one embodiment, Formula I does not contain one or more deuterium atoms.
[0032] In one modality, for Formula I, the pro-










[0033] In a further embodiment, for Formula I, the procatalyst is selected from the group consisting of the following: from I1 to I20, additionally from I1 to I12, additionally from I1 to I6, each as described above .
[0034] In one embodiment, for Formula I, R2, R4, R5, R7, R8, R9, R10, R12, R13 and R15 are each hydrogen.
[0035] In one embodiment, for Formula I, M is zirconium or hafnium; n is 2; each X, independently, is a (C1-C40)hydrocarbyl, a (C1-C40)heterohydrocarbyl, or a 2 4 5 7 8 9 10 12 13 15 halide; and R, R, R, R, R, R, R , R , R , and R are each hydrogen.
[0036] In one embodiment, for Formula I, M is zirconium; and each Z is an oxygen atom.
[0037] In one embodiment, for Formula I, R1 and R16 are each independently selected from the following i) to v):

[0038] In an additional embodiment, both R1 and R16 are the same. In each of the structures 1) av), the dashed line
indicates the point of attachment to the remaining structure of Formula I.
[0039] In one embodiment, for Formula I, R1 and R16 are each independently selected from the following i) to ii). In an additional embodiment, both R1 and R16 are the same.
[0040] In one embodiment, for Formula I, R17 or R18 is a hydrogen atom, and the other is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl ,-Si(RC)3,-Ge(RC)3,-P(RC)2,-NC CC CCC (R)2,-OR,-SR,-NO2,-CN,-CF3,-S(O )R,-S(O)2R,-N=C(R)2,-OC(O)RC,-C(O)ORC,-N(R)C(O)RC,-C(O)N (RC)2, or to a halogen atom; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl. In a further embodiment, R19 or R20 is a hydrogen atom, and the other is a substituted or unsubstituted (C1-C40)hydrocarbyl, a substituted or unsubstituted (C1-C40)heterohydrocarbyl, -Si(RC)3 ,-Ge(RC)3,-P(RC)2,-N(RC)2,-ORC,-SRC,-NO2,-CN,-CF3,-S(O)RC,-S(O)2RC -N=C(RC)2, -OC(O)RC, -C(O)ORC, -N(R)C(O)RC, -C(O)N(RC)2, or an atom of halogen; and wherein each RC is independently a substituted or unsubstituted (C1-C30)hydrocarbyl, or a substituted or unsubstituted (C1-C30)heterohydrocarbyl.
[0041] In one embodiment, R17 or R18 is hydrogen, and the other is an unsubstituted hydrocarbyl. In a further embodiment, R19 or R20 is hydrogen, and the other is an unsubstituted hydrocarbyl.
[0042] In one embodiment, for Formula I, R17, R18, R19 and R20 are each independently an unsubstituted (C1-C40)hydrocarbyl. In a further embodiment, R17, R18, R19 and R20 are each independently an unsubstituted (C1-C30)hydrocarbyl, additionally an unsubstituted (C1-C20)hydrocarbyl, additionally an unsubstituted (C1-C10)hydrocarbyl, additionally an unsubstituted (C1-C5)hydrocarbyl, and additionally an unsubstituted (C1-C3)hydrocarbyl.
[0043] In one embodiment, for Formula I, R3 and R14 are each independently an unsubstituted (C1-C40)hydrocarbyl. In a further embodiment, R3 and R14 are each independently an unsubstituted (C1-C30)hydrocarbyl, additionally an unsubstituted (C1-C20)hydrocarbyl, additionally an unsubstituted (C1-C10)hydrocarbyl, additionally a (C1 unsubstituted -C5)hydrocarbyl, and additionally an unsubstituted (C1-C3)hydrocarbyl.
[0044] In one embodiment, for Formula I, R6 and R11 are each independently an unsubstituted (C1-C40)hydrocarbyl or a halogen. In a further embodiment, R6 and R11 are each independently an unsubstituted (C1-C30)hydrocarbyl, additionally an unsubstituted (C1-C20)hydrocarbyl, additionally an unsubstituted (C1-C10)hydrocarbyl, additionally a (C1) unsubstituted -C5)hydrocarbyl, and additionally an unsubstituted (C1-C3)hydrocarbyl. In another embodiment, for Formula I, R6 and R11 are each independently a halogen, and additionally Cl or F, and additionally F.
[0045] In one embodiment, two or more cocatalysts are used in an inventive process.
[0046] In one embodiment, the process comprises polymerizing one or more α-olefins in the presence of at least one or more catalyst systems, and optionally one or more other catalyst systems in one or more polymerization reactors, connected in parallel, in series or combinations thereof.
[0047] In another embodiment, the process comprises the steps of: (1) providing at least one or more catalyst systems of the invention and, optionally, one or more other catalyst systems; (2) polymerizing one or more α-olefins in the presence of at least one or more catalyst systems of the invention and, optionally, one or more other catalyst systems in one or more polymerization reactors, connected in parallel, in series or combinations of the same; and (3) thereby producing an olefin-based polymer.
[0048] In another embodiment, the process is a solution polymerization in a double reactor system, for example a double loop reactor system, in which the olefin and, optionally, one or more α-olefins are polymerized in the presence of one or more catalyst systems. In a further embodiment, the olefin is ethylene.
[0049] In another embodiment, the process is a solution polymerization in a single reactor system, for example a single loop reactor system, in which the olefin and, optionally, one or more α-olefins are polymerized in the presence of one or more catalyst systems. In another embodiment, the olefin is ethylene.
[0050] As mentioned above, the present invention employs one or more metal-ligand complexes of Formula (I), which is described herein using conventional chemical group terminology. When used to describe certain carbon atom-containing chemical groups (e.g. (C1-C40) alkyl), the expression in parentheses (C1-C40) can be represented by the form “(Cx-Cy)”, which means that the The unsubstituted version of the chemical group comprises from a number x carbon atoms to a number y carbon atoms, where each x and y is independently an integer as described for the chemical group. The term "substituted", as used herein, in relation to a chemical compound, refers to a substituent comprising at least one heteroatom (e.g., O, S, N, P, etc.). The substituents include, but are not limited to, the Rs substituents, as noted above, such as the following: a halogen atom, a polyfluor substituent, a perfluoro substituent, F3C-, FCH2O-, F2HCO-, F3CO-, ( RC)3Si-, (RC)3Ge-, CCC CCC (R)O-, (R)S-, (R)S(O)-, (R)S(O)2-, (R)2P-, (R)2N-, (RC)2C=N-, NC-, (RC)C(O)O-, (RC)OC(O)-, (RC)C(O)N(RC)-, and (RC)2NC(O)- where RC is described above.
[0051] The term "unsubstituted", as used herein, in relation to a chemical compound, refers to the absence of a substituent comprising at least one heteroatom (e.g., O, S, N, P, etc.) .
[0052] The term "hydrocarbyl", as used herein, refers to a monovalent chemical group (monoradical or radical) containing only hydrogen and carbon atoms.
[0053] The term "substituted hydrocarbyl", as used herein, refers to a hydrocarbyl, in which at least one hydrogen atom is substituted with a substituent comprising at least one heteroatom.
[0054] The term "heterohydrocarbyl", as used herein, refers to a hydrocarbyl, in which at least one carbon atom, or CH group, or CH2 group, is substituted with a heteroatom or a chemical group containing at least least one heteroatom. Heteroatoms include, but are not limited to, O, N, P and S.
[0055] The term "substituted heterohydrocarbyl", as used herein, refers to a heterohydrocarbyl in which at least one hydrogen atom is substituted with a substituent comprising at least one heteroatom.
[0056] The term "hydrocarbylene", as used herein, refers to a divalent (diradical) chemical group containing only hydrogen and carbon atoms.
[0057] The term "substituted hydrocarbylene", as used herein, refers to a hydrocarbylene, in which at least one hydrogen atom is substituted with a substituent comprising at least one heteroatom.
[0058] The term "heterohydrocarbylene", as used herein, refers to a hydrocarbylene, in which at least one carbon atom, or CH group, or CH2 group, is substituted with a heteroatom or a chemical group containing at least least one heteroatom. Heteroatoms include, but are not limited to, O, N, P, and S.
[0059] The term "substituted heterohydrocarbylene", as used herein, refers to a heterohydrocarbylene, in which at least one hydrogen atom is substituted with a substituent comprising at least one heteroatom.
[0060] In some embodiments, each of the chemical groups (e.g., X, L, R1 to R22, etc.) of the metal-ligand complex of Formula (I) may be unsubstituted (e.g., without use of a substituent RS). In other embodiments, at least one of the chemical groups of the metal-ligand complex of Formula (I) independently contains one or more of the substituents (e.g., RS). Preferably, representing all chemical groups, there are no more than a total of 20 RS, more preferably, not more than a total of 10 RS, and even more preferably, not more than a total of 5 RS in the metal-ligand complex of formula (I). When the compound of the invention contains two or more Rs substituents independently, each RS is bonded to the same or different atom.
[0061] As used herein, the term "(C1-C40)hydrocarbyl" refers to a hydrocarbon radical of 1 to 40 carbon atoms. Each hydrocarbon radical independently may be aromatic (6 carbon atoms or more) or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including mono- and polycyclic, fused and unfused polycyclic, including bicyclic or acyclic , or a combination of two or more thereof; and each hydrocarbon radical independently is the same as, or different from, another hydrocarbon radical, respectively, wherein each hydrocarbon radical may be optionally substituted with one or more substituents RS , as defined above A "(C1-C30) hydrocarbyl" is also defined, as discussed above for the "(C1-C40) hydrocarbyl".
[0062] Preferably, a (C1-C40)hydrocarbyl is independently a (C1-C40)alkyl, or a (C3-C40)cycloalkyl. More preferably, each of the (C1-C40)hydrocarbyl groups mentioned above independently has a maximum of 20 carbon atoms (i.e., (C1-C20)hydrocarbyl), and even more preferably a maximum of 12 carbon atoms. Additionally, the (C1-C40)hydrocarbyl is optionally substituted with one or more RS substituents as defined above.
[0063] As used herein, the term "(C1-C40)hydrocarbylene" refers to a hydrocarbon diradical of 1 to 40 carbon atoms. Each hydrocarbon diradical independently may be aromatic (6 carbon atoms or more) or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including mono- and polycyclic, fused or unfused polycyclic, including bicyclic or acyclic , or a combination of two or more thereof; and each hydrocarbon diradical independently is the same as, or different from, another hydrocarbon diradical, respectively. Additionally the hydrocarbon radical may be optionally substituted with one or more substituents RS, as defined above.
[0064] Preferably, a (C1-C40)hydrocarbylene independently is a (C3-C20)cycloalkyl-(C1-C20)alkylene, (C6-C40)aryl, or (C6-C20)aryl-(C1-C20) alkylene. More preferably, each of the above-mentioned (C1-C40)hydrocarbylene groups independently has a maximum of 20 carbon atoms (i.e., (C1-C20)hydrocarbyl), and even more preferably, a maximum of 12 carbon atoms. . The (C1-C40)hydrocarbylene may be optionally substituted with one or more RS substituents as defined above.
[0065] The term "(C1-C40)heterohydrocarbyl" refers to a heterohydrocarbon radical of 1 to 40 carbon atoms. Each heterohydrocarbon independently may comprise one or more O heteroatoms; S; ONLY); S(O)2; Si(RC)2; Ge(RC)2; P(RP); and N(RN), wherein independently each RC is unsubstituted (C1-C18)hydrocarbyl, each RP is unsubstituted (C1-C18)hydrocarbyl; and each RN is unsubstituted (C1-C18)hydrocarbyl. Each (C1-C40)heterohydrocarbyl independently may be saturated or unsaturated, straight-chain or branched-chain, cyclic (including mono- and polycyclic, fused or unfused polycyclic), or acyclic, or a combination of two or more thereof ; and each is respectively the same or different from one another. "(C1-C30)heterohydrocarbyl" is similarly defined, as discussed above for "(C1-C40)heterohydrocarbyl".
[0066] The term “(C1-C40)heterohydrocarbylene refers to a hydrocarbon heterodiradical of 1 to 40 carbon atoms. Each heterohydrocarbon independently may comprise one or more O heteroatoms; S; ONLY); S(O)2; Si(RC)2; Ge(RC)2; P(RP); and N(RN), wherein independently each RC is unsubstituted (C1-C18)hydrocarbyl, each RP is unsubstituted (C1-C18)hydrocarbyl; and each RN is (C1-C18) unsubstituted. Each (C1-C40)heterohydrocarbylene is independently unsubstituted or substituted (e.g. by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including mono- and polycyclic , fused or unfused polycyclic) or acyclic, or a combination of two or more thereof; and each is respectively the same or different from one another.
[0067] Preferably, the (C1-C40)heterohydrocarbyl independently is (C1-C40)heteroalkyl, (C1-C40)hydrocarbyl-O-, (C1-C40)hydrocarbyl-S-, (C1-C40)hydrocarbyl -S(O)-, (C1-C40)hydrocarbyl-S(O)2-, (C1-C40)hydrocarbyl-Si(RC)2-, (C1-C40)hydrocarbyl-Ge(RC)2-, ( C1-C40)hydrocarbyl-N(RN)-, (C1-C40)hydrocarbyl-P(RP)-, (C2-C40)heterocycloalkyl.
