WO2011146044A1 - Procédé pour polymériser sélectivement l'éthylène et catalyseur pour celui-ci - Google Patents

Procédé pour polymériser sélectivement l'éthylène et catalyseur pour celui-ci Download PDF

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Publication number
WO2011146044A1
WO2011146044A1 PCT/US2010/035096 US2010035096W WO2011146044A1 WO 2011146044 A1 WO2011146044 A1 WO 2011146044A1 US 2010035096 W US2010035096 W US 2010035096W WO 2011146044 A1 WO2011146044 A1 WO 2011146044A1
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Prior art keywords
bis
butyl
independently
carbazol
trimethylpentan
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PCT/US2010/035096
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English (en)
Inventor
Jerzy Klosin
Pulikkottil J. Thomas
Robert D. Froese
Xiuhua Cui
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Dow Global Technologies Llc
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Application filed by Dow Global Technologies Llc filed Critical Dow Global Technologies Llc
Priority to PCT/US2010/035096 priority Critical patent/WO2011146044A1/fr
Priority to BR112012022591-0A priority patent/BR112012022591B1/pt
Priority to MX2012007036A priority patent/MX350592B/es
Priority to KR1020127018508A priority patent/KR101788892B1/ko
Priority to US13/105,018 priority patent/US8609794B2/en
Priority to CN201180024264.5A priority patent/CN102906129B/zh
Priority to EP11724080.4A priority patent/EP2491062B1/fr
Priority to PCT/US2011/036004 priority patent/WO2011146291A1/fr
Priority to JP2013511220A priority patent/JP5767318B2/ja
Publication of WO2011146044A1 publication Critical patent/WO2011146044A1/fr
Priority to US14/076,322 priority patent/US9000108B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention generally relates to a process that selectively polymerizes ethylene in the presence of an alpha-olefin, and to a metal-ligand complex (precatalyst) and catalyst useful in such process, and to related compositions.
  • the present invention also generally relates to ligands and intermediates useful for preparing the metal-ligand complex and to processes of their preparation. Other related inventions are described herein.
  • Polyolefins that are polyethylene polymers, poly(ethylene alpha-olefin) copolymers, and mixtures or blends of such polyolefins are examples of types of polyolefins widely used in industry. They are desirable for making, for example, containers, tubing, films and sheets for packaging, and synthetic lubricants.
  • polyethylene- containing polyolefins examples include those that are commercially available from The Dow Chemical Company under the trade names DOWLEX, ATTANE, AFFINITY, ELITE, ENGAGE, Unipol DFDA-7441 polymer, or Tuflin HS-7028; or those that are available from Exxon Chemical Corporation under the trade names EXCEED and EXACT; or those that are available from Mitsui Petrochemical Industries under the trade name TAFMER; or those that are available from Equistar, Inc. under the trade name Petrothene GA501020 polymer; and or those that are available from Nova Chemicals Corporation under the trade name Novapol TF-0 1 19-FP.
  • Patent Numbers US 6,869,904 B2 and US 7,060,848 B2 mention, among other things, ligands, compositions, metal-ligand complexes and arrays with substituted bridged bis- aromatic or bridged bis-biaromatic ligands.
  • the patents also mention methods of making and using the same and catalysts useful in transformations such as the polymerization of monomers into polymers.
  • the catalysts have, among other things, high comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example 1-octene, propylene or styrene.
  • the catalysts also polymerize propylene into isotactic polypropylene.
  • ligands including ligands LL102 to LL105; wherein ligand LL104:
  • PCT International Patent Application Publication Number WO 2007/136494 A2 mentions, among other things, a catalyst composition comprising a zirconium complex of a polyvalent aryloxy ether and the use thereof in a continuous solution polymerization of ethylene, one or more C3-C30 olefins, and a conjugated or non-conjugated diene to prepare interpolymers having improved processing properties.
  • the catalyst system contains a catalyst covalently bonded to an activator.
  • Chemical industry desires new processes and catalysts for selectively polymerizing ethylene in the presence of an alpha-olefin. Such processes would be especially useful for preparing poly ethylenes, poly olefin mixtures or blends, and poly (ethylene alpha-olefin copolymers), including olefin block copolymers.
  • the present invention relates to a process for selectively polymerizing ethylene in a mixture comprising ethylene and an alpha-olefin, and to a metal-ligand complex
  • the present invention also generally relates to ligands and intermediates useful for preparing the metal-ligand complex and to processes of their preparation. Other related inventions are described herein.
  • the invention process is especially useful for preparing poly ethylenes, polyolefin mixtures or blends, and poly(ethylene alpha- olefin copolymers), including poly(ethylene alpha-olefin) block copolymers, also known as olefin block copolymers.
  • the present invention is a process for selectively polymerizing ethylene in the presence of an alpha-olefin, the process comprising a step of contacting together a catalytic amount of a catalyst, ethylene, and an alpha-olefin, wherein the catalyst comprises a mixture or reaction product of ingredients (a) and (b) that is prepared before the contacting step, wherein ingredient (a) comprises a metal-ligand complex (also referred to herein as a precatalyst) and ingredient (b) comprises an activating co-catalyst; ethylene comprises ingredient (c); and the alpha-olefin comprises ingredient (d) (ingredient letters are for ease of reference herein);
  • the metal-ligand complex of ingredient (a) being one or more metal-ligand complexes of formula (I):
  • M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
  • n is an integer of from 0 to 3, wherein when n is 0, X is absent (i.e., (X) n is absent);
  • Each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic; or two
  • X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
  • X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
  • Each Z independently is O, S, N(C j -C4Q)hydrocarbyl, or P(C j -C4Q)hydrocarbyl;
  • L is (C j -C4Q)hydrocarbylene or (C j -C4Q)heterohydrocarbylene, wherein the
  • (C j -C4o)hydrocarbylene has a portion that comprises a 1 -carbon atom to 6-carbon atom linker backbone linking the Z atoms in formula (I) (to which L is bonded) and the
  • (C j -C4o)heterohydrocarbylene has a portion that comprises a 1-atom to 6-atom linker backbone linking the Z atoms in formula (I), wherein each atom of the 1-atom to 6-atom linker backbone of the
  • (C j -C4Q)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(0) 2 , Si(R3 ⁇ 4, Ge(R c ) 2 , P(R P ), or N(R N ), wherein independently each R c is unsubstituted
  • At least one of R l a , R 2a , R lb , and R 2b independently is a (C r C 0 )hydrocarbyl
  • each of the others of R ⁇ a , R 2a , R ⁇ b , and R 2b independently is a hydrogen atom, (Cj-C4Q)hydrocarbyl, (Cj-C4Q)heterohydrocarbyl, or halogen atom;
  • Each of R 3a , R 4a , R 3b , R 4b , R 6c , R 7c , R 8c , R 6d , R 7d , and R 8d independently is a hydrogen atom; (Cj-C4o)hydrocarbyl; (Cj-C4o)heterohydrocarbyl; or halogen atom;
  • R ⁇ c and R ⁇ d independently is a (Cg-C4Q)aryl or (Cj-C4o)heteroaryl;
  • Each R s independently is a halogen atom, polyfluoro substitution (that is one of the one or more substituents R s stands for two or more fluoro substituents, which formally respectively replace two or more hydrogen atoms of an unsubstituted version of the substituted group), perfluoro substitution (that is the one R s stands for as many fluoro substituents as carbon-bonded hydrogen atoms (i.e., H-C) of an unsubstituted version of the substituted group that is substituted thereby), unsubstituted (Cj-Cj ⁇ alkyl,
  • the activating co-catalyst of the ingredient (b) comprises one or more activating co- catalysts, or a reaction product thereof, wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more activating co- catalysts is from 1:10,000 to 100:1;
  • the contacting step is performed under olefin polymerizing conditions (described later) and prepares a rich polyethylene in presence of unpolymerized alpha-olefin (e.g., a (C3-C4g)alpha- olefin); and
  • unpolymerized alpha-olefin e.g., a (C3-C4g)alpha- olefin
  • reaction rate constant kj j for adding the ethylene (a monomer) to a first reactive chain end comprising an ethylene residual
  • reaction rate constant k ⁇ for adding the alpha-olefin (a comonomer) to a second reactive chain end comprising an ethylene residual
  • r ⁇ k j j /k ⁇ 20
  • the first and second reactive chain ends, and thus the ethylene residuals thereof, can be different or, preferably, the same.
  • the term "rich polyethylene” means a polymeric molecule, or rich polyethylene segment thereof, substantially comprising ethylene repeat units (as a result of high ethylene polymerization selectivity characterized by the high reactivity ratio r ⁇ ); or a mixture or blend of two or more such polymeric molecules.
  • the rich polyethylene segment of the latter polymeric molecule typically is a portion of a poly(ethylene alpha-olefin) copolymer.
  • the invention process can prepare the poly(ethylene alpha-olefin) copolymer when it further employs an optional promiscuous olefin polymerization catalyst according to one of the embodiments described later, including preparing a poly(ethylene alpha-olefin) block copolymer according to one of the chain shuttling embodiments described later.
  • the invention process produces a rich polyethylene or a polyolefin blend or mixture comprising the rich polyethylene, preferably wherein the rich polyethylene contains no or a minimal amount (e.g., less than 5 mole percent by nuclear magnetic resonance) of alpha-olefin-derived repeat units.
  • the present invention is the catalyst comprising or prepared from the one or more metal-ligand complexes of formula (I) and one or more activating co-catalysts, or a reaction product thereof (i.e., a reaction product of a reaction of at least one of the one or more metal-ligand complexes of formula (I) with at least one of the one or more activating co-catalysts), wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more activating co-catalysts is from 1 : 10,000 to 100: 1.
  • the present invention also contemplates a catalyst system (i.e., a catalyst composition) comprising the aforementioned ingredients (a) and (b).
  • a catalyst system i.e., a catalyst composition
  • the invention catalyst system further comprises a molecular weight control agent as an ingredient (e), and, optionally the promiscuous olefin polymerization catalyst as an ingredient (f).
  • Ingredients (e) and (f) are described later.
  • the invention also contemplates additional ingredients of the catalyst system as described later.
  • the present invention is the metal-ligand complex of formula (I).
  • the present invention is a ligand of formula (Q):
  • Group 1 or 2 metal salt thereof wherein the Group 1 or 2 metal is a cation of any one of the metals of Groups 1 and 2 of the Periodic Table of the Elements; and L, Z, R l a , R 2a , R 3a , R 4a , R lb , R 2b , R 3b ,
  • R 4b , R 5c , R 6c , R 7c , R 8c , R 5d , R 6d , R 7d , and R 8d are as defined previously except at least one of R l a , R ⁇ b , R 3a , and R 3b is not methyl when R 7c and R 7d are each methyl.
  • the invention also contemplates a process for preparing the metal-ligand complex of formula (I); a process for preparing the ligand of formula (Q) or the Group 1 or 2 metal salt thereof; and contemplates intermediates in the preparation thereof.
  • the processes are as described later herein.
  • the ligand of formula (Q) or the Group 1 or 2 metal salt thereof is useful in the process of preparing the metal-ligand complex of formula (I), which in turn is useful in the process of preparing the invention catalyst.
  • the metal-ligand complex of formula (I) and invention catalyst derived therefrom with the one or more activating co-catalysts are useful in the invention process.
  • Preferred embodiments of the invention process independently are characterizable by one or more activities of the invention catalyst, one or more properties of the poly olefin prepared thereby, or a combination thereof. Especially preferred properties are those improved over closest prior art, if any.
  • the invention process is characterizable by its aforementioned high selectivity for polymerizing ethylene in presence of the alpha-olefin (e.g., (C3-C4g)alpha-olefin) or other polymerizable olefin (e.g., styrene).
  • R ⁇ c sterically interacts with either R ⁇ a or R 2a , or both R ⁇ a and R 2a , as the case may be; or R ⁇ d sterically interacts with either R ⁇ b or R 2b , or both R ⁇ b and R 2b , as the case may be; or a combination of such steric interactions thereof when the at least one of R l a , R lb , R 2a , and
  • R 2b is not a hydrogen atom. It is also believed that these steric interactions happen in such a way so as to cause the invention catalyst prepared from the metal- ligand complex of formula (I) to polymerize ethylene more selectively than it polymerizes the sterically larger alpha-olefin (or other larger olefin comonomer) during the invention process (i.e., the invention catalyst preferentially polymerizes ethylene in the presence of the alpha-olefin).
  • the process of the first embodiment selectively gives the rich polyethylene (e.g., a high density polyethylene) or rich polyethylene segment of the poly(ethylene alpha-olefin) copolymer in the presence of alpha-olefin, which is substantially unpolymerized thereby.
  • the rich polyethylene e.g., a high density polyethylene
  • the rich polyethylene segment of the poly(ethylene alpha-olefin) copolymer in the presence of alpha-olefin, which is substantially unpolymerized thereby.
  • the invention process advantageously is versatile.
  • the invention process can be adapted as described later to further employ a molecular weight control agent so as to prepare a molecular weight-controlled rich polyethylene or molecular weight-controlled poly(ethylene alpha-olefin) copolymer, as the case may be.
  • the invention process can be adapted as described later to further employ a combination of a chain shuttling agent (CSA) and a promiscuous olefin polymerization catalyst so as to prepare the poly(ethylene alpha-olefin) copolymer, and preferably a poly(ethylene alpha-olefin) block copolymer.
  • CSA chain shuttling agent
  • a promiscuous olefin polymerization catalyst so as to prepare the poly(ethylene alpha-olefin) copolymer, and preferably a poly(ethylene alpha-olefin) block copolymer.
  • the poly(ethylene alpha- olefin) block copolymer comprises one or more rich polyethylene segments and one or more segments having higher mole percent incorporation of the alpha-olefin (as a residual thereof) than has the rich polyethylene segment(s).
  • the rich polyethylene segment(s) of the poly(ethylene alpha-olefin) block copolymer are sometimes referred to herein as polyethylene hard segment(s) or simply hard segments.
  • the segments of the poly(ethylene alpha-olefin) block copolymer having the higher mole percent incorporation of the alpha-olefin are formed with the invention process further employing a promiscuous olefin polymerization catalyst having a reactivity ratio r ⁇ ⁇ 10 and are sometimes referred to herein as soft segments.
  • the CSA shuttles a growing polymeryl chain between the invention catalyst and the promiscuous olefin polymerization catalyst.
  • the poly(ethylene alpha-olefin) block copolymer so prepared comprises hard and soft segments.
  • the invention process lacks a CSA and can be adapted as described later to prepare a polyolefin polymer blend or mixture, wherein at least one polyolefin of the polymer blend or mixture comprises at least a rich polyolefin or the rich polyethylene segment of the poly(ethylene alpha-olefin) copolymer.
  • the rich polyethylene or rich polyethylene segment-containing poly(ethylene alpha-olefin) copolymer prepared by the invention process can be readily separated, if desired, from any remaining (unpolymerized) ethylene and polymerizable higher olefin monomer (e.g., (C3-C40) alpha-olefin) by conventional means (e.g., filtering/washing the rich polyethylene-containing material or stripping or evaporating of the higher polymerizable olefin monomer).