[0068] Preferably, the (C1-C40)heterohydrocarbylene independently is (C2-C19)heterocycloalkyl-(C1-C20)alkylene, (C3-C20)cycloalkyl-(C1-C19)heteroalkylene, (C2-C19) heterocycloalkyl-(C1-C20)heteroalkylene, (C1-C40)heteroaryl, (C1-C19)heteroaryl-(C1-C20)alkylene, (C6-C20)aryl-(C1-C19)heteroalkylene, or (C1-C19) heteroaryl-(C1-C20)heteroalkylene.
[0069] The term "halogen atom" means radical of fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). Preferably each halogen atom independently is the Br, F, or Cl radical, and more preferably the F or Cl radical. The term "halide" means fluoride (F-), chloride (Cl-), bromide (Br-), or iodide (I-) anion.
[0070] Preferably, there is no O-O, S-S, or O-S bond other than O-S bonds on an S(O) or S(O)2 diradical functional group in the metal-ligand complex of Formula (I). More preferably, there is no OO, NN, PP, NP, SS, or OS bond, other than OS bonds on a diradical functional group S(O) or S(O)2, in the metal-ligand complex of Formula (I).
[0071] The term "saturated" means the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and carbon-nitrogen double bonds (in heteroatom-containing groups), carbon-phosphorus, and carbon-silicon.
[0072] The term unsaturated means that it contains one or more carbon-carbon double bonds, carbon-carbon triple bonds, and carbon-nitrogen double bonds (in groups containing heteroatoms), carbon-phosphorus, and/or carbon-silicon.
[0073] M is titanium, zirconium or hafnium. In one embodiment, M is zirconium or hafnium, and in another embodiment, M is hafnium. In another embodiment, M is zirconium. In some embodiments, M is in a formal oxidation state of +2, +3, or +4. In some embodiments, n is 0, 1, 2, or 3. Each X is independently a monodentate ligand that is neutral, monoanionic, or dianionic; or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic. X and n are chosen such that the metal-ligand complex of Formula (I) is, in general, neutral. In some embodiments each X is independently the monodentate linker. In one embodiment, when there are two or more monodentate X ligands, each X is the same. In some embodiments the monodentate ligand is the monoanionic ligand. The monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand can independently be hydride, (C1-C40)hydrocarbyl carbanion, (C1-C40)heterohydrocarbyl carbanion, halide, nitrate, HC(O)O-, (C1-C40)hydrocarbyl,C(O)O- , HC(O)N(H)-, (C1-C40)hydrocarbyl-C(O)N(H)-, (C1-C40)hydrocarbylC(O)N((C1-C20)hydrocarbyl)-, KL- KL-K-K-KL-MKL-K RRB , RRN , RO , RS , RRP , or RRRSi , where each R, RL, and RM independently is hydrogen, (C1-C40)hydrocarbyl, or (C1-C40) heterohydrocarbyl, or RK and RL are taken together to form a (C2-C40)hydrocarbylene or (C1-C40)heterohydrocarbylene and RM is as defined above.
[0074] In some embodiments, at least one monodentate ligand of X independently is the neutral ligand. In one embodiment, the neutral ligand is a Lewis base group such that X KL KLKLX KL X is RNRR, ROR, RSR, or RPRR, where each R independently is hydrogen, (C1-C40)hydrocarbyl, [(C1-C10 )hydrocarbyl]3Si, [(C1-C10)hydrocarbyl]3Si(C1-C10)hydrocarbyl, or (C1-C40)heterohydrocarbyl and each RKe RL independently is as defined above.
[0075] In some embodiments, each X is a monodentate ligand that is independently a halogen atom, unsubstituted (C1-C20)hydrocarbyl, unsubstituted (C1-C20)hydrocarbylC(O)O-, or RKRLN- where each one of RK and RL independently is an unsubstituted (C1-C20)hydrocarbyl. In some embodiments each monodentate linker X is a chlorine atom, (C1-C10)hydrocarbyl (e.g., (C1-C6)alkyl or benzyl), unsubstituted (C1-C10)hydrocarbylC(O)O-, or RKRLN- wherein each of RK and RL independently is an unsubstituted (C1-C10)hydrocarbyl.
[0076] In some embodiments, there are at least two X's and the two X's are taken together to form the bidentate ligand. In some embodiments the bidentate ligand is a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand is a diene of Formula (RD)2C=C(RD)-C(RD)=C(RD)2, wherein each RD independently is H, unsubstituted (C1-C6)alkyl , phenyl, or naphthyl. In some embodiments the bidentate ligand is a monoanionic-mono (Lewis base) ligand. The monoanionic-mono(Lewis base) ligand may be a 1,3-dionate of Formula (D): RE-C(O-)=CH-C(=O)-RE(D), where each RD is independently is H, (C1-C6)alkyl, phenyl, or unsubstituted naphthyl. In some embodiments the bidentate ligand is a dianion ligand. The dianionic ligand has a formal oxidation state of -2. In one embodiment, each dianion linker independently is carbonate, oxalate (i.e., -O2CC(O)O-), (C2-C40)hydrocarbylene dicarbanion, (C1-C40)dicarbanion heterohydrocarbylene, or sulfate.
[0077] As mentioned earlier, the number and charge (neutral, monoanionic, dianionic) of X are selected depending on the formal oxidation state of M such that the metal-ligand complex of Formula (I) is, in general, neutral. .
[0078] In some embodiments, each X is the same, where each X is methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments n is 2 and each X is the same.
[0079] In some embodiments, at least two X's are different. In some embodiments, n is 2 and each X is different from a methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine.
[0080] The integer n indicates the number of X. In one embodiment, n is 2 or 3, and at least two X independently are monoanionic monodentate ligands, and a third X, if present, is a neutral monodentate ligand. In some embodiments n is 2, at least two X's are taken together to form a bidentate linker. In some embodiments, the bidentate linker is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.
[0081] In some embodiments, each Z independently is O, S,-N[(C1-C40)hydrocarbyl]-, or -P[(C1-C40)hydrocarbyl]-. In some modalities, each Z is different. In some embodiments, a Z is O, and a Z is -N(CHβ)-. In some embodiments, a Z is O, and a Z is S. In some embodiments, a Z is S, and a Z is -N[(C1-C40)hydrocarbyl]-(eg, -N(CH3)-) . In some embodiments, each Z is the same. In some embodiments, each Z is O. In some embodiments, each Z is S. In some embodiments, each Z is -N[(C1-C40)hydrocarbyl]-(eg, -N(CH3)-). In some embodiments, at least one, and in some embodiments each Z is -P[(C1-C40)hydrocarbyl]-(e.g., -P(CH3)-).
[0082] In some embodiments, L is selected from the following: -CH2-, -CH2CH2-, -CH2CH2CH2-;-CH(CH3)CH2CH(CH3)-;-CH(CH3)CH(CH3)CH(CH3)- ;-CH2C(CH3)2CH2-; 1,3-cyclopentane-diyl; or 1,3-cyclohexane-di-yl. In some embodiments L comprises the linker backbone of 4 carbon atoms (e.g., L is -CH2CH2CH2CH2-; -CH2C(CH3)2C(CH3)2CH2-; 1,2-bis(methylene)cyclohexane; or 2,3-bis(methylene)-bicyclo[2.2.2]octane). In some embodiments L comprises the linker backbone of 5 carbon atoms (for example, L is -CH2CH2CH2CH2CH2- or 1,3-bis(methylene)cyclohexane). In some embodiments L comprises the linker backbone of 6 carbon atoms (for example, L is -CH2CH2CH2CH2CH2CH2- or 1,2-bis(ethylene)cyclohexane). Cocatalyst Components
[0083] The procatalyst comprising the metal-ligand complex of Formula (I) becomes catalytically active by contacting, or combining it with, the activating cocatalyst, or using an activation technique, such as those that are known in the art for use with metal-based olefin polymerization reactions. Activating cocatalysts suitable for use in the present invention include alkyl aluminums; polymeric 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 suitable activation technique is bulk electrolysis. Combinations of one or more of the above activation techniques and cocatalysts are also contemplated. The term "aluminum alkyl" means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkyl aluminum. Aluminoxanes and their preparations are known from, for example, United States Patent Number (USPN) US 6,103,657. Examples of preferred polymeric or oligomeric alumoxanes are methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.
[0084] Many activation techniques and activation cocatalysts were previously taught with regard to different metal-ligand complexes in the following USPNs: US 5,064,802; US 5,153,157; US 5,296,433; US 5,321,106; US 5,350,723; US 5,425,872; US 5,625,087; US 5,721,185; US 5,783,512; US 5,883,204; US 5,919,983; US 6,696,379; and US 7,163,907. Examples of suitable hydrocarbyl oxides are described in US 5,296,433.
[0085] In one embodiment, the procatalyst comprising the metal-ligand complex of Formula (I) may be activated to form an active catalyst composition, by combination with one or more cocatalysts, such as a cation-forming cocatalyst , a strong Lewis acid, or a combination thereof. Suitable cocatalysts for use include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as non-coordinating, compatible, inert 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-)amine, triethylaluminum (TEA), and any combinations thereof. of the same.
[0086] In some embodiments, one or more of the above activating cocatalysts are used in combination with each other. An especially preferred combination is a mixture of a tri((C1-C4)hydrocarbyl)aluminum compound, tri((C1-C4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound.
[0087] The ratio of the total number of moles of one or more metal ligand complexes of Formula (I) to the total number of moles of one or more of the activating cocatalysts is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an aluminoxane alone is used as the activating cocatalyst, preferably, the number of moles of the alumoxane that is used is at least 10 times, at least 40 times more, yet at least 100 times the number of moles of the alumoxane complex. metal ligand of formula (I). When tris(pentafluorophenyl)borane alone is used as the activation cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane that is used to the total number of moles of one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, in some other embodiments, from 1:1 to 6:1, in some other embodiments, from 1:1 to 5:1. The remaining activating cocatalysts are generally used in approximately molar amounts equal to the total mole amounts of one or more metal-ligand complexes of formula (I).
[0088] The catalyst composition of the invention comprises a) the procatalyst and b) one or more cocatalysts as described herein have a catalytic efficiency
[0089] The catalyst composition of the invention comprising the procatalyst and one or more cocatalysts, as described herein, has catalytic efficiency in the range of greater than 100,000 g of polymer per gram of metal active center; for example, greater than 500,000 g of polymer per gram of metal active center. Catalytic efficiency is measured in terms of the amount of polymer produced in relation to the amount of catalyst used in the solution polymerization process, where the polymerization temperature is at least 130°C, for example in the range 150 to 195°C , and the ethylene concentration is greater than 5 g/L, for example, greater than 6 g/L, and where the ethylene conversion is greater than 70 percent, for example, or greater than 80 percent, or in alternative, greater than 90 percent. Process for Pro-catalyst Production
[0090] In some embodiments, the binders of the invention may be prepared using known procedures. Specifically, the binders of the invention can be prepared using a variety of synthetic routes, depending on the desired variation in the binder. In general, building blocks are prepared which are then linked together with a bridge group. Variations in R group substituents can be introduced in the synthesis of building blocks.
[0091] Bridge variations can be introduced with bridge group synthesis. Specific binders within the scope of this invention can be prepared according to the general schemes shown below, in which the building blocks are prepared first, and then coupled together. There are several different ways to use these building blocks. In one embodiment, in general, each of the optionally substituted phenyl rings is prepared as a separate building block. The desired optionally substituted phenyl groups are then combined into the bi-phenyl building block, which are then bridged together. In another embodiment, the optionally substituted phenyl building blocks are bridged, and then optionally substituted phenyl building blocks are added to form the bi-aryl bridged structures. The starting materials or reagents used are generally commercially available, or are prepared by routine synthetic means.
[0092] In the schemes below, the term ligand refers to the organic precursor to the procatalyst. The procatalyst is derived from a reaction of the ligand with a suitable metallic precursor (titanium, zirconium or hafnium). Common abbreviations are listed in the main system below. LG: Generic output group
[0093] PG: Generic protection group, common examples include:
R, L, M, Z, X: as defined above Ha: halide, most commonly Br or I; Me: methyl; Et: ethyl; Ph: phenyl; i-Pr: iso-propyl; t-Bu: tert-butyl; t-Oct: tert-octyl; Ts: toluene sulfonate; THF: tetrahydrofuran; Et2O: diethyl ether; DMF: dimethylformamide; AcOEt: ethyl acetate; DIAD: diisopropyl azodicarboxylate; GC: gas chromatography; LC: Liquid chromatography; TLC: thin layer chromatography; NMR: nuclear magnetic resonance; PTSA: para-toluene sulfonic acid; NIS: N-iodosuccinimide 1a. Preparation of 2-substituted protected phenols (protocol 1, carbon-nitrogen coupling).

[0094] A three-necked, round-bottomed flask in a glove box is charged with the desired protected phenol (approximately 1.0 equivalent), the desired aryl-nitrogen compound, or heterocyclic nitrogen (approximately 0.6 equivalent). ), K3PO4 (approximately 2.1 equivalents), anhydrous CuI (approximately 0.03 equivalents), dry toluene (approximately 2 mL per mmol of phenol), and an N,N'-disubstituted diamine (approximately 0.08 equivalents). The reaction mixture is then heated under reflux. Reaction progress can be monitored by a suitable technique (eg GC/MS, NMR spectroscopy, TLC), and in some cases additional anhydrous CuI (approximately 0.03 equivalent) and N,N'-disubstituted diamine (approximately 0.08 equivalent) are added to the mixture, and heated under continued reflux, until such time as the conversion is observed to be complete. The reaction is then allowed to cool to room temperature, filtered through a small plug of silica, washed with THF and concentrated to yield the crude product. This crude material can be purified either by recrystallization or flash chromatography on silica gel. 1b. Preparation of 2-substituted protected phenols (protocol 2, carbon-carbon coupling).

[0095] A three-necked round-bottom flask, placed under an atmosphere of nitrogen, is charged with approximately equimolar amounts of the aryl halide and the aryl borated compound, NaOH (approximately 6 equivalents with respect to the aryl halide), Pd( PPh3)4 (approximately 0.02 equivalent to aryl halide), degassed toluene (approximately 5 mL per mmol of aryl halide), and degassed water (approximately 1 mL per mmol of aryl halide). The system is sparged with nitrogen, and the contents are then heated to 110°C for approximately 24 hours. The reaction is cooled and the volatiles removed under vacuum. The residue is taken up in Et2O, washed with brine, dried over anhydrous magnesium sulfate, filtered through a pad of silica gel and then concentrated. This crude material can be purified either by recrystallization or flash chromatography on silica gel. 2. Preparation of borated 2-substituted protected phenols:

[0096] To an oven-dried, three-necked, round-bottom flask under a nitrogen atmosphere, add the desired protected phenol (approximately 1.0 equivalent) and dry THF (approximately 6 mL per mmol of protected phenol). This solution is cooled to about 0-10°C (ice water bath), and 2.5M n-butyllithium in hexanes (approximately 2.2 equivalents) is slowly added. After stirring for about 4 hours, the desired boronic ester or boronic acid (approximately 2.2 equivalents) is slowly added. The mixture is stirred for one hour at about 0-10°C, before allowing the reaction to warm to room temperature, and then stirred for approximately 18 hours. To the reaction mixture is added cold saturated aqueous sodium bicarbonate solution, (approximately 6 ml per mmol of protected phenol. The mixture is extracted with several portions of methylene chloride. The organic phases are combined and washed with saturated aqueous sodium bicarbonate. cold and brine, then dried over anhydrous magnesium sulfate, filtered, and concentrated to yield the crude product Purification can be accomplished by recrystallization from a suitable solvent (e.g., acetonitrile, toluene, hexane, or methanol). .Preparation of symmetrical bridge fragments.
LG1 and LG2 may or may not be equivalent
[0097] Mitsonobu type: An oven-dried three-necked round-bottom flask equipped with an addition funnel is placed under a nitrogen atmosphere and charged with the desired aryl halide (approximately 1.0 equivalent), the unit of desired connection (containing fraction L and groups R17-R22, approximately 0.45 equivalent), triphenylphosphine (approximately 1.0 equivalent), and THF (approximately 1.0 mL per mmol of aryl halide). The addition funnel is then charged with DIAD (approximately 1.0 equivalent) and THF (approximately 0.5 mL per mmol of aryl halide). The contents of the flask are cooled to approximately 2-5°C in an ice-water bath and the DIAD solution in the addition funnel is added at such a rate to maintain the reaction temperature at 2-5°C. . The resulting mixture is stirred at 2-5°C for an additional hour after the addition of DIAD, then allowed to warm to room temperature, and stirred overnight. Volatiles are removed under vacuum, and the resulting residue is extracted with an alkane solvent, and washed sequentially with 1M NaOH, water, 1N HCl, and water. The organic portion is collected and dried under vacuum. Purification can be accomplished by recrystallization from a suitable solvent (for example, acetonitrile, toluene, hexane or methanol), or by silica gel column chromatography.
[0098] SN2- Type: A solution of the desired aryl halide (approximately 1.0 equivalent) and desired connecting unit (containing the L fraction and the R17-R22 groups, approximately 0.45 equivalent) in acetone (approximately 7.0 mL per mmol of aryl halide), K2CO3 (approximately 2.5 equivalents) is added. The reaction mixture is then heated under reflux for approximately 36 hours. The resulting suspension is then cooled, filtered, and concentrated under vacuum. Purification can be accomplished by recrystallization from a suitable solvent (for example, acetonitrile, toluene, hexane or methanol), or by silica gel column chromatography. 3b. Preparation of non-symmetrical bridge fragments.

[0099] For a solution of the desired aryl halide (approximately 1.0 equivalent) and desired connection unit (containing the L fraction and the R17-R22 groups, approximately 1.5 equivalent), in acetone (approximately 7.0 mL per mmol of aryl halide) K2CO3 (approximately 2.5 equivalents) is added. The reaction mixture is then heated under reflux for approximately 36 hours. The resulting suspension is then cooled, filtered, and concentrated under vacuum. Purification can be carried out at this stage by recrystallization from a suitable solvent (eg acetonitrile, toluene, hexane or methanol), or by silica gel column chromatography. The material obtained is then subjected to an analogous sequential reaction, combining it with another aryl halide (approximately 1.0 equivalent), and K2CO3 (approximately 2.5 equivalent), in acetone (approximately 7.0 mL per mmol of aryl halide), and heating under reflux. The resulting suspension is then cooled, filtered and concentrated under vacuum. Purification can be accomplished by recrystallization from a suitable solvent (e.g. acetonitrile, toluene, hexane or methanol), or by silica gel column chromatography. 5th Ligand preparation (simultaneous double Suzuki reaction).

[00100] To a three-neck round-bottom flask dried in an oven, under a nitrogen atmosphere, add the bis-aryl halide (approximately 1.0 equivalent) and the boron protected phenol (about 2.2 equivalents) dissolved in toluene (approximately 5 mL per mmol of bis-aryl halide) under an atmosphere of nitrogen with stirring. To this mixture, NaOH (approximately 1.0 equivalent) dissolved in water, (approximately 10 mL per mmol of NaOH) is added, followed by rapid addition of Pd(PPh3)4 (approximately 0.04 equivalent), and the reaction was heated to 88°C. The course of the reaction can be monitored by means of LC. When the reaction is considered complete, the reaction vessel is cooled to room temperature, and stirring is stopped. The caustic layer is removed from the resulting biphasic mixture, and a 20% aqueous HCl solution is added (approximately 1.5 mL per mmol bis-arylhalide) to the remaining organic portion. The resulting mixture is heated under reflux for approximately 8 hours. The reactor is cooled to room temperature, the aqueous layer is removed, and the organic layer is washed with brine, then dried over MgSO4. This mixture is filtered, and concentrated, to provide the crude product, which can be purified by recrystallization from a suitable solvent (eg, acetonitrile, toluene, hexane, or methanol), or by silica gel column chromatography. 5b. Ligand preparation (sequential Suzuki reactions).

[00101] To a three-neck round bottom flask dried in an oven, under a nitrogen atmosphere, add the dissolved bis-aryl halide (approximately 1.0 equivalent) and the boron protected phenol (approximately 1.0 equivalent). in toluene (approximately 5 mL per mmol of bis-aryl halide) under a nitrogen atmosphere with stirring. To this mixture is added NaOH (approximately 1.0 equivalent) dissolved in water, (approximately 10 mL per mmol of NaOH), followed by rapid addition of a suitable palladium catalyst (approximately 0.04 equivalent), and the reaction is heated. at 88°C. The course of the reaction can be monitored by means of LC. When the reaction is considered complete, the reaction vessel is cooled to room temperature, followed by boron-protected phenol (approximately 1.0 equivalent), and a suitable palladium catalyst (approximately 0.04 equivalent). The reaction is heated to 88°C, and the course of the reaction can be monitored again by LC. When the reaction is considered complete, the reaction vessel is cooled to room temperature, and stirring is stopped. The caustic layer is removed from the resulting biphasic mixture, and a 20% aqueous HCl solution (approximately 1.5 mL per mmol bis-aryl halide) is added to the remaining organic portion. The resulting mixture is heated under reflux for approximately 8 hours. The reactor is cooled to room temperature, the aqueous layer is removed, and the organic layer is washed with brine, then dried over MgSO4. This mixture is filtered, and concentrated, to provide the crude product, which can be purified by recrystallization from a suitable solvent (eg, acetonitrile, toluene, hexane, or methanol), or by silica gel column chromatography. 7. Procatalyst preparation.

[00102] An oven-dried, three-necked, round-bottomed flask under a nitrogen atmosphere is charged with MCl4 (approximately 1.0 equivalent) and cold toluene or hexane (approximately 10 mL per mmol of binder, at a temperature of -40 to -20°C. XMgBr (approximately 4.0 equivalents) is then added to the cold suspension, and the resulting mixture is stirred for 2-15 minutes.The binder (approximately 0.95 equivalents) is then added, and the reaction mixture is allowed to warm to room temperature, and stirred for approximately 4 hours, and then dried under vacuum. The resulting residue is extracted with hexane and/or toluene, filtered and dried under vacuum. This crude material can be further purified by recrystallization at from a suitable solvent (e.g. hexane, toluene). Definitions
[00103] The term "polymer", as used herein, refers to a polymeric compound prepared by polymerizing monomers, either of the same type or a different type. The generic term polymer thus encompasses the term homopolymer (used to refer to polymers prepared from just one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and the term interpolymer as defined in follow. Trace amounts of impurities, for example catalyst residues, may be incorporated into and/or within the polymer.
[00104] The term "interpolymer", as used herein, refers to polymers prepared by polymerizing at least two different types of monomers. The generic term interpolymer thus includes copolymers (used to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
[00105] The term, "olefin-based polymer", as used herein, refers to a polymer comprising, in polymerized form, a greater amount of olefin monomer, e.g., ethylene or propylene (based on weight of the polymer) and, optionally, may comprise one or more comonomers.
[00106] The term, "ethylene-based polymer", as used herein, refers to a polymer comprising, in polymerized form, a greater amount of ethylene monomer (based on the weight of the polymer), and optionally , may comprise one or more comonomers.
[00107] The term, "propylene-based polymer", as used herein, refers to a polymer comprising, in polymerized form, a greater amount of propylene monomer (based on the weight of the polymer), and, optionally, , may comprise one or more comonomers. EXPERIMENTAL
[00108] The following examples illustrate the present invention, but are not intended to limit the scope of the invention. The preparation of comparative procatalysts C1 and C3 are described in WO 2007136496 and US 2011/0282018, respectively, incorporated herein by reference insofar as comparative procatalysts C1 and C3 are taught. Specific Embodiments for Synthesis of Inventive Catalyst Example 1. 1a. Preparation of Linker 1 (L1).
[00109] A round bottom flask was charged with 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (7.285 g, 11.91 mmol) and meso-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-methyl-benzene) (2.194 g, 4.96 mmol), and 60 mL of THF. Na2CO3 (3.156 g, 29.78 mmol) was dissolved in 30 mL of water, and added to the THF solution, forming a biphasic solution, which was then sparged with N2 for 15 minutes. Pd(P(t-Bu)3)2 (0.076 g, 0.15 mmol) was dissolved in 20 mL of degassed THF in a nitrogen-filled glove box, then added to the reaction mixture, which was heated at reflux, under nitrogen, for 24 hours. The reaction mixture was allowed to cool to room temperature, then the aqueous phase was separated and discarded. THF was removed from the organic phase on a rotary evaporator, and dichloromethane (120 ml) was added to the residue, and the solution was washed with 120 ml of water. Brine (30 mL) was added to aid phase separation.
[00110] The organic phase was collected and evaporated to dryness under vacuum. The residue was dissolved in 50 ml of diethyl ether, filtered through a plug of silica gel and evaporated to dryness under reduced pressure. MeOH (100 mL), THF (40 mL) and concentrated HCl (4 drops) were added to the residue, and the solution was refluxed for two hours. The reaction mixture was allowed to cool to room temperature, but no precipitation occurred. Therefore, the solution was concentrated to approximately half of its original volume on a rotary evaporator, causing orange solids to form. The solids were filtered, washed with methanol and dried under vacuum (1.83 g). The mother liquor was evaporated to dryness, then the residue was dissolved in diethyl ether (approximately 15 ml), and poured into approximately 200 ml of methanol, causing a small amount of precipitate to form. The volume was halved under vacuum, causing more solids to collide. The pale orange solids were filtered, washed with methanol and dried under vacuum to provide pure product (1.90 g). A third group of product (0.26 g) was recovered from the mother liquor. Overall yield isolated: 3.99 g, 64%. 1H NMR (400 MHz, CDCl3) δ 8.16 (t, J = 2.1 Hz, 4H), 7.40 (m, 8H), 7.17 (d, J = 2.2 Hz, 2H), 7.11 (t, J = 8.1 Hz, 4H), 6.88 (dd, J = 8.4, 2.2 Hz, 2H), 6.64 (d, J = 8.3 Hz, 2H ), 6.22 (s, 2H), 4.43 (m, 2H), 2.31 (s, 6H), 2.09 (dt, J = 13.8, 6.8 Hz, 1H), 1 .75 (s, 4H), 1.64 (dt, J = 16.1, 5.9 Hz, 1H), 1.47 (s, 18H), 1.45 (s, 18H), 1.39 ( s, 12H), 1.08 (d, J = 6.0 Hz, 6H), and 0.82 (s, 18H). 1b. Preparation of Pro-Catalyst 1 (I1).