  • the process of the present invention works with any mole ratio of moles of alpha-olefin to moles of ethylene.
  • Another advantage of the present invention process is that it is capable of preparing the rich polyethylene or rich polyethylene segment of the poly(ethylene alpha- olefin) copolymer in circumstances where it would be desirable to do so in the presence of the larger polymerizable olefin (i.e., a higher polymerizable olefin wherein "higher” means higher number of carbon atoms).
  • Such circumstances include, but are not limited to, use of ethylene/alpha-olefin feed mixtures to prepare the aforementioned polyolefin polymer blend or mixture, wherein at least one polyolefin of the polyolefin polymer blend or mixture comprises the rich polyethylene or the rich polyethylene segment of the poly(ethylene alpha-olefin) copolymer.
  • Another advantage is that in some embodiments the invention process functions as a continuous process that is capable of preparing in some embodiments new polyolefin polymer blends or mixtures or new poly(ethylene alpha-olefin) block copolymers, both of which are thus part of the present invention.
  • the invention process advantageously can prepare novel rich polyethylenes and rich polyethylene segment-containing poly olefins.
  • the present invention also contemplates new rich polyethylenes and rich polyethylene segment-containing poly(ethylene alpha-olefin) copolymers, including block copolymers thereof, i.e., the poly(ethylene alpha-olefin) block copolymers, prepared by the invention process.
  • the rich polyethylenes prepared by the invention process typically contain vinyl groups.
  • the invention also contemplates modified polymers prepared by functionalizing by known means such vinyl groups to give polar group functionalized derivatives thereof. If desired the polar group functionalized derivatives can be reacted with complimentary-reacting monomers or oligomers so as to form polar group functionalized copolymers.
  • poly(ethylene alpha-olefin) block copolymer is used interchangeably herein with the terms “olefin block copolymer,” “OBC,” “ethylene/a-olefin block interpolymer,” and
  • ethylene/a-olefin block copolymer The terms “alpha-olefin” and “a-olefin” are used interchangeably herein.
  • the term “ethylene” means ethene, i.e., The rich polyethylenes (e.g., a high density polyethylene) and rich polyethylene -containing materials (e.g., the rich polyethylene -containing poly(ethylene alpha-olefin) copolymers, including the poly(ethylene alpha-olefin) block copolymers) prepared by embodiments of the invention process are useful in numerous applications such as, for example, synthetic lubricants and, especially for the OBCs, elastic films for hygiene applications (e.g., for diaper covers); flexible molded goods for appliances, tools, consumer goods (e.g., toothbrush handles), sporting goods, building and construction components, automotive parts, and medical applications (e.g., medical devices); flexible gaskets and profiles for appliance (e.g., refrigerator door gaskets and profiles), building and construction, and automotive
  • Figure (Fig.) 1 shows an illustrative procedure of Scheme 1 for preparing a first primary intermediate useful in a convergent synthesis of the ligand of formula (Q).
  • Fig. 2 shows an illustrative procedure of Scheme 2 for preparing a second primary intermediate useful in the convergent synthesis of the ligand of formula (Q).
  • Fig. 3 shows an illustrative procedure of Scheme 3 for preparing the ligand of formula (Q) from the first and second primary intermediates.
  • Fig. 4 shows an illustrative procedure of Scheme 4 for preparing the metal-ligand complex of formula (I) from the ligand of formula (Q).
  • Fig. 5 shows structures of ligands (Ql) to (Q8) of Examples Ql to Q8.
  • Fig. 6 shows structures of ligands (Q9) to (Q16) of Examples Q9 to Q16.
  • Fig. 7 shows structures of ligands (Q17) to (Q22) of Examples Q17 to Q22.
  • Fig. 8 shows an Oak Ridge Thermal Ellipsoid Plot (ORTEP) depiction of a single crystal structure derived by x-ray analysis of invention metal-ligand complex (2) (Example 2) with hydrogen atoms omitted for clarity.
  • ORTEP Oak Ridge Thermal Ellipsoid Plot
  • Fig. 9 shows an ORTEP depiction of a single crystal structure derived by x-ray analysis of invention metal-ligand complex (3) (Example 3) with hydrogen atoms omitted for clarity.
  • Fig. 10 shows structures of metal-ligand complexes (1) to (8) of Examples 1 to 8.
  • Fig. 11 shows structures of metal-ligand complexes (9) to (16) of Examples 9 to 16.
  • Fig. 12 shows structures of metal-ligand complexes (17) to (24) of Examples 17 to 24.
  • Fig. 13 shows a structure of metal-ligand complex (25) of Example 25.
  • the rich polyethylene and rich polyethylene segment of the poly (ethylene alpha-olefin) copolymer is sometimes referred to herein simply as the rich polyethylene.
  • any lower limit of a range of numbers may be combined with any upper limit of the range, or any preferred upper limit of the range, to define a preferred aspect or embodiment of the range.
  • Each range of numbers includes all numbers, both rational and irrational numbers, subsumed within that range (e.g., the range from about 1 to about 5 includes, for example, 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
  • each Markush group independently consists of its own members (e.g., for illustration purposes a general Markush group "A” consisting of members Al, A2, and A3; or Markush group “A3” consisting of preferred members A3a, A3b, A3c, and A3d)
  • the invention contemplates preferred embodiments that (i) select any single member from one of the one or more Markush groups (e.g., for illustration purposes selecting A2 from Markush group A or selecting A3c from Markush group A3), thereby limiting scope of the one Markush group (e.g., A or A3) to the selected single member (e.g., A2 or A3c); or (ii) delete any single member from one of the one or more Markush groups (e.g., for illustration purposes deleting Al from Markush group A or deleting A3a from Markush group A3), thereby limiting the one Markush group (e.g.,
  • the forty carbon atom upper limit in such groups or olefins is a practical upper limit. Nevertheless in some embodiments the invention contemplates such unsubstituted chemical groups having a maximum number of carbon atoms that is higher than 40 (e.g., 100, 1000, or more).
  • the open-ended terms “comprising,” “comprises,” and the like may be replaced by the respective partially closed phrases “consisting essentially of,” consists essentially of,” and the like or the respective closed phrases “consisting of,” “consists of,” and the like to give another aspect or embodiment of the instant invention.
  • the term “characterizable” is open-ended and means distinguishable. In the present application, when referring to a preceding list of elements (e.g., ingredients), the phrases “mixture thereof,” “combination thereof,” and the like mean any two or more, including all, of the listed elements.
  • the invention process employs one or more metal-ligand complexes of formula (I), which is described herein using conventional chemical group terminology.
  • the parenthetical expression (C ⁇ -C ⁇ Q) and like expressions can be generically represented by the form "(C x -Cy)," which means that the unsubstituted version of the chemical group comprises from a number x carbon atoms to a number y carbon atoms, wherein each x and y independently is an integer as described for the chemical group.
  • the R s substituted version of the chemical group can contain more than y carbon atoms depending on nature of R s .
  • the substituted (C x -Cy) chemical group may comprise more than y total carbon atoms; i.e., the total number of carbon atoms of the carbon atom-containing substituent(s)- substituted (C x -Cy) chemical group is equal to y plus the sum of the number of carbon atoms of each of the carbon atom-containing substituent(s).
  • Any atom of a chemical group that is not specified herein is understood to be a hydrogen atom.
  • each of the chemical groups (e.g., X, L, R ⁇ a , etc.) of the metal-ligand complex of formula (I) is unsubstituted, that is, can be defined without use of a substituent R s .
  • at least one of the chemical groups of the metal-ligand complex of formula (I) independently contain one or more of the substituents R s .