[00111] The binder (0.500 g, 0.40 mmol) was dissolved in 10 mL of hexane, under an atmosphere of dry nitrogen, and the solution was added to a stirred suspension of ZrCl4 (0.093 g, 0.40 mmol) in 5 ml of hexane. MeMgBr (0.63 mL, 1.64 mmol; 2.6 M in Et2O) was added dropwise via syringe at room temperature. The mixture was stirred for 14 hours. The color of the reaction mixture slowly turned black. The suspension was filtered, and the filtrate was evaporated to dryness under vacuum. Hexane (10 mL) was added to the residue, the light suspension was filtered, and the filtrate was evaporated to dryness under vacuum. The hexane treatment was repeated, and the product was dried completely under vacuum to yield I1 in good purity as a brown solid (0.193 g, 35%). 1H NMR (400 MHz, C6D6): δ 8.69 (t, J = 2.0 Hz, 2H), 8.45 (d, J = 1.7 Hz, 1H), 8.40 (d, J = 1.7 Hz, 1H), 7.38-7.85 (m, 16H), 7.13 (d, J = 2.2 Hz, 1H), 7.08 (d, J = 2.3 Hz, 1H), 6.65 (dd, J = 8.4, 2.1 Hz, 1H), 6.62 (dd, J = 8.3, 2.1 Hz, 1H), 5.02 (d, J = 6.5 Hz, 1H), 4.85 (d, J = 6.8 Hz, 1H), 4.33 (dt, J = 13.2, 6.8 Hz, 1H), 3.86 (m , 1H), 1.88 (s, 3H), 1.87 (s, 3H), 0.79-1.71 (m, 70H), 0.73 (d, J = 6.7 Hz, 3H), 0.54 (d, J = 6.7 Hz, 3H), -0.70 (s, 3H), and -0.86 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 151.4, 147.9, 142.5, 142.2, 139.8, 139.7, 132.7, 131.7, 129.9, 129, 0, 128.8, 127.8, 126.6, 125.0, 123.4, 123.2, 116.2, 115.5, 109.5, 73.4, 57. 1, 42.4, 38.2, 34.7, 32.4, 32.1, 32.1, 31.9, 31.7, 31.6, 20.6, and 19.7. Example 2. 2a. Preparation of meso-4,4'-pentane-2,4-diylbis(oxy)bis(1-(tert-butyl)-3-iodobenzene).

[00112] A round bottom flask was charged with meso-ditosylate (3.1 g, 7.5 mmol), 2-iodo-4-t-octylphenol (5.0 g, 15.1 mmol), and DMF ( 100ml). K2CO3 (4.2 g, 30.1 mmol) was added, and the reaction was heated under reflux for one day. The volatiles were then removed by flask to flask distillation, yielding a brown solid. The solid was taken up in Et2O (250 mL), washed with 3M NaOH solution (2 x 100 mL), brine (100 mL), and then dried over MgSO4. The reaction mixture was filtered, and concentrated on a rotary evaporator, to yield the crude product, which was further purified by column chromatography (SiO 2 , hexanes/EtOAc 95:5) to provide the desired product (1.6 g, 29 % of theoretical value 5.5 g). 1H NMR (400 MHz, CDCl3) δ 7.74 (d, J = 2.3 Hz, 2H), 7.28 (dd, J = 8.7, 2.3 Hz, 1H), 6.87 (d , J = 8.7 Hz, 2H), 4.77 - 4.61 (m, 2H), 2.42 (dt, J = 13.8, 6.8 Hz, 1H), 1.84 (dt, J = 14.0, 5.9 Hz, 1H), 1.68 (s, 4H), 1.36 (d, J = 6.1 Hz, 6H), 1.33 (s, 12H), 0. 74 (s, 18H). 2d. Preparation of Ligand 2 (L2).

[00113] A round bottom flask was charged with meso-4,4'-pentane-2,4-diylbis(oxy))bis(1-(tert-octyl)-3-iodobenzene)) (0.790 g, 1.08 mmol) and 9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2 - dioxaborolan-2-yl)phenyl)-9H-carbazole (1.052 g, 2.37 mmol), and 40 mL of THF. Na2CO3 (0.686 g, 6.47 mmol) was dissolved in 20 mL of water, and added to the THF solution, forming a biphasic solution, which was then sparged with N2 for 15 minutes. Pd(P(t-Bu)3)2 (0.017 g, 0.03 mmol) was dissolved in 6 mL of degassed THF in the dry box, and then added to the reaction mixture, which was heated to reflux under nitrogen for three days. After allowing the reaction mixture to cool to room temperature, the aqueous phase was discarded and the THF was removed from the organic phase using a rotary evaporator. Dichloromethane (80 ml) was added, and the solution was washed with 80 ml of water mixed with 20 ml of brine. The organic phase was evaporated to dryness under vacuum and the residue was dissolved in 50 ml of diethyl ether, filtered through a plug of silica gel, and evaporated to dryness under vacuum. Methanol (80 mL), THF (15 mL) and conc. (6 drops) were added, and the solution was refluxed overnight, then the solvent was removed under vacuum and the residue was triturated with a small amount of methanol, and again dried under vacuum. The resulting material was purified by silica gel column chromatography, gradient elution with 1% EtOAc in hexane ^ 5% EtOAc in hexane, yielding pure binder L2 (0.820 g, 74%). 1H NMR (400 MHz, CDCl3): δ 8.15 (dd, J = 7.5, 1.2 Hz, 4H), 7.40 (d, J = 2.5 Hz, 2H), 7.33 ( m, 10H), 7.23 (m, 6H), 7.16 (dd, J = 8.5, 2.3 Hz, 2H), 6.66 (d, J = 8.7 Hz, 2H), 6.23 (s, 2H), 4.52 (m, 2H), 2.47 (s, 6H), 2.22 (m, 1H), 1.74 (s, 4H), 1.71 (m , 1H), 1.38 (d, J = 6.1 Hz, 12H), 1.18 (d, J = 6.0 Hz, 6H), and 0.75 (s, 18H). 13C{1H} NMR (101 MHz, CDCl3) δ 151.1, 148.3, 144.0, 141.3, 141.2, 131.7, 130.3, 130.3, 129.2, 129, 1, 127.19, 126.8, 125.6, 125.6, 125.2, 123.3, 123.2, 120.2, 120.6, 119.5, 113.8, 110.3, 110.2, 72.7, 57.0, 42.7, 38.1, 32.4, 31.8, 31.5, 20.7, and 19.8. 2d. Preparation of Pro-Catalyst 2 (I2).

[00114] L4 ligand (0.500 g, 0.49 mmol) was dissolved in 10 mL of toluene, under an atmosphere of dry nitrogen, and the solution was added to a stirred suspension of ZrCl4 (0.114 g, 0.490 mmol) in 5 ml of toluene. MeMgBr (0.77 mL, 2.00 mmol; 2.6 M in Et2O) was added dropwise via syringe at room temperature. The mixture was stirred for two hours. The color of the reaction mixture slowly turned black. Hexane (5 ml) was added to the suspension, which was then filtered, and the filtrate was evaporated to dryness under vacuum. Toluene (15 mL) and hexane (5 mL) were added to the residue, the light suspension was filtered, and the filtrate was evaporated to dryness under vacuum, yielding I4 in high purity (292 mg, 52%). 1H NMR (400 MHz, C6D6) δ 8.35 (m, 2H), 8.10 (m, 2H), 7.67 (m, 1H), 7.57 — 7.32 (m, 12H), 7 .23 — 7.08 (m, 5H), 6.84 (ddd, J = 10.8, 8.5, 2.5 Hz, 2H), 5.04 (d, J = 8.5 Hz, 1H ), 4.87 (d, J = 8.6 Hz, 1H), 4.04 (m, 1H), 3.68 (m, 1H), 2.22 (s, 6H), 1.76 — 1 , 60 (m, 4H), 1.24 (s, 3H), 1.22 (s, 3H), 1.21 (s, 3H), 1.19 (s, 3H), 0.76 (s, 3H), 9H), 0.75 (s, 9H), 0.50 (d, J = 6.2 Hz, 3H), 0.32 (d, J = 6.5 Hz, 3H), -0.77 (s , 3H), and -0.91(s, 3H). Example 3. 3a. Preparation of 3,6-bis(1,1-dimethylethyl)-9H-carbazole.

[00115] A 500 mL three-necked round bottom flask, equipped with a mechanical stirrer, a nitrogen gas bubbler, and an addition funnel, was charged with 20.02 g (120.8 mmol) of carbazole, 49 .82g (365.5 mmol) of ZnCl2, and 300 mL of room temperature nitromethane. To the resulting dark brown suspension, 49.82g (365.5 mmol) of 2-chloro-2-methyl-propane (also known as tertiary butyl chloride) was added dropwise from the addition funnel to the over the period of 2.5 hours. After the addition was complete, the resulting suspension was stirred for an additional 18 hours, and the reaction mixture was poured into 800 mL of ice water, and extracted with methylene chloride (3 x 500 mL). The combined extracts were dried with anhydrous magnesium sulfate, filtered and concentrated, first by rotary evaporation and then by high vacuum evaporation to remove nitromethane. The resulting residue was dissolved in hot methylene chloride (70 mL), followed by hot hexanes (50 mL), and the resulting solution was cooled to room temperature, then placed in a refrigerator overnight. . The resulting solids that formed were isolated, washed with cold hexanes, then dried under high vacuum to yield 10.80g (32.0%) of the desired product as off-white crystals. 1H NMR (400 MHz, CDCl3) δ 8.11 (d, J = 1.6 Hz, 2H), 7.75 (s, 1H), 7.48 (dd, J = 8.5, 1.9 Hz , 2H), 7.31 (d, J = 8.5 Hz, 2H), 1.48 (s, 18H). 13C{1H} NMR (101 MHz, CDCl3) δ 142.17 (s), 137.96 (s), 123.45 (s), 123.28 (s), 116.11 (s), 109.97 (s), 34.73 (s), 32.09 (s). 3b. Preparation of 2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenol

[00116] To a stirred solution of 10.30 g (50.00 mmol) of 4-(2,4,4-trimethylpentan-2-yl)phenol, in 125 mL of methanol at 0°C, were added 7.48 g (50.00 mmol) of NaI and 2.00 g (50.0 mmol) of NaOH. To the resulting mixture, 86 ml of 5% aqueous NaOCl solution (commercial bleach) was added over a period of one hour. The resulting suspension was stirred for a further hour at 0°C, then 30 ml of 10% aqueous Na2S2O3 solution was added, and the resulting reaction mixture was acidified with the addition of dilute hydrochloric acid. The resulting mixture was extracted with methylene chloride, and the resulting organic layer was washed with brine, and then dried over anhydrous magnesium sulfate. The volatiles were removed under vacuum, and the resulting residue was purified by flash chromatography on silica gel, eluting with 5 percent by volume (% vol) ethyl acetate in hexanes to yield 11.00 g (66%) of the desired product as a viscous oil. 1H NMR (CDCl3) δ 7.60 (d, J = 2.5 Hz, 1H), 7.25 (dd, J = 8.5 and 2.2 Hz, 1H), 6.90 (d, J = 8.5 Hz, 1H), 5.13 (s, 1H), 1.69 (s, 2H), 1.32 (s, 6H) and 0.74 (s, 9H). 13C{1H} NMR (CDCl3) δ 152.21, 144.52, 135.56, 128.03, 114.17, 85.36, 56.92, 38.01, 32.43, 31.90 and 31 .64. GC/MS (m/e): 332 (M+). 3c. Preparation of 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran.

[00117] For a stirred solution of 4.91 g (14.8 mmol) of 4-(2,4,4-trimethylpentan-2-yl)phenol and 1.50 g (17.8 mmol) of 3.4 - dihydropyran, in 5 ml of methylene chloride, at 0°C, was added 0.039 g (0.205 mmol) of para-toluenesulfonic acid monohydrate. The resulting solution was allowed to warm to room temperature, and thereafter stirred for about 10 minutes. Then triethylamine (0.018 g, 0.178 mmol) was added, and the resulting mixture was diluted with 50 mL of methylene chloride, and washed successively with 50 mL each of 1M NaOH, water and brine. The organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated to yield a crude material which was purified by flash chromatography on silica gel using 5% by volume ethyl acetate in hexanes to yield 5.18 g (93.12%) of the desired product as a golden oil. 1H NMR (CDCl 3 ) δ 7.74 (d, J = 2.3 Hz, 1H), 7.27 (dd, J = 2.3 and 8.6 Hz, 1H), 6.99 (d, J = 8.6 Hz, 1H), 5.49 (m, 1H), 3.91 (m, 1H), 3.61 (m, 1H), 2.20-1.60 (m, 6H), 1, 69 (s, 2H), 1.34 (s, 6H) and 0.75 (s, 9H). 13C{1H} NMR (CDCl3) δ 153.27, 145.49, 136.98, 127.08, 114.44, 96.72, 87.09, 61.69, 56.91, 37.95, 32 .33, 31.81, 31.52, 31.44, 30.26, 25.27, 18.36. 3d. Preparation of 3,6-di-tert-butyl-9-(2-(tetrahydro-2H-pyran-2-yloxy)-5-(2,4,4-trimethyl-pentane-2-yl)phenyl) -9H carbazole.

[00118] To a 50 mL three-necked round bottom flask equipped with a stir bar and condenser, under ambient N2 atmosphere, the following was added: 20 mL dry toluene, 5.00 g (12.01 mmol ) from 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran; 3.56 g (12.01 mmol) of 3,6-di-tert-butyl carbazole, 0.488 g (2.56 mmol) of CuI, 7.71 g (36.2 mmol) of K3PO4, and 0.338 g (3 .84 mmol) of N,N-dimethylethylenediamine. The resulting reaction mixture was heated under reflux for 48 hours, cooled, and filtered through a bed of silica gel. The silica gel was washed with tetrahydrofuran (THF), and the resulting solution was concentrated to yield a crude residue. Purification was accomplished by recrystallization from acetonitrile to give 4.57 g (67.0%) of the desired product as a white solid. 1H NMR (CDCl3) δ 8.13 (t, J=1.71 Hz, 1H), 7.48 (d, J=2.4 Hz, 1H), 7.40 (m, 3H), 7.31 (d, J = 8.68 Hz, 1H), 7.14 (d, J = 8.68 Hz, 1H), 7.08 (d, J = 8.56 Hz, 1H), 5.22 (t , J = 2.81 Hz, 1H), 3.72(td, J = 11.12 and 2.8 Hz, 1H), 3.47 (dt, J = 11.12 and 3.47 Hz, 1H) , 1.75 (s, 2H), 1.474 (s, 9H), 1.472 (s, 9H), 1.394 (s, 3H), 1.391 (s, 3H), 1.37-1.12 (m, 6H) , 0.82 (s, 9H). 13C{1H} NMR (CDCl3) δ 150.96, 144.22, 142.07, 140.02, 127.49, 126.60, 126.56, 123.14, 123.12, 122.96, 116 .37, 115.88, 115.72, 110.18, 109.52, 97.02, 61.56, 57.03, 38.23, 34.69, 32.41, 32.07, 31.86 , 31.72, 31.50, 29.98, 25.06, 17.61. 3e. Preparation of 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3 ,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole.

[00119] For a stirred solution of 2.5 g (4.4 mmol) of the carbazole derivative, in 40 mL of THF, at 0°C, under a nitrogen atmosphere, 2.8 mL (7.0 mmol) of n-butyl lithium (2.5M solution in hexanes) was added over a period of five minutes. The solution was stirred at 0°C for a further three hours. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.44 mL, 7.0 mmol) was added to the solution, and stirring was continued at 0°C for an additional hour. The reaction mixture was slowly warmed to room temperature, and stirred for 18 hours. The reaction mixture was concentrated to dryness and by rotary evaporation, and 100 mL of ice water was added. The mixture was extracted with methylene chloride. The organic layer was washed with brine, and dried over anhydrous magnesium sulfate. Removal of the solvent, followed by recrystallization from acetonitrile, gave 2.4 g (78.6%) of the title product as a white solid. 1H NMR (CDCl 3 ) δ 8.30-7.96 (m, 2H), 7.81(d, J = 2.5 Hz, 1H), 7.58-7.32 (m, 3H), 7, 14 (d, J = 8.6 Hz, 2H), 4.85 (d, J = 2.8 Hz, 1H), 2.76 (td, J = 11.0, 2.7 Hz, 1H), 2.59 (dd, J = 7.9, 3.5 Hz, 1H), 1.73 (s, 2H), 1.67-0.87 (m, 6H), 1.46 (s, 9H) , 1.45 (s, 9H), 1.38 (s, 9H), 1.37 (s, 9H), 0.78 (s, 9H); 13C{1H} NMR (CDCl3) δ 156.25, 145.86, 142.05, 142.01, 139.79, 139.78, 133.82, 130.61, 129.72, 123.39, 123 .37, 123.05, 115.59, 115.55, 110.20, 110.11, 101.41, 83.64, 61.20, 56.95, 38.37, 34.68, 32.42 , 32.08, 31.90, 31.45, 29.97, 25.06, 25.04, 24.79, 18.16. MS m/e 716.38 (M+Na). 3f. Preparation of meso-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene).

[00120] A three-necked round-bottom flask of 2 Equipped with a thermometer, a magnetic stirrer, an addition funnel, and a nitrogen pad, was charged with 2,4-pentanediol (30.46 g, 292.5 mmol, 1 equiv), 2-bromo-4-fluorophenol (114.39 g, 598.9 mmol, 2.04 equiv), triphenylphosphine (157.12 g, 599.0 mmol, 2.04 equiv), and THF (600 mL), and the contents were cooled to 2°C in an ice-water bath. A solution of DIAD (121.11 g, 598.9 mmol, 2.04 equiv) in THF (130 mL) in the addition funnel was added at such a rate to keep the reaction below 5°C ( addition took approximately four hours). The resulting mixture was stirred at 2°C for an additional hour, and a sample was taken for analysis by GC-MS, which indicated that the reaction was nearing completion. After stirring overnight at room temperature, the volatiles were removed under reduced pressure. Cyclohexane (700 ml) was added to the residue and the suspension was stirred at room temperature for 30 minutes. The insoluble solid was filtered, washed with cyclohexane (100 mL x 3). The cyclohexane solution was washed with 1N NaOH (200 mL), water (200 mL), 1N HCl (200 mL), water (500 mL x 2), and then concentrated under reduced pressure to yield an oil residue. The oil residue was dissolved in hexane (100 mL), and then passed through a pad of silica gel (315 g), eluting with hexane (300 mL), and hexane-AcOEt (20:1 by volume, from hexane 2 L + EtOAc 100 mL), concentrated, and dried to give the desired background group (123.8 g, 94% yield). 1H NMR (400 MHz, C6D6) δ 7.14 (dd, J = 8.4, 3.9 Hz, 2H), 6.64 (dt, J = 9.1, 3.9 Hz, 2H), 6 .48 (dd, J=9.0, 3.7Hz, 2H), 4.22 (m, 2H), 2.17 (dt, J=13.6, 6.5Hz, 1H), 1, 45 (dt, J = 13.6, 5.6 Hz, 1H), and 0.98 (d, J = 6.1 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 156.9 (d, J = 235.8 Hz), 150.9 (d, J = 2.8 Hz), 120.9 (d, J = 25.8 Hz) , 115.62 (d, J = 7.7 Hz), 114.9 (d, J = 21.5 Hz), 113.7 (d, J = 10.1 Hz), 72.8, 42.7 , and 19.6. 19F NMR (376 MHz, C6D6) δ -121.33. 3g. Preparation of Linker 3 (L3).
Method 1: To a 2 L reactor vessel, meso-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene) (80 g, 177 .7 mmol) and 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (271.3 g, 391.0 mmol), dissolved in 800 mL of toluene, under an atmosphere of nitrogen, with stirring. To this mixture, NaOH (42.7g dissolved in 100 mL of water, 1.0 mol) was added, followed by the rapid addition of Pd(PPh3)4 (8.21 g, 7.11 mmol), and the reaction was heated to 88°C. The course of the reaction was monitored by means of LC, until it was considered complete at the five hour mark. At this point, the reaction vessel was cooled to rt (room temperature), the caustic layer was removed, and 200 mL of a 20% HCl solution was added, and the reaction was heated once more to 88°C for five o'clock. The reactor was cooled to room temperature, the aqueous layer was removed, and the organic layer was washed with brine, and dried over MgSO4. Filtration to remove MgSO4, followed by concentration by rotary evaporation, produced an off-white solid, which was washed with acetonitrile and the remaining solid was dried under vacuum to provide pure DOC-6163 binder (199.5 grams, 89% yield). ). Method 2 (two-step procedure)
[00121] Ph3P (1.05 g, 4 mmol), meso-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene) (45.01 g, 100.0 mmol), aliquot 336 (0.326 g) and toluene (500 mL) were added to a 2L three-necked round bottom flask equipped with a cold water condenser, magnetic stirrer, a thermometer, and a nitrogen in an oil bath. The mixture was sparged with nitrogen for 30 minutes. Pd(OAc)2 (449.02 mg, 2.0 mmol, 0.02 equiv) was added, and the mixture was stirred for 5-10 minutes, until solid Pd(OAc)2 dissolved, during nitrogen sparge. . Then 2N NaOH (300 mL, pre-sparged with nitrogen) was added, under nitrogen, and the mixture was sparged with nitrogen for five minutes. The reaction mixture was heated to 75-78°C, and a solution of 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (156.64 g , 220 mmol) in 400 mL of toluene (sparged with nitrogen for 30 minutes) was added over three hours via a syringe pump. The reaction mixture was heated at 80-86°C overnight (reaction was complete over 4-6 hours as monitored by LC) under nitrogen atmosphere in an oil bath at 105° C, which resulted in a dark mixture. After being cooled to 50°C, air was bubbled into the reaction mixture for one hour to destroy the catalyst. The reaction mixture was then decanted to the shear stage. The bottom aqueous layer was removed, and extracted with toluene (100 mL). The toluene phase was washed with water (500 mL x 2). 2N HCl (300 mL, prepared from 100 mL 6N HCl + 200 mL H2O) was added to the toluene solution. The resulting mixture was stirred at 80-86°C, in an oil bath at 105-108°C, under nitrogen overnight. LC analysis of the reaction mixture indicated that the deprotection of the THP group was complete. The reaction mixture was allowed to cool to room temperature. The bottom aqueous layer was removed, which was subsequently extracted with toluene (100 mL). The yellow to brown toluene phase was washed with water (500 mL x 2). The toluene solution was filtered through a pad of silica gel (60-100g). The wet silica gel cake was washed with toluene (100 mL). The slightly yellow toluene solution was concentrated under reduced pressure by rotary evaporation, which produced a thick residue (~185.5 g). Acetonitrile (500 mL) was added to the residue, and the mixture was roto-vap centrifuged at 60°C. The thick residue dissolved gradually, forming a clear, slightly yellow solution. The white solid precipitated out of solution after some time. After cooling to room temperature overnight, the solid was collected by filtration, washed/rinsed with acetonitrile (200 mL x 2), suction dried, and dried in a vacuum oven to yield the desired product (115 .5 g, 92.0% yield. 1H NMR (400 MHz, C6D6) δ 8.45 (t, J = 2.4 Hz, 4H), 7.50-7.56 (m, 6H), 7.41 (d, J = 8.8 Hz , 2H), 7.16 (obscured by CD5H), 6.32 (s, 2H), 6.30 (dd, J = 9.3, 4.7 Hz, 2H), 6.23 (s, 2H) , 4.16 (m, 2H), 2.01 (dt, J = 14.3, 6.9 Hz, 1H), 1.55 (s, 4H), 1.37 (dt, J = 14.2 , 5.0 Hz, 1H), 1.44 (s, 18H), 1.43 (s, 18H), 1.20 (s, 12H), 0.83 (d, J = 6.0 Hz, 6H ), and 0.80 (s, 18H). 13C{1H} NMR (101 MHz, C6D6) δ 158.2 (d, J = 241.2 Hz), 149.8 (d, J = 1.7 Hz), 148.9, 143.2, 143, 0, 143.0, 140.7 (d, J = 5.5 Hz), 131.1 (d, J = 7.5 Hz), 129.4, 127.2, 126.1, 124.2 ( d, J = 2.7 Hz), 118.9 (d, J = 23.4 Hz), 117.3 (d, J = 9.2 Hz), 116.8, 115.8 (d, J = 22.8 Hz), 110.2 (d, J = 10.0 Hz), 73.7, 57.1, 42.66, 38.3, 34.9, 32.5, 32.2, 32, 1, 31.7, 31.6, and 19.5. 19F NMR (376 MHz, C6D6) δ -120.95. 3g. Preparation of Pro-Catalyst 3 (I3).