  • there are not more than a total of 20 R s there are not more than a total of 20 R s , more preferably not more than a total of 10 R s , and still more preferably not more than a total of 5 R s in the metal-ligand complex of formula (I).
  • each R s independently is bonded to a same or different substituted chemical group.
  • R s independently is bonded to a same or different substituted chemical group.
  • they independently are bonded to a same or different carbon atom or heteroatom, as the case may be, in the same chemical group up to and including persubstitution of the chemical group.
  • persubstitution means each hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group, as the case may be, is replaced by a substituent (e.g., R s ).
  • substitution means at least two, but not all, hydrogen atoms (H) bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group, as the case may be, are replaced by substituents (e.g., R s ).
  • R s substituents
  • at least one R s is polyfluoro substitution or perfluoro substitution.
  • polyfluoro substitution and “perfluoro substitution” each count as one R s substituent.
  • poly as in “polyfluoro substitution” means that two or more H, but not all H, bonded to carbon atoms of a corresponding unsubstituted chemical group are replaced by a fluoro in the substituted chemical group.
  • poly as used in polysubstitution and polyfluorosubstitution means two substituents (e.g., two fluorine atoms).
  • per as in “perfluoro substitution” means each H bonded to carbon atoms of a corresponding unsubstituted chemical group is replaced by a fluoro in the substituted chemical group.
  • R s are taken together to form an unsubstituted (C j -C j ⁇ alkylene. Still more preferably substitutents R s independently are unsubstituted (C j -C j ⁇ alkyl, F, unsubstituted (C j -C j ⁇ aikylene, or a combination thereof; and even more preferably unsubstituted
  • (C j -Cg)alkyl or unsubstituted (C j -Cg)aikylene are especially useful for forming substituted chemical groups that are bicyclic or tricyclic analogs, as the case may be, of corresponding monocyclic or bicyclic unsubstituted chemical groups.
  • (C j -C4o)hydrocarbyr' means a hydrocarbon radical of from 1 to 40 carbon atoms
  • (C j -C4o)hydrocarbylene means a hydrocarbon diradical of from 1 to 40 carbon atoms, wherein each hydrocarbon radical and diradical independently is aromatic (6 carbon atoms or more) or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic, including bicyclic; 3 carbon atoms or more) or acyclic, or a combination of two or more thereof; and each hydrocarbon radical and diradical independently is the same as or different from another hydrocarbon radical and diradical, respectively, and independently is unsubstituted or substituted by one or more R S .
  • hydrocarbylene groups e.g., (C2-C j 2)hyclrocarbylene) are defined in an analogous manner.
  • a (C j -C4o)hydrocarbyl independently is an unsubstituted or substituted (C j -
  • each of the aforementioned (C j -C4Q)hydrocarbyl groups independently has a maximum of 20 carbon atoms (i.e., (C j -C2o)hyclrocarbyl), and still more preferably a maximum of 12 carbon atoms.
  • (C2-C4Q)alkyl and "(C j -C j ⁇ aikyl” mean a saturated straight or branched hydrocarbon radical of from 1 to 40 carbon atoms or from 1 to 18 carbon atoms, respectively, that is unsubstituted or substituted by one or more R S .
  • Other alkyl groups e.g., (C r C 12 )alkyl)
  • (C j -C4Q)aikyl has a maximum of 20 carbon atoms (i.e., (C j -
  • Examples of unsubstituted (C j -C4o)aikyl are unsubstituted (C j -C2o) ai kyl; unsubstituted (C ⁇ -C ⁇ Q) alkyl;
  • C j -C ⁇ alkyl unsubstituted (C j -C ⁇ alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1- dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl.
  • substituted (C j -C ⁇ alkyl methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1- dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl.
  • C4o)alkyl are substituted (C j -C2o) ai kyl, substituted (C j -C ⁇ alkyl, trifluoromethyl, and (C45)alkyl.
  • each (C j -C ⁇ alkyl independently is methyl, trifluoromethyl, ethyl, 1-propyl, 2- methylethyl, or 1,1 -dimethylethyl.
  • (Cg-C4Q)aryl means an unsubstituted or substituted (by one or more R S ) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 40 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms, and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings, respectively; wherein the 1 ring is aromatic and the 2 or 3 rings independently are fused or non-fused and at least one of the 2 or 3 rings is aromatic.
  • Other aryl groups e.g., (Cg-C ⁇ Q)aryl) are defined in an analogous manner.
  • (Cg-C4Q)aryl has a maximum of 20 carbon atoms (i.e., (Cg-C2 Q ) ryl), more preferably 18 carbon atoms, still more preferably 10 carbon atoms, and even more preferably 6 carbon atoms.
  • Examples of unsubstituted (Cg-C4g)aryl are unsubstituted (Cg-C2())aryl; unsubstituted (Cg-C j g)aryl; 2-(C j -C5)aikyl -phenyl; 2,4-bis(C j -C5)aikyl -phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl;
  • (C3-C4Q)cycloalkyl means a saturated or unsaturated (but not aromatic) cyclic hydrocarbon radical of from 3 to 40 carbon atoms that is unsubstituted or substituted by one or more R s .
  • Other cycloalkyl groups e.g., (C- ⁇ -C ⁇ alkyl) are defined in an analogous manner.
  • C4o)cycloalkyl is saturated.
  • (C3-C4Q)cycloalkyl is unsaturated, preferably it is mono- or diunsaturated (i.e., contains 1 or 2 carbon-carbon double bonds, respectively), and more preferably it is monounsaturated.
  • (C3-C4Q)cycloalkyl has a maximum of 20 carbon atoms (i.e., (C3-
  • C3o)cycloalkyl more preferably 10 carbon atoms, and still more preferably 6 carbon atoms.
  • Examples of unsubstituted (C3-C4g)cycloaikyl are unsubstituted (C3-C2o)cycloalkyl, unsubstituted
  • Examples of (C j -C4Q)hydrocarbylene are unsubstituted or substituted (Cg-C4g)arylene, (C3-C4Q)cycloalkylene, and (C j -C4Q)alkylene (e.g., (C j -C2o)aikylene).
  • the diradicals are on a same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart by one, two, or more intervening carbon atoms (e.g., respective 1,3 -diradicals, 1,4- diradicals, etc.).
  • the alpha,omega-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. More preferred is a 1 ,2-diradical version of (Cg-C j g)arylene,
  • (Cg-C2o)cycloalkylene, or (C4-C2 Q )alkylene means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 40 carbon atoms that is unsubstituted or substituted by one or more R S .
  • Other alkylene groups e.g., (CJ-CJ 2 ) alkylene)
  • Examples of unsubstituted (CJ-C 4 Q) alkylene are unsubstituted (C j -C ⁇ alkylene, including unsubstituted 1,2-(C 2 -C 10 )alkylene; 1,3-(C 3 -C 10 )alkylene; 1,4-(C 4 -C 10 )alkylene; -CH 2 -, -CH 2 CH 2 -,
  • substituted (CJ-C 4 Q) alkylene are substituted (C j -C 2 Q)alkylene, -CF 2 -, -C(O)-, and
  • substituted (C J -C 4Q )alkylene also include 1 ,2-bis(methylene)cyclopentane, 1,2- bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3- bis(methylene)bicyclo[2.2.2]octane.
  • (C 3 -C 4Q )cycloalkylene means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 40 carbon atoms that is unsubstituted or substituted by one or more R S .
  • unsubstituted (C 3 -C 4Q )cycloalkylene are 1,2-cyclopropylene, 1,1-cyclopropylene, and 1,2- cyclohexylene.
  • Examples of substituted (C 3 -C 4Q )cycloalkylene are 2-oxo-l,3-cyclopropylene and 1,2- dimethyl- 1 ,2-cyclohexylene.
  • (C j -C ⁇ heterohydrocarbyl means a heterohydrocarbon radical of from 1 to 40 carbon atoms and the term "(C j -C 4Q )heterohydrocarbylene means a heterohydrocarbon diradical of from 1 to 40 carbon atoms, and each heterohydrocarbon independently has one or more heteroatoms O; S; S(O); S(0) 2 ; Si(R C ) 2 ; Ge(R c ) 2 ;P(R P ); and N(R N ), wherein independently each R C is unsubstituted
  • each R P is unsubstituted (C j -C j ⁇ hydrocarbyl; and each R N is unsubstituted
  • heterohydrocarbylene groups are defined in an analogous manner.
  • the heterohydrocarbon radical and each of the heterohydrocarbon diradicals independently is on a carbon atom or heteroatom thereof, although preferably is on a carbon atom when bonded to a heteroatom in formula (I) or to a heteroatom of another heterohydrocarbyl or heterohydrocarbylene.
  • (C j -C4Q)heterohydrocarbylene independently is unsubstituted or substituted (by one or more R s ), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic) or acyclic, or a combination of two or more thereof; and each is respectively the same as or different from another.
  • the (C j -C4Q)heterohydrocarbyl independently is unsubstituted or substituted (C j -
  • C 2 Q)alkylene (Cg-C 2 Q)aryl-(C j -C ⁇ )heteroalkylene, or (C j -C j oJheteroaryHC j -C ⁇ heteroalkylene.
  • each of the aforementioned groups has a maximum of 20 carbon atoms (not counting carbon atoms from any R s ).
  • (C j -C4o)heteroaryr means an unsubstituted or substituted (by one or more R s ) mono-, bi- or tricyclic heteroaromatic hydrocarbon radical of from 1 to 40 total carbon atoms and from 1 to 4 heteroatoms, and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings, respectively, wherein the 2 or 3 rings independently are fused or non-fused and at least one of the 2 or 3 rings is heteroaromatic.
  • Other heteroaryl groups e.g., (C j -C j ⁇ heteroaryl)
  • the monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring.
  • the 5- membered ring has from 1 to 4 carbon atoms and from 4 to 1 heteroatoms, respectively, each heteroatom being O, S, N, or P, and preferably O, S, or N. Examples of 5-membered ring
  • heteroaromatic hydrocarbon radical are pyrrol-l-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-l-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-l-yl; 1,3,4- oxadiazol-2-yl; l,3,4-thiadiazol-2-yl; tetrazol-l-yl; tetrazol-2-yl; and tetrazol-5-yl.
  • the 6-membered ring has 4 or 5 carbon atoms and 2 or 1 heteroatoms, the heteroatoms being N or P, and preferably N.
  • 6-membered ring heteroaromatic hydrocarbon radical are pyridine -2-yl; pyrimidin-2-yl; and pyrazin-2-yl.
  • the bicyclic heteroaromatic hydrocarbon radical preferably is a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-1- yl; and benzimidazole-l-yl.
  • Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-l-yl.
  • the tricyclic heteroaromatic hydrocarbon radical preferably is a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system.
  • An example of the fused 5,6,5-ring system is l ,7-dihydropyrrolo[3,2- ]indol-l-yl.
  • An example of the fused 5,6,6-ring system is 1H- benzo[ ]indol-l -yl.
  • An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl.
  • fused 6,5,6-ring system is 9H-carbazol-9-yl.
  • fused 6,6,6-ring system is acrydin-9-yl.
  • the 5-membered rings and 6-membered rings of the fused 5,6-; 6,6-; 5,6,5-; 5,6,6-; 6,5,6-; and 6,6,6- ring systems independently can be as described above for 5-membered and 6-membered rings, respectively, except where the ring fusions occur.
  • heteroalkyl and heteroalkylene groups are saturated straight or branched chain radicals or diradicals, respectively, containing ( C ⁇ Q) carbon atoms, or fewer carbon atoms as the case may be, and one or more of the heteroatoms Si(R c ) 2 , Ge(R c ) 2 ,P(R P ), N(R N ), N, O, S, S(O), and
  • halogen atom means fluorine atom (F), chlorine atom (CI), bromine atom (Br), or iodine atom (I) radical.
  • each halogen atom independently is the Br, F, or CI radical, and more preferably the F or CI radical.
  • halide means fluoride (F “ ), chloride (CI “ ), bromide (Br “ ), or iodide ( ⁇ ) anion.
  • heteroatom means O, S, S(O), S(0)2, Si(R c )2,
  • germanium (Ge) atom there is no germanium (Ge) atom in the invention compound or complex.
  • the metal-ligand complex of formula (I) there are no O-O, S-S, or O-S bonds, other than O-S bonds in an S(O) or S(0)2 diradical functional group, in the metal-ligand complex of formula (I). More preferably, there are no O- O, N-N, P-P, N-P, S-S, or O-S bonds, other than O-S bonds in an S(O) or S(0) 2 diradical functional group, in the metal-ligand complex of formula (I).
  • saturated means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds. Where a saturated chemical group is substituted by one or more substituents R s , one or more double and/or triple bonds optionally may or may not be present in substituents R s .
  • unsaturated means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds, not including any such double bonds that may be present in substituents R s , if any, or in (hetero) aromatic rings, if any.
  • R 6d , R 7d , and R 8d are preferred. Examples of such preferred groups follow.
  • M is zirconium or hafnium, and more preferably M is hafnium.
  • M is zirconium. In some embodiments M is titanium. In some embodiments M is in a formal oxidation state of +2. In some embodiments M is in a formal oxidation state of +3. In some embodiments M is in a formal oxidation state of +4.
  • the invention contemplates any combination of a preferred M and a preferred formal oxidation state.
  • n is 0. In some embodiments n is 1. In some embodiments n is 2. In some embodiments n is 3.
  • each X independently is the monodentate ligand. Preferably when there are two or more X monodentate 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 preferably independently is hydride, (C j -C4Q)hydrocarbyl carbanion, (C j -C4Q)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(0)0 “ , (C 1 -C 40 )hydrocarbylC(O)O " , HC(0)N(H) ⁇ , (C r C 40 )hydrocarbylC(O)N(H) " , (C r C4 0 )hydrocarbylC(0)N((C r C2o)hydrocarbyl) " , R K R L B " ,
  • R K R L N , R K 0 " , R K S ⁇ , R K R L P " , or R M R K R L Si ⁇ , wherein each R K , R L , and R M independently is hydrogen, (C j -C4Q)hydrocarbyl, or (C j -C4o)heterohydrocarbyl, or R K and R L are taken together to form a
  • At least one monodentate ligand of X independently is the neutral ligand.
  • the neutral ligand is a neutral Lewis base group that is R X NR K R L , R K OR L , R K SR L , or R X PR K R L , wherein each R x independently is hydrogen, (C j -C4Q)hydrocarbyl, [(C J -C J Q)hydrocarbyl] 3S1, [(C -C Q)hydrocarbyl] ⁇ SiCC ⁇ - ⁇ Q)hydrocarbyl, or
  • each X is a monodentate ligand that independently is a halogen atom, unsubstituted (Cj-C2o)hydrocarbyl, unsubstituted (Cj-C2o)hydrocarbylC(0)0-, or R K R L N- wherein each of R K and R L independently is an unsubstituted (Cj -C2o)hyclrocarbyl.
  • each monodentate ligand X is a chlorine atom, (Cj-C ⁇ hydrocarbyl (e.g., (Cj-Cg)alkyl or benzyl), unsubstituted or R K R L N- wherein each of R K and R L independently is an unsubstituted (C j -C j Q)hydrocarbyl.