[00122] A 5 L reactor was charged with 4.5 L of toluene, and cooled to -30°C. To the same, ZrCl4 (38.81 g, 166.8 mmol) was added, followed by MeMgBr (211.8 mL of a 3M solution, 635.5 mmol). The resulting mixture was allowed to stir for five minutes, after which time L3 linker (199.5 g, 158.9 mmol) was added. The suspension was allowed to gradually warm to room temperature, and stirred for an additional three hours, then filtered. The toluene was then removed under vacuum to provide I3 as an off-white solid of good purity (quantitative, 234 grams). 1H NMR (400 MHz, C6D6) δ 8.53 (m, 2H), 8.41 (dd, J = 2.0, 12.0 Hz, 2H), 7.72 (m, 2H), 7.67 (d, J = 3.0 Hz, 1H), 7.57-7.61 (m, 6H), 7.44 (ddd, J = 2.9, 8.1, 9.4 Hz, 2H), 7.24 (dd, J = 2.0, 14 Hz, 2H), 7.01 (dd, J = 3.7, 8.9 Hz, 2H), 6.95 (dd, 4.0, 7, 3 Hz, 1H), 6.60 (m, 2H), 4.95 (dd, J = 4.4, 8.2 Hz, 2H), 4.82 (dd, J = 4.4, 8.2 Hz, 2H), 4.21 (m, 2H), 3.78 (m, 2H), 1.64 (s, 3H), 1.58 (s, 3H), 1.48 (s, 9H), 1.46 (s, 9H), 1.32 (s, 9H), 1.30 (s, 9H), 0.770.90 (m, 8H), 1.20-1.28 (m, 8H), 0 .60 (d, J = 7.3 Hz, 3H), 0.41 (d, J = 7.3 Hz, 3H), -0.72 (s, 3H), and -0.88 (s, 3H ). 19F NMR (376 MHz, C6D6) δ -114.83. Example 4. 4a. Preparation of 2-bromo-1-(methoxy-methoxy)-4-methylbenzene.

[00123] 2-Bromo-4-methylphenol (13.1 g, 70.0 mmol), dimethoxymethane (35 mL), p-toluenesulfonic acid (100 mg) and methylene chloride (300 mL) were heated under reflux in nitrogen atmosphere for three days, using a Soxhlet condenser containing activated 3Â molecular sieves. Molecular sieves were replaced with freshly activated sieves after every 24 hours. The reaction mixture was cooled, and the volatiles were removed by rotary evaporation. The residue was taken up in 100 ml of ether, and washed successively with 100 ml of 2M sodium hydroxide solution, 100 ml of water and 100 ml of brine. The organic layer was dried over anhydrous magnesium sulfate and passed through a short bed of silica gel. Removal of solvent gave 14.5 g (92%) of 2 as a pale yellow oil, which was used as such for the next step. 1H NMR (CDCl3) δ 7.40 (m, 1H), 7.07 (m, 2H), 5.25 (s, 2H), 3.55 (s, 3H) and 2.31 (s, 3H) .
[00124] 4c. Preparation of 9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2 - yl)phenyl)-9H-carbazole

[00125] 9-(5-Methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole (40 g, 0.11 mol) was dissolved in 300 mL of THF, in a nitrogen-filled glove box, and deprotonated by the slow addition of PhLi (74.6 mL, 0.13 mol; 1.8 M in n-Bu2O). The reaction mixture was stirred for one hour. 2-Isopro-poxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25.1 mL, 0.12 mol) was added slowly, and the reaction mixture was stirred for an additional hour. Removal of the solvent in vacuo gave an oil residue, which was dissolved in 450 ml of chloroform and washed with water (2 x 450 ml). The organic layer was dried over MgSO 4 , filtered, and the filtrate was concentrated in vacuo to yield a dark oil, which was then mixed with 600 mL of hexane, and concentrated to approximately 250 mL, causing a large amount of solids. light browns formed. The solids were filtered and dried under vacuum (42 g, 78%). 1H NMR (400 MHz, CDCl3) δ 7.99 (m, 2H), 7.59 (d, J = 2.3 Hz, 1H), 7.28 (ddd, J = 15.4, 8.2, 1.1 Hz, 2H), 7.14 (m, 5H), 4.78 (t, J = 3.0 Hz, 1H), 2.44 (m, 2H), 2.25 (s, 3H) , 1.59 (m, 1H), 1.28 (s, 6H), 1.27 (s, 6H), 1.09 (m, 4H), 0.82 (m, 1H). 4d. Preparation of meso-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-methyl-benzene).

[00126] A 2L three-necked round bottom flask equipped with a thermometer, a magnetic stirrer and an addition funnel was charged with meso-2,4-pentanediol, (30.50 g, 293 mmol), 2- bromo-4-methylphenol (112.03 g, 599 mmol), triphenylphosphine (157.12 g, 599 mmol), and THF (600 mL). The reaction vessel was then placed under an atmosphere of nitrogen, and the addition funnel was charged with diisopropyl azodicarboxylate (DIAD, 121.11 g, 599 mmol) and THF (250 mL). The contents of the flask were cooled to 2°C in an ice-water bath, the DIAD solution in the addition funnel was added at such a rate to maintain the reaction temperature at 2-5°C (the addition took approximately 3.5 h). The resulting mixture was stirred at 25°C for an additional hour (a sample was taken for analysis by GC-MS, which showed that the reaction was close to completion) and then allowed to warm to room temperature for one day. To the other. Volatiles were removed under reduced pressure to yield a solid residue (~424 g). The residue was extracted with cyclohexane (1000 ml) at 35°C by centrifugation on a rotary evaporator for 30 minutes, without drawing vacuum. This process was repeated three more times with cyclohexane (350 mL x 3) at 35°C. The combined cyclohexane solution was washed with 1N NaOH (350 mL x 2), water (500 mL), 1N HCl (350 mL), and water (500 mL x 2). The washed cyclohexane solution was concentrated to approximately 300 mL, passed through a pad of silica gel (350 g), and eluted with hexane/EtOAc (20:1 by volume), concentrated, and dried to yield the group desired background (119.0 grams, 91.5%). 1H NMR (400 MHz, CDCl3) δ 7.26 (d, J = 2.3 Hz, 2H), 7.04 (dd, J = 8.5, 2.3 Hz, 2H), 6.94 (d , J = 8.5 Hz, 2H), 4.63 (m, 2H), 2.39 (dt, J = 13.8, 6.7 Hz, 1H), 2.26 (s, 6H), 1 .82 (dt, J = 14.1, 5.9 Hz, 1H), and 1.37 (d, J = 6.1 Hz, 6H). 13C{1H} NMR (101 MHz, CDCl3) δ 152.1, 133.9, 131.8, 115.2, 114.77, 112.9, 72.5, 42.9, 20.3, and 20 ,0.
[00127] 4e. Preparation of Linker 4 (L4).

[00128] To a 2 L reactor vessel, meso-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-methyl-benzene) (40, 0 g, 90.5 mmol) and 9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (96.2 g, 199.0 mmol, 2.2 equiv), dissolved in 300 mL of toluene, under an atmosphere of nitrogen, with stirring. To this mixture, NaOH (21.7 g dissolved in 100 mL of water, 0.5 mol, 6 equiv) was added, followed by the rapid addition of Pd(PPh3)4 (4.18 g, 3.61 mmol, 0 .04 equiv). The reaction was then heated to 88°C until complete. The course of the reaction was monitored by means of LC, until it was considered complete at the seven hour mark. At this point, the reaction vessel was cooled to room temperature, the caustic layer was removed, 200 mL of a 20% HCl solution was added, and the reaction was heated under reflux for five hours. The reactor was cooled to room temperature, the stirring was stopped, and the aqueous layer removed. The organic layer was washed with brine, dried over MgSO4 , then filtered, and concentrated by rotary evaporation to yield an off-white solid. The crude residue was washed with acetonitrile and dried under vacuum to provide pure L2 binder (44.2 grams, 60% yield). 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 7.6 Hz, 4H), 7.25 (m, 18H), 6.91 (dd, J = 8.3, 2.0 Hz , 2H), 6.64 (d, J = 8.3 Hz, 2H), 6.30 (s, 2H), 4.45 (m, 2H), 2.41 (s, 6H), 2.32 (s, 6H), 2.16 (m, 1H), 1.68 (m, 1H), and 1.14 (d, J = 6.1 Hz, 6H). 13C{1H} NMR (101 MHz, CDCl3) δ 151.4, 148.4, 141.4, 141.3, 133.1, 131.9, 130.6, 130.1, 129.3, 128, 8, 128.0, 125.8, 125.4, 123.4, 123.4, 120.3, 119.6, 114.9, 110.4, 110.3, 73.3, 42.7, 20.8, 20.7, and 19.9.
[00129] 4f. Preparation of Pro-Catalyst 4 (I4).

[00130] A 5 L reaction vessel was charged with 3 L of toluene, and cooled to -30°C. To this vessel was added ZrCl4 (29.6 g, 127 mmol), followed by MeMgBr (161 mL of a 3M solution, 484 mmol). The resulting mixture was allowed to stir for five minutes, after which the binder (100 g, 121 mmol) was added. The suspension was allowed to gradually warm to room temperature, stirred for an additional three hours, and then filtered. The filtrate was concentrated, and analyzed by 1H NMR spectroscopy, which showed the presence of I4, but with low purity. The filter cake was then extracted with methylene chloride (1.5 L), and concentrated, to provide I4 in high purity (66 g, 58% yield). 1H NMR (400 MHz, CDCl3) δ 8.30 (dd, J = 8.5, 12.1 Hz, 2H), 8.12 (dd, J = 7.4, 10.3 Hz, 2H), 7 .57 (d, J=8.25Hz, 1H), 7.26-7.0 (m, 21H), 6.40 (dd, J=2.2, 8.5Hz, 1H), 6 .30 (dd, J = 2.5, 7.15 Hz, 1H), 4.44 (d, J = 8.1 Hz, 1H), 4.30 (d, J = 7.9 Hz, 1H) , 4.05 (m, 1H), 3.70 (m, 1H), 2.38 (s, 3H), 2.37 (s, 3H), 2.23 (s, 6H), 1.35 ( m, 1H), 0.59 (d, J = 6.8 Hz, 3H), 0.43 (d, J = 7.2 Hz, 3H), -1.51 (s, 3H), and -1 .68 (s, 3H).
[00131] Example 5. 5a. Preparation of rac-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene).