  • the bidentate ligand is a neutral bidentate ligand.
  • the bidentate ligand is a monoanionic-mono(Lewis base) ligand.
  • the bidentate ligand is a dianionic ligand.
  • the dianionic ligand has a net formal oxidation state of -2.
  • each dianionic ligand independently is carbonate, oxalate (i.e., " 02CC(0)0 " ),
  • carbonate means an ionic substance consisting of zero or one cations x 9
  • nitrate means an ionic substance consisting of an anion of the empirical formula NO3 " , the ionic substance having an overall -1 charge.
  • oxalate means an ionic substance consisting of zero or one cations Q x and an anion of the empirical formula OC(0)C(0)0 ⁇ , the ionic substance having an overall -1 or -2 charge.
  • phosphate means an ionic substance consisting of zero, one, or two cations Q and an anion of the empirical formula PO4 , the ionic substance having an overall -1 , -2, or -3 charge.
  • sulfate means an ionic substance consisting of zero or one
  • Q x independently is an inorganic cation of hydrogen atom, lithium, sodium, potassium, calcium, or magnesium, including hemi calcium and hemi magnesium.
  • 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, overall, neutral.
  • each X is the same, wherein each X is methyl; ethyl; 1 -propyl; 2-propyl; 1 -butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro.
  • n is 2 and each X is the same.
  • At least two X are different.
  • n is 2 and each X is a different one of methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro.
  • n indicates number of X.
  • 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.
  • n is 2 at two X are taken together to form a bidentate ligand.
  • the bidentate ligand is 2,2-dimethyl-2-silapropane-l,3-diyl or 1,3-butadiene.
  • X and n independently are as defined as in any one of the Examples described later in the EXAMPLES OF THE PRESENT INVENTION section.
  • each Z is different. In some embodiments one Z is O and one Z is NCH 3 . In some embodiments one Z is O and one Z is S. In some embodiments one Z is S and one Z is N(C j -C4Q)hydrocarbyl (e.g., NCH 3 ). In some embodiments each
  • 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(C j -C4Q)hydrocarbyl (e.g., NCH 3 ). In some embodiments at least one, and in some embodiments each Z is P(C j -C4o)hydrocarbyl (e.g., PCH 3 ).
  • L is the
  • the aforementioned portion that comprises a 1 -carbon atom to 6- carbon atom linker backbone of the (C j -C4Q)hydrocarbylene of L comprises a 2-carbon atom to 5- carbon atom, and more preferably a 3-carbon atom or 4-carbon atom linker backbone linking the Z atoms in formula (I) to which L is bonded.
  • L comprises the 2-carbon atom linker backbone (e.g., L is -CH2CH2- or -CH(CH 3 )CH(CH 3 )-). In some embodiments L comprises the 3- carbon atom linker backbone (e.g., L is -CH 2 CH 2 CH 2 -; -CH(CH 3 )CH 2 CH(CH 3 )-;
  • L comprises the 4-carbon atom linker backbone (e.g., L is -CH2CH2CH2CH2-;
  • L comprises the 5-carbon atom linker backbone (e.g., L is -CH2CH2CH2CH2- or l,3-bis(methylene)cyclohexane).
  • L comprises the 6- carbon atom linker backbone (e.g., L is -CH2CH2CH2CH2CH2CH2- or l,2-bis(ethylene)cyclohexane).
  • L is the (C j -C4o)hydrocarbylene and the (C j -C4o)hydrocarbylene of L is a
  • (C j -C4Q)hydrocarbylene is an unsubstituted (C j -C4Q)aikylene.
  • (C j -C4o)hydrocarbylene is a substituted (C j -C4Q)alkylene.
  • (C j -C4o)hydrocarbylene is an unsubstituted (C 3 -C4Q)cycloaikylene or substituted
  • each substituent independently is R s , wherein preferably the R s independently is (C j -C4)alkyl.
  • L is the unsubstituted (C j -C4Q)aikylene, and more preferably L is an acyclic unsubstituted (C j -C4Q)alkylene, and still more preferably the acyclic unsubstituted
  • (C r C 40 )alkylene is -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, cis -CH(CH 3 )CH 2 CH(CH 3 )-, trans
  • L is the substituted (C j -C4o)aikylene, and more preferably L is a (C j -C4Q)alkylene-substituted
  • (C j -C4Q)aikylene and still more preferably the (C j -C4Q)aikylene-substituted (C j -C4Q)alkylene is trans- 1 ,2-bis(methylene)cyclopentane, cis-l,2-bis(methylene)cyclopentane, trans-
  • the (C j -C4Q)alkylene-substituted (C j -C4Q)alkylene is exo-2,3-bis(methylene)bicyclo[2.2.2]octane or exo-
  • L is the unsubstituted (C 3 -C4Q)cycloalkylene, and more preferably L is cis-l,3-cyclopentane-diyl or cis-l,3-cyclohexane-diyl.
  • L is the substituted (C 3 -C4Q)cycloalkylene, and more preferably L is a
  • L is the (Cj-C4o)heterohydrocarbylene.
  • the aforementioned portion that comprises a 1- atom to 6- atom linker backbone of the (Cj-C4Q)heterohydrocarbylene of L comprises a from 2-atom to 5-atom, and more preferably a 3-atom or 4-atom linker backbone linking the Z atoms in formula (I) to which L is bonded.
  • L comprises the 1-atom linker backbone (e.g., L is -CEKOCH- ⁇ )- or -SiCCH- ⁇ -). In some embodiments L comprises the 2-atom linker backbone (e.g., L is -CEf ⁇ CE ⁇ OCH ⁇ )- or -CEf ⁇ SiCCH- ⁇ -)- In some embodiments L comprises the 3- atom linker backbone (e.g., L is -CH 2 CH 2 CH(OCH 3 )-, - ⁇ 3 ⁇ 48 ⁇ ( ⁇ 3 ⁇ 4) 2 ⁇ 3 ⁇ 4-, or -CH 2 Ge(CH 3 ) 2 CH 2 -).
  • L comprises the 1-atom linker backbone (e.g., L is -CEKOCH- ⁇ )- or -SiCCH- ⁇ -).
  • L comprises the 2-atom linker backbone (e.g., L is -CEf ⁇ CE ⁇ OCH ⁇ )- or -CEf ⁇ SiCCH- ⁇ -)-
  • L comprises the 3- atom linker
  • the "-CE ⁇ SiCCH- ⁇ CE ⁇ -" may be referred to herein as a 1 ,3-diradical of 2,2-dimethyl-2-silapropane.
  • L comprises the 4-atom linker backbone (e.g., L is -CH2CH2OCH2- or
  • L comprises the 5-atom linker backbone (e.g., L is
  • L comprises the 6-atom linker backbone (e.g., L is -CH 2 CH2C(OCH3)2CH2CH 2 CH2-, -CH 2 CH2CH2S(0)2CH 2 CH2-, or
  • each atom of the 1-atom to 6-atom linker backbone is a carbon atom (the heteroatom(s) of the (Cj-C4o)heterohydrocarbylene thereby being elsewhere therein).
  • one of the atoms of the 1-atom to 6-atom linker backbone is a heteroatom and the rest of the from 1 to 6 atoms, if any, are carbon atoms.
  • two of the from 2 to 6 atoms of the 2-atom to 6-atom linker backbone independently are heteroatoms and the rest of the from 2 to 6 atoms, if any, are carbon atoms.
  • at least one heteroatom is the Si(R c ) 2 .
  • each R c is unsubstituted (Cj-Cj ⁇ hydrocarbyl.
  • the two R c are taken together to form a (C2-Cj )alkylene (i.e., the 3-membered to 20- membered silacycloalkyl).
  • at least one heteroatom is the O.
  • at least one heteroatom is the S(O).
  • at least one heteroatom is the S(0)2-
  • at least one heteroatom is the P(R P ).
  • at least one heteroatom is the N(R N ).
  • O-O, N-N, P-P, N-P, S-S, or O-S bonds there are no O-O, N-N, P-P, N-P, S-S, or O-S bonds, other than O-S bonds in an S(O) or S(0)2 diradical functional group, in -Z-L-Z-.
  • O-O bonds there are no O-O, N-N, P-P, N-P, S-S, or O-S bonds, other than O-S bonds in an S(O) or S(0)2 diradical functional group, in -Z-L-Z-.
  • (Cj-C4o)heterohydrocarbylene is (Cj-Cj ⁇ heterohydrocarbylene, and more preferably
  • the (C r C 7 )heterohydrocarbylene of L is - ⁇ 3 ⁇ 48-( ⁇ 3 ⁇ 4) 2 ⁇ 3 ⁇ 4-, - ⁇ 3 ⁇ 48 ⁇ ( ⁇ 3 ⁇ 4 ⁇ 3 ⁇ 4) 2 ⁇ 3 ⁇ 4-,
  • -CH2Si(tetramethylene)CH2- is named l-silacyclopentan-l,l-dimethylene.
  • -CH2Si(pentamethylene)CH2- is named l-silacyclohexan-l,l-dimethylene.
  • L is defined as in any one of the Examples described later in the EXAMPLES
  • R ⁇ a , R 2a , R ⁇ b , and R 2b groups are preferred. In some embodiments one of R ⁇ a , R 2a ,
  • R ⁇ b , and R 2b independently is a (C j -C4o)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom; and each of the others of R ⁇ a , R 2a , R ⁇ b , and R 2b is a hydrogen atom. In some such embodiments it is each of R 2a , R lb , and R 2b that is a hydrogen atom. In other such embodiments it is each of R ⁇ a , R ⁇ b , and R 2b that is a hydrogen atom.
  • R ⁇ a , R 2a , R ⁇ b , and R 2b independently are a
  • R 2a , R lb , and R 2b is a hydrogen atom. In some such embodiments it is each of R ⁇ b and R 2b that is a hydrogen atom. In other such some embodiments it is each of R 2a and R 2b that is a hydrogen atom. In still other such some embodiments it is each of R ⁇ a and R ⁇ b that is a hydrogen atom.
  • R ⁇ a , R 2a , R ⁇ b , and R 2b independently are a
  • R ⁇ a , R 2a , R ⁇ b , and R 2b is a hydrogen atom.
  • R ⁇ b is a hydrogen atom.
  • R 2b is a hydrogen atom.
  • each of R ⁇ a , R 2a , R ⁇ b , and R 2b independently is a
  • one of R ⁇ a and R ⁇ b independently is a (C j -C4o)hydrocarbyl
  • R ⁇ a and R ⁇ b independently is a hydrogen atom, (C j -C4 Q )hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom.
  • one of R ⁇ a and R ⁇ b independently is a (C j -C4 Q )hydrocarbyl or halogen atom
  • the other of R ⁇ a and R ⁇ b independently is a hydrogen atom, (C j -C4o)hydrocarbyl, (C j -C4Q)heterohydrocarbyl, or halogen atom
  • each of R and R independently is a (C j -C4o)hydrocarbyl or halogen atom.
  • R lb is (C r C 40 )hydrocarbyl. In some embodiments at least one of R ⁇ a and R ⁇ is halogen atom.
  • R 2a and R 2b independently is a (C j -C4Q)hydrocarbyl
  • R 2a and R 2b independently is a hydrogen atom, (C j -C4o)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom.
  • one of R 2a and R 2b independently is a (C j -C4o)hydrocarbyl or halogen atom
  • the other of R 2a and R 2b independently is a hydrogen atom, (C j -C4Q)hydrocarbyl
  • R 2b is (C r C 40 )hydrocarbyl. In some embodiments at least one of R 2a and R 2b is halogen atom.
  • R 3a and R 3b are preferred.
  • each of R 3a and R 3b is a hydrogen atom.
  • one of R 3a and R 3b independently is a (C j -C4o)hydrocarbyl,
  • R 3a and R 3b independently is a hydrogen atom, (C j -C4o)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom.
  • one of R 3a and R 3b independently is a (C j -C4Q)hydrocarbyl or halogen atom
  • the other of R 3a and R 3b independently is a hydrogen atom, (C j -C4Q)hydrocarbyl,
  • each of R 3a and R 3b independently is a (C j -C4o)hydrocarbyl or halogen atom.
  • at least one of R 3a and R 3b is (C r C 40 )hydrocarbyl. In some embodiments at least one of
  • R 3a and R 3b is halogen atom.
  • R ⁇ a is a hydrogen atom
  • R ⁇ b is a (C j -C4Q)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom
  • R 2a independently is a (C j -C4o)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom
  • R 2b independently is a hydrogen atom, (C j -C4Q)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom.
  • R ⁇ b independently is (C j -C4o)hydrocarbyl or halogen atom.
  • each of R ⁇ a and R ⁇ b is a hydrogen atom; and at least one, and preferably each of R 2a and R 2b independently is a (C j -C4Q)hydrocarbyl, (C j -C4Q)heterohydrocarbyl, or halogen atom. In some embodiments at least one and preferably each of the R 2a and R 2b independently is (C j -C4Q)hydrocarbyl or halogen atom.
  • At least three of R ⁇ a , R ⁇ b , R 2a , and R 2b independently is a
  • each of R ⁇ a , R ⁇ b , R 2a , and R 2b independently is a (C j -C4o)hydrocarbyl or halogen atom.
  • R is a hydrogen atom
  • R 2b is a (C j -C4o)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom
  • R 3a independently is a (C j -C4Q)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom
  • R 3b independently is a hydrogen atom, (C j -C4o)hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom.
  • R 2b independently is (C j -C4Q)hydrocarbyl or halogen atom.
  • each of R 2a , R 2b , R 3a , and R 3b independently is a
  • each of the R 2a , R 2b , R 3a , and R 3b independently is (C j -C4Q)hydrocarbyl or halogen atom.
  • At least three of R 2a , R 2b , R 3a , and R 3b independently is a
  • each of R ⁇ a , R ⁇ R 3a , and R 3b independently is a (C j -C4o)hydrocarbyl or halogen atom.
  • R ⁇ a , R ⁇ , R ⁇ a , R ⁇ R 3a , and R 3b are more preferred.
  • R ⁇ a and R ⁇ are each hydrogen atom and R ⁇ a , R ⁇ , R 3a , and R 3b independently is (C j -C4 Q )hydrocarbyl, (C j -C4o)heterohydrocarbyl, or halogen atom; and more preferably R ⁇ a and R ⁇ are each hydrogen atom and each of R ⁇ a and R ⁇ independently is (C j -Cg)hydrocarbyl,
  • each of R 3a , and R 3b independently is (C j -C ⁇ hydrocarbyl, (C j -C j ⁇ heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom.
  • R ⁇ a and R ⁇ are each hydrogen atom; each of R ⁇ a and R ⁇ independently is (C j -Cg)hydrocarbyl, (C ⁇ -C '7 )heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom; and each of R 3a , and R 3b independently is (C j -C ⁇ hyclrocarbyl, (C j -C j ⁇ heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom.
  • each hydrocarbyl whenever used to define R ⁇ a , R ⁇ , R ⁇ a , R ⁇ R 3a , or R ⁇ , independently is an alkyl or cycloalkyl.