[00132] A 2-L round bottom flask equipped with a magnetic stirrer was charged with rac-2,4-pentanediol (16.9 g, 162.3 mmol), 2-bromo-4-fluorophenol (65 .09 g, 340.8 mmol), triphenyl phosphine (89.38 g, 340.76 mmol), and THF (600 mL), and cooled to 0 °C in an ice water bath. A solution of DIAD (67.09 g, 340.76 mmol) in THF (130 mL) was slowly added to the flask via the addition funnel. The resulting mixture was stirred overnight at room temperature and the next day the volatiles were removed under reduced pressure. Pentane (700 mL) was added to the residue, and the suspension was stirred at room temperature for 30 minutes. The insoluble solid was filtered, rinsed with pentane (100 mL x 3), and then concentrated under reduced pressure to yield an oil residue. The oil residue was dissolved in hexane (100 mL), and then passed through a pad of silica gel, eluting first with hexane (300 mL), followed by hexane-EtOAc (4:1 by volume), providing the desired product. with high purity (42.1 grams, 48% yield). 1H NMR (400 MHz, CDCl3): δ 7.20 (dd, J = 7.8, 3.0 Hz, 2H), 6.83 (ddd, J = 9.1, 7.7, 3.0 Hz , 2H), 6.74 (dd, J = 9.1, 4.9 Hz, 2H), 4.68 (sixtet, J = 6.1 Hz, 2H), 2.05 (dd, J = 7, 3, 5.5 Hz, 2H), and 1.35 (d, J = 6.2 Hz, 6H). 13C{1H} NMR (101 MHz, CDCl3): δ 156.5 (d, J = 243.2 Hz), 151.1 (d, J = 2.8 Hz), 120.1 (d, J = 25 .8 Hz), 116.0 (d, J = 8.4 Hz), 114.8 (d, J = 22.7 Hz), 113.3 (d, J = 10.1 Hz), 73.4 , 44.8, and 20.2. 19F NMR (376 MHz, C6D6) δ -121.22. 5e. Preparation of Linker 5 (L5).

[00133] To one flask, rac-4,4'-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene) (0.602 g, 1.34 mmol) was added. and the top group (2.04 g, 2.94 mmol) dissolved in 5 mL of toluene, under a nitrogen atmosphere, with stirring. To this, NaOH (0.321 g dissolved in 1 mL of water, 8.02 mmol) was added, followed by the rapid addition of Pd(PPh3)4 (0.060 g, 0.054 mmol), and the reaction was heated to 88°C. The course of the reaction was monitored by means of LC, until it was considered complete at the five hour mark. At this point, the reaction vessel was cooled to room temperature, the caustic layer was removed, 2 mL of a 20% HCl solution was added, and the reaction was heated to reflux once more for 5 h. The reactor was cooled to room temperature, the aqueous layer was removed, and the organic layer was washed with brine, and dried over MgSO4. Filtration to remove MgSO4, followed by concentration by rotary evaporation, produced an off-white solid, which was washed with acetonitrile and the remaining solid dried under vacuum to provide pure L5 (1.41 grams, 84% yield). 1H NMR (400 MHz, CDCl3): δ 8.19 (dt, J = 3.3, 1.5 Hz, 4H), 7.44 (m, 6H), 7.32 (t, J = 1.8 Hz, 2H), 7.07 (m, 6H), 6.66 (td, J = 8.3, 3.1 Hz, 2H), 6.41 (dd, J = 9.2, 4.6 Hz , 2H), 5.91 (s, 2H), 4.36 (m, 2H), 1.74 (s, 4H), 1.71 (m, 2H), 1.49 (s, 18H), 1 .47 (s, 18H), 1.39 (s, 12H), 0.92 (d, J = 5.8 Hz, 6H), and 0.80 (s, 18H). 13C NMR (101 MHz, CDCl3): δ 157.5 (d, J = 241.3 Hz), 150.0 (d, J = 1.8 Hz), 147.9, 142.8, 142.6 ( d, J = 8.4 Hz), 139.8 (d, J = 10.9 Hz), 130.2 (d, J = 7.8 Hz), 129.0, 127.2, 126.56, 124.8, 123.6 (d, J = 13.3 Hz), 123.3, 123.1, 118.2 (d, J = 23.4 Hz), 116.4, 116.3, 115, 4 (d, J = 22.8 Hz), 109.2 (d, J = 31.6 Hz), 73.1, 57.0, 44.7, 38.2, 34.7 (d, J = 1.6 Hz), 32.4, 32.0, 31.9, 31.7, 31.6, and 19.7. 19F NMR (376 MHz, C6D6) δ -121.96. 5e. Preparation of Procatalyst 5 (I5).

[00134] A flask was charged with 30 mL of cold (30°C) toluene and ZrCl4 (0.340 grams, 1.50 mmol). To the resulting cold suspension, MeMgBr (1.90 mL of a 3M solution in Et2O, 5.70 mmol) was added. The resulting mixture was allowed to stir for 2-3 minutes, at which point, L5 linker (1.79 grams, 1.43 mmol) was added. The suspension was allowed to warm to room temperature naturally and stirred for two hours. The solvent was then removed in vacuo, and the dark brown suspension was extracted with hexanes (100 mL) and filtered. The filtrate was collected, and dried under vacuum, yielding I5 as an off-white solid of good purity (1.46 grams, 75% yield). 1H NMR (400 MHz, C6D6) δ 8.59 (m, 2H), 8.40 (m, 2H), 7.79 — 7.52 (m, 8H), 7.43 (dd, J = 8, 4, 1.9 Hz, 2H), 7.23 (dd, J = 12.7, 2.5 Hz, 2H), 6.98 (dt, J = 9.0, 3.2 Hz, 2H), 6.66 (ddd, J = 8.9, 7.4, 3.2 Hz, 1H), 6.59 (ddd, J = 8.9, 7.4, 3.1 Hz, 1H), 5, 04 (dd, J = 8.9, 5.0 Hz, 1H), 4.88 (dd, J = 8.9, 4.9 Hz, 1H), 4.16 (m, 1H), 3.74 (m, 1H), 1.80 (m, 1H), 1.67 — 1.57 (m, 5H), 1.48 (s, 9H), 1.47 (s, 9H), 1.31 ( s, 9H), 1.30 (s, 9H), 1.28 - 1.20 (m, 12H), 0.86 (s, 9H), 0.85 (s, 9H), 0.59 (d , J = 6.4 Hz, 3H), 0.40 (d, J = 6.6 Hz, 3H), -0.82 (s, 3H), -0.82 (s, 3H). 19F NMR (376 MHz, C6D6) δ -114.59, and -114.68. Preparation of ethylene-based polymers in a single reactor
[00135] All raw materials (ethylene, 1-octene) and the process solvent (an ISOPAR E trademarked high-purity isoparaffinic narrow boiling range solvent, commercially available from ExxonMobil Corporation) are sieved purified. molecules before introduction into the reaction medium. Hydrogen is supplied in pressurized cylinders as a high purity grade, and is not yet purified. The monomer feed stream from the reactor (ethylene) is pressurized by means of a mechanical compressor from reaction pressure above 525 psig. The solvent and comonomer (1-octene) feed is pressurized through a mechanical positive displacement pump at reaction pressure above 525 psig. Individual catalyst components are manually batch diluted to specified component concentrations with purified solvent (ISOPARE) and pressurized to reaction pressure above 525 psig. All reaction feed flows are metered with mass flow meter and independently controlled with automated computer valve control systems.
[00136] The continuous solution polymerization reactor consists of a complete liquid, non-adiabatic, isothermal, circulating, and independently controlled loop. The reactor has independent control of all feeds of freshly prepared solvents, monomers, comonomers, hydrogen and catalyst components. The combined solvent, monomer, comonomer and hydrogen feed to the reactor is temperature controlled anywhere between 5°C to 50°C, and typically at 25°C, by passing the feed stream through a heat exchanger. The freshly prepared comonomer feed to the polymerization reactor is fed with the solvent feed. Total freshly prepared feed to each polymerization reactor is injected into the reactor at two locations, with more or less equal reactor volumes between each injection site. Freshly primed feed is typically controlled with each injector receiving half the mass flow of total freshly primed feed. Catalyst components are injected into the polymerization reactor through specifically designated injection stingers and are each injected separately at the same relative location in the reactor with no contact time prior to the reactor. Feeding the primary catalyst component is computer controlled to maintain the monomer concentration in the reactor at a specified target. The cocatalyst components are fed, based on specified molar ratios calculated for the primary catalyst component. Immediately after each freshly prepared injection site (or feed or catalyst), the feed streams are mixed with the contents of the circulating polymerization reactor with Kenics static mixing elements. The contents of each reactor are continuously circulated through heat exchangers responsible for removing the heat of reaction, and with the temperature on the coolant side responsible for maintaining the isothermal reaction environment at the specified temperature. Circulation around each reactor loop is provided by a screw pump.
[00137] The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and the molten polymer) leaves the first loop of the reactor and passes through a control valve (responsible for maintaining the pressure of the first reactor to a specified target). As the stream leaves the reactor, it is brought into contact with water to stop the reaction. In addition, various additives, such as antioxidants, can be added at this point. The stream passes through another set of Kenics static mixing elements to evenly disperse catalyst death and additives.
[00138] After addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the temperature of the stream in preparation for polymer separation from other lower boiling reaction components. The stream then enters a two-phase devolatilization and separation system, in which the polymer is removed from the solvent, hydrogen, and the unreacted monomer and comonomer. The recycled stream is purified before entering the reactor again. The separated and devolatilized polymer melt is pumped through a specially designed submerged pelletizing mold, cut into solid uniform pellets, dried, and transferred to a funnel. After validating the initial polymer properties, the solid polymer pellets are manually poured into a box for storage. Each box typically holds approximately 1200 pounds of polymer pellets.
[00139] The non-polymeric portions, removed in the devolatilization step, pass through several process steps, which separate most of the ethylene, which is removed from the system, to a vent destruction unit (which is recycled into manufacturing units). Most of the solvent is recycled back to the reactor after passing through purification beds. This solvent may still have an unreacted comonomer in it, which is enriched with the freshly prepared comonomer before re-entry into the reactor. This comonomer fortification is an essential part of the product density control method. This recycling solvent may still have some hydrogen, which is then enriched with freshly prepared hydrogen to reach the target molecular weight of the polymer. A very small amount of solvent leaves the system as a co-product, due to solvent in the carrier in the catalyst streams and a small amount of solvent that is part of commercial grade comonomers. Inventive Examples
Comparative Examples
Single Reactor Ethylene/Octene Copolymerizations in Batch Reactor
[00140] A stirred one gallon (3.79 L) autoclave reactor was charged with about 1.35 kg of alkane solvent mixed with ISOPAR E and 1-octene (250 g). The reactor was then heated to the desired temperature (140°C or 175°C), and charged with hydrogen (if desired), followed by an amount of ethylene to bring the total pressure to about 450 psig (2.95 MPa). . The ethylene feed was passed through an additional purification column before entering the reactor. The catalyst composition was prepared in a dry box, under an inert atmosphere, by mixing the desired procatalyst and a cocatalyst (a mixture of 1.2 equivalents of tetrakis(pentafluorophenyl)borate(1-)amine, and 50 equiv of alumoxane modified with triisobutylaluminum (MMAO-3A)) with additional solvent to yield a total volume of about 17 mL. The activated catalyst mixture was then quickly injected into the reactor. Reactor pressure and temperature were kept constant by feeding ethylene during polymerization, and cooling the reactor as needed. After 10 minutes, the ethylene feed was stopped, and the solution was transferred to a nitrogen-purged resin boiler. The polymer was dried completely in a vacuum oven, and the reactor was carefully rinsed with hot ISOPAR E between polymerization runs. Table 1: Examples of inventive batch reactors at 140°C
The. Efficiency calculated in units of 106 grams of polymer/gram of active metal (Hf or Zr). B. MWD is defined as the ratio of weight average molecular weight to number average molecular weight. ç. MW red It is defined as the % decrease in weight average molecular weight for the test with 40 mmol of hydrogen added, versus the analog test performed without hydrogen. {[MW(in zero hydrogen) - Mw(at 40 mmoles of H2)]/Mw (in zero hydrogen)} x 100. Table 2: Comparative examples of batch reactors at 140°C
The. See footnote to Table 1 above. B. See footnote to Table 1 above. ç. See footnote to Table 1 above. Table 3: Examples of inventive batch reactors at 175°C
The. See footnote to Tables 1-2 above. B. See footnote to Tables 1-2 above. ç. See footnote to Tables 1-2 above. Table 4: Comparative Examples of Batch Reactors at 175°C
The. See footnote to Tables 1-2 above. B. See footnote to Tables 1-2 above. ç. See footnote to Tables 1-2 above. Ethylene/Octene Copolymerizations in Continuous Reactor
[00141] The raw materials (ethylene, 1-octene) and the process solvent (a trademarked SBP 100/140 high purity narrow boiling range isoparaffinic solvent, commercially available from Shell) are purified with sieves molecules, prior to introduction into the reaction environment. Hydrogen is supplied at 1160 psig (80 bar), and reduced to about 580 psig (40 bar); and is supplied as a high degree of purity, and is not yet purified. The reactor monomer (ethylene) feed stream is pressurized, through a mechanical compressor, to the reaction pressure above 525 psig. The solvent and comonomer (1-octene) feed is pressurized, via a mechanical positive displacement pump, to reaction pressure above 525 psig. Modified methylaluminoxane (MMAO), commercially available from AkzoNobel, is used as an impurity scavenger. The individual catalyst components (cocatalyst, procatalyst) are manually diluted in batch to specified component concentrations with purified solvent (ISOPAR E), and pressurized to 525 psig. The cocatalyst is [HNMe(C18H 37)2][B(C6F5)4], commercially available from Boulder Scientific, and is used at a molar ratio of 1.2 to the procatalyst. All reaction feed flows are metered with the mass flow meter, and independently controlled with computer automated valve control systems.
[00142] Continuous solution polymerizations are carried out in a 5L continuously stirred tank reactor (CSTR). The reactor has independent control of all solvent, monomer, comonomer, hydrogen, and freshly prepared catalyst components. The combined solvent, monomer, comonomer and hydrogen feeds to the reactor are temperature controlled, for anywhere from 5°C to 50°C, and typically at 25°C. The freshly prepared comonomer feed to the polymerization reactor is fed with the solvent feed. The cocatalyst is fed based on a specified calculated molar ratio (1.2 molar equivalents) to the procatalyst component. Immediately after each freshly prepared injection site, the feed streams are mixed, with the contents of the polymerization reactor circulating, with static mixing elements. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and the molten polymer) leaves the first loop of the reactor and passes through a control valve (responsible for maintaining the pressure of the first reactor at a specified target). As the stream leaves the reactor, it is brought into contact with water to stop the reaction. In addition, various additives, such as antioxidants, can be added at this point. The stream passes through another set of static mixing elements to evenly disperse the death of catalyst and additives.
[00143] After the addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and the molten polymer) passes through a heat exchanger to raise the temperature of the stream in preparation for separation of the polymer from the other components of the lower boiling reaction. The stream then enters a two-phase separation and devolatilization system, in which the polymer is removed from the solvent, hydrogen, and the unreacted monomer and comonomer. The separated and devolatilized polymer melt is pumped through a specially designed submerged pelletizing mold, cut into solid uniform pellets, dried, and transferred to a box for storage.


[00144] As seen in the tables above, the polymerizations of the invention can be used to produce high molecular weight polymers at high polymerization temperatures and with a good response to dihydrogen (H2). As seen in the tables above, the polymerizations of the invention can be used to effectively polymerize high molecular weight polymers (most average molecular weights greater than 100 kg/mol) at sufficiently high temperatures (>140°C). Ethylene conversions greater than 78% were seen in continuous polymerizations. For both batch and continuous polymerizations, high catalytic efficiencies were observed. Density Test Methods
[00145] Samples that are measured for density are prepared in accordance with ASTM D-1928. Measurements are made within one hour of pressing the sample using ASTM D-792, Method B. Fusion Index
[00146] Melt index (I2) is measured according to ASTM D1238, condition 190°C/2.16 kg, and is expressed in grams eluted per 10 minutes. Melt flow rate (I10) is measured according to ASTM D-1238, Condition 190°C/10 kg, and is expressed in grams eluted per 10 minutes. Conventional Gel Permeation Chromatography (GPC conv.)
[00147] A GPC-IR high temperature chromatography system from PolymerChAR (Valencia, Spain), was equipped with a Precision Detector (Amherst, MA), Model 2040 2-angle laser light scattering detector, an IR5 infrared detector and a 4 capillary viscometer, both from PolymerChAR. Data collection was performed using PolymerChARInstrumentControl software and data collection interface. The system was equipped with an in-line solvent degas pumping system and device from Agilent Technologies (Santa Clara, CA).
[00148] The injection temperature was controlled at 150 degrees Celsius. The columns used were three 10 micron "B mix" columns from Polymer Laboratories (Shropshire, UK). The solvent used was 1,2,4 trichlorobenzene. Samples were prepared at a concentration of "0.1 grams of polymer in 50 mL of solvent". The chromatographic solvent and solvent sample preparation each contained "200 ppm butylated hydroxytoluene (BHT)". Both solvent sources were sprayed with nitrogen. The ethylene-based polymer samples were gently shaken at 160 degrees Celsius for three hours. The injection volume was 200 microliters, and the flow rate was 1 mL/minute. The GPC column set was calibrated by test 21 of "narrow molecular weight distribution" polystyrene standards. The molecular weight (MW) of the standards ranged from 580 to 8,400,000 g/mol, and the standards were contained in six “cocktail” mixtures. Each master mix had at least one series of ten separations between individual molecular weights. Standard blends were purchased from Polymer Laboratories. Polystyrene standards were prepared at “0.025 g in 50 mL of Solvent” for molecular weights greater than or equal to 1,000,000 g/mol, and at “0.050 g in 50 mL of solvent” for molecular weights less than 1,000,000 g /mol.
[00149] The polystyrene standards were dissolved at 80°C, with gentle agitation, for 30 minutes. Mixtures of narrow standards were tested first, and in descending order of "highest molecular weight component" to minimize degradation. Peak standard molecular weights of polystyrene were converted to molecular weight of polyethylene using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Letters, 6, 621 (1968)):
[00150] Mpolyethylene = A x (Mpolystyrene)B (Eq. 1), where M is the molecular weight, A is equal to 0.4316 and B is equal to 1.0.
[00151] The number average molecular weight (Mn(conv gpc)), the weight average molecular weight (Mw-conv GPC), and the Z-average molecular weight (Mn(conv gpc)), were calculated according to

[00152] In Equations 2-4, the RV is the column retention volume (linearly spaced), collected at “1 point per second”, the IR is the IR detector signal subtracted from the baseline, in Volts, from the IR5 measurement channel of the GPC instrument, and MPE is the MW equivalent of polyethylene, determined from Equation 1. Data calculations were performed using a “GPC software (version 2.013H)” from PolymerChar. Zero Deformation Shear Viscosity Measurement Method
[00153] Zero shear viscosities were obtained through strain tests, which were performed on an AR-G2 controlled stress rheometer (TA Instruments; New Castle, Del), using 25 mm diameter parallel plates, at 190° Ç. The rheometer oven was set to the test temperature for at least 30 minutes before resetting the settings. At the test temperature, a compression molded sample plate was inserted between the plates, and allowed to equilibrate for 5 minutes. The top plate was then lowered to 50 μm (instrument adjustment) above the desired test gap (1.5 mm). Any superfluous material was trimmed, and the top plate was lowered to the desired range. Measurements were taken under nitrogen purge at a flow rate of 5 l/min. The standard deformation time was set to 2 hours.
[00154] Each sample was compression molded in a circular plate of “2 mm thick x 25 mm diameter” at 177oC, for 5 minutes, under a pressure of 10 MPa, in air. The sample was then removed from the press and placed on a bench to cool.
[00155] A constant low shear stress of 20 Pa was applied to all samples to ensure that the steady state shear rate was low enough to be in the Newtonian region. The resulting steady-state shear rates were in the range of 10-3 to 10-4 s-1 for the samples under study. Steady state was determined by a linear regression for all data, in the last 10% time window of the plot of a “log(J(t)) vs. log(t)”, where J(t) is strain compliance and t is strain time. If the slope of the linear regression was greater than 0.97, steady state was considered to be reached, then the strain test was stopped. In all cases in this study, the slope meets the criterion within two hours. The steady-state shear rate was determined from the slope of the linear regression of all data points, in the last 10% time window of the plot of “ε vs. t” where ε was the stretch. The zero shear viscosity was determined from the ratio between the applied stress and the steady state shear rate.
[00156] In order to determine if the sample was degraded during the strain test, a small amplitude oscillatory shear test was performed before and after the strain test on the same sample from 0.1 to 100 rad/s. The complex viscosity values of the two tests were compared. If the difference in viscosity values at 0.1 rad/s was greater than 5%, the sample was considered to have degraded during the strain test, and the result was discarded.
[00157] Zero Shear Viscosity Ratio (ZSVR) is defined as the ratio of the zero shear viscosity (ZSV) of the branched polyethylene material to the ZSV of a linear polyethylene material (see ANTEC process below) with the molecular weight equivalent weight average ((Mw(conv gpc)), according to the following equation 5:

[00158] The ZSV value was obtained from the deformation test, at 190°C, using the method described above. The value of Mw(conv gpc) was determined by the conventional GPC method (Equation 3), as discussed above. The correlation between linear polyethylene ZSV and its Mw(conv gpc) was established, based on a series of reference linear polyethylene materials. A description for the ZSV-Mw relationship can be found in the ANTEC procedure: Karjala et al., Detection of Low Levels of Long-chain Branching in Polyolefins, Annual Technical Conference - Society of Plastics Engineers (2008), 66° 887- 891.
[00159] The present invention can be implemented in other ways, without departing from the spirit and essential attributes of the same, and, consequently, reference should be made to the appended claims, instead of the previous descriptive report, as indicating the scope of the invention .

权利要求:
Claims (15)
[0001]
1. Process for forming an olefin-based polymer, said process being characterized in that it comprises polymerizing at least one olefin, in the presence of at least one catalyst system comprising the reaction product of the following: A) at least one cocatalyst; and B) a procatalyst comprising a metal-ligand complex of Formula (I):
[0002]
2. Process according to claim 1, characterized in that the polymerization is a solution polymerization.
[0003]
3. Process according to any one of claims 1 or 2, characterized in that the cocatalyst is selected from a borate, an aluminum alkyl or an aluminoxane.
[0004]
4. Process according to any one of claims 1 to 3, characterized in that the polymerization takes place at a temperature of 25°C to 250°C.
[0005]
5. Process according to any one of claims 1 to 4, characterized in that the polymerization takes place at a pressure of 68.94 kPa (10 psi) and 13.8 kPa (2000 psi).
[0006]
6. Process according to any one of claims 1 to 5, characterized in that the olefin-based polymer is an ethylene-based polymer.
[0007]
7. Process according to any one of claims 1 to 5, characterized in that the olefin-based polymer is a propylene-based polymer.
[0008]
8. Process according to any one of claims 1 to 7, characterized in that for Formula I, each Z is an oxygen atom.
[0009]
9. Process according to any one of claims 1 to 8, characterized in that for Formula I, R21 and R22 are each C (carbon).
[0010]
10. Process according to any one of claims 1 to 9, characterized in that for Formula I, L is selected from the following: -CH2CH2CH2-, -CH2CH2- or -CH2-.
[0011]
11. Process according to any one of claims 1 to 10, characterized in that for Formula I, each (C1-C40)-hydrocarbyl, and each (C1-C40) heterohydrocarbyl, is unsubstituted.
[0012]
12. Process according to any one of claims 1 to 11, characterized in that, for Formula I, M is zirconium or hafnium; n is 2; each X, independently, SQ T- m / C * t * 1—> i ■y"' t' —I i ”1 2—' 11 m I >2 | > 4 i > 5 i > 7 i > 8 i > 9 i > 10 is a (C 1 -C 40 ) hydrocarbyl, and an R, R, R , R , R , R , R , R 12 , R 13 and R 15 are each hydrogen.
[0013]
13. Process according to any one of claims 1 to 12, characterized in that for Formula I, M is zirconium; and each Z is an oxygen atom.
[0014]
14. Process according to any one of claims 1 to 13, characterized in that for formula I, R1 and R16 are each independently selected from the following (i) to (v):
[0015]
15. Process according to claim 1, characterized in that the procatalyst is selected from the group consisting of:

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WO2021243213A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Catalyst systems and processes for producing polyethylene using the same|

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WO2021242800A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Attenuated post-metallocene catalysts|

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WO2021243214A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Catalyst systems and processes for producing polyethylene using the same|

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WO2021242801A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Attenuated hybrid catalysts|

法律状态:
2020-01-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/06/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201462018855P| true| 2014-06-30|2014-06-30|

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US62/018,855|2014-06-30|

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PCT/US2015/038272|WO2016003879A1|2014-06-30|2015-06-29|Process for olefin polymerization|

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