  • the alkyl is (C j -C ⁇ alkyl * more preferably (C j -Cg)alkyl, still more preferably (C j -Cg)alkyl, and even more preferably (C j -C4)aikyl.
  • the cycloalkyl is (Cg-C ⁇ cycloalkyl, and more preferably (C3-C4)cycloalkyl.
  • the alkyl is (C j -C ⁇ alkyl * more preferably (C j -Cg)alkyl, still more preferably (C j -Cg)alkyl, and even more preferably (C j -C4)aikyl.
  • the cycloalkyl is (Cg-C ⁇ cycloalkyl, and more preferably (
  • (C3"C4)cycloalkyl is cyclopropyl.
  • the (C j -C4)aikyl is methyl, ethyl, 1-propyl, 2-propyl, 1- butyl, 2-butyl, 2-methylpropyl, or 1,1-dimethylethyl, and more preferably methyl, ethyl, 2-propyl, or 1,1-dimethylethyl.
  • the (C j -C4)alkyl is ethyl, 2-propyl, or 1,1-dimethylethyl.
  • each halogen atom whenever used to define R ⁇ a , R ⁇ , R ⁇ a , R ⁇ R 3a , and R- ⁇ , independently is a fluorine atom or chlorine atom.
  • each of R ⁇ a and R ⁇ is a hydrogen atom and at least one, and in some embodiments each of R l a , R lb , R 3a , and R 3b independently is methyl; ethyl; 2-propyl; 1,1-dimethylethyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom; cyano; nitro; dimethylamino; aziridin-l-yl; or cyclopropyl.
  • each of R ⁇ a and R ⁇ b is a hydrogen atom and each of R ⁇ a , R ⁇ , R 3a , and R 3b independently is methyl; ethyl; 1- propyl; 2-propyl; 1 -butyl; 1,1 -dime thylethyl; cyano; dimethylamino; methoxy; trifluoromethyl; bromine atom; fluorine atom, or chlorine atom.
  • each of R ⁇ a and is a hydrogen atom and at least one, and in some embodiments each of R 2a , R ⁇ 3 , R ⁇ a , and R- ⁇
  • each of R ⁇ a and independently is methyl; ethyl; 1- propyl; 2-propyl; 1 -butyl; 1,1 -dime thylethyl; cyano; dimethylamino; methoxy; trifluoromethyl; bromine atom; fluorine atom, or chlorine atom.
  • metal-ligand complex of formula (I) and ligand of formula (Q) one of
  • R ⁇ a and R ⁇ is methyl; the other of R ⁇ a and R ⁇ is as in any one of the preferred embodiments described herein. More preferably in some of such embodiments each of R 2a and R ⁇ is a hydrogen atom and each of R ⁇ a and independently is as in any one of the preferred embodiments described herein.
  • the metal-ligand complex of formula (I) and ligand of formula (Q) at least one, and more preferably at least one of R ⁇ a and R ⁇ independently is ethyl; 2-propyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom; cyano; nitro; dimethylamino; aziridin-l-yl; or cyclopropyl. More preferably in such embodiments at least one, and more preferably each of R 2a and R ⁇ 5 is a hydrogen atom and each of R ⁇ a and R ⁇ independently is as in any one of the preferred embodiments described herein.
  • At least one, and more preferably each of R ⁇ a and R ⁇ is a halogen atom or (C j -Cg)alkyl, and still more preferably a (C j -C ⁇ Jalkyl, fluorine or chlorine atom.
  • at least one, and preferably each of R ⁇ a and R ⁇ is the fluorine atom.
  • at least one, and preferably each of R ⁇ a and R ⁇ is the chlorine atom.
  • at least one, and preferably each of R ⁇ a and R ⁇ is (C j -C ⁇ Jalkyl, and more preferably methyl.
  • R ⁇ a and R ⁇ are the same as each other. In other embodiments R ⁇ a and are the same as each other. In other embodiments R 2a and R 2b are different. In some embodiments R ⁇ a and R- ⁇ are the same as each other. In other embodiments R ⁇ a and are different. In some embodiments R ⁇ a and R ⁇ b are the same as each other and R 3a and R 3b are the same as each other. In some embodiments R ⁇ a and R 3a are the same as each other and R ⁇ b and R 3b are the same as each other. In some embodiments R l a , R lb , R 3a , and R 3b are all the same. In some embodiments R ⁇ a and R 3a are different and R ⁇ b and R 3b are different. Preferably in such embodiments each of R 2a and R 2b is a hydrogen atom.
  • R 2a and R 2b are the same as each other and R 3a and R 3b are the same as each other. In some embodiments R 2a and R 3a are the same as each other and R 2b and R 3b are the same as each other. In some embodiments R 2a , R 2b , R 3a , and R 3b are all the same. In some embodiments R 2a and R 3a are different and R 2b and R 3b are different. Preferably in such embodiments each of R ⁇ a and R ⁇ b is a hydrogen atom.
  • At least one of R ⁇ a , R ⁇ b , R 3a , R 3b , R 7c , and R 7d is not methyl. In some embodiments of the metal- ligand complex of formula (I) or the ligand of formula (Q) at least one of R 7c , R 7d , R 3a , and R 3b is not methyl.
  • each of R l a , R lb , R 2a , R 2b , R 3a , and R 3b independently is methyl; ethyl; 1 -propyl; 2-propyl; 1 -butyl; 1,1 -dime thy lethyl; cyano;
  • R ⁇ a , R ⁇ b , R 2a , R 2b , R 3a , and R 3b are defined as in any one of the Examples described later in the EXAMPLES OF THE PRESENT INVENTION section.
  • each of R 4a and R 4b is a hydrogen atom. In some embodiments at least one and in some embodiments each of R 4a and R 4b independently is as defined previously for R ⁇ a and R ⁇ b , respectively. When R 4a or R 4b independently is as defined previously for R ⁇ a or R ⁇ b , respectively, or both, R 4a and R ⁇ a independently may be the same or different and R 4b and R ⁇ b independently may be the same or different.
  • each of R 4a and R 4b independently is methyl; ethyl; 1 -propyl; 2-propyl; 1 -butyl; 1,1 -dime thylethyl; cyano; dimethylamino; methoxy; trifluoromethyl; bromine atom; fluorine atom, or chlorine atom.
  • R ⁇ c , R ⁇ c , R ⁇ d , and R ⁇ d are preferred.
  • each of R ⁇ c , R ⁇ c , R ⁇ d , and R ⁇ d is a hydrogen atom.
  • one of R ⁇ c , R ⁇ c , R ⁇ , and independently is (C j -C4Q)hydrocarbyl; (C j -C4o)heterohydrocarbyl; or halogen atom, and each of the remainder of R ⁇ c ,
  • R° ⁇ , R uu , and R ou is a hydrogen atom.
  • two or more of R u ⁇ , R° ⁇ , R uu , and R ou independently is (C j -C4o)hydrocarbyl; (C j -C4o)heterohydrocarbyl; or halogen atom, and each of the remainder, if any, of R 6c , R 8c , R 6d , and R 8d is a hydrogen atom.
  • R 7c and R 7d are preferred.
  • at least one of R 7c and R 7d independently is (C j -C4Q)hydrocarbyl; (C j -C4Q)heterohydrocarbyl; or halogen atom and the remainder, if any, of R 7c and R 7d is a hydrogen atom.
  • each of R 7c and R independently is (C j -C4o)hydrocarbyl; (C j -C4o)heterohydrocarbyl; or halogen atom.
  • each of R 7c and R 7d independently is (C j -C4o)hydrocarbyl or halogen atom.
  • R 7c and R 7d independently is a halogen atom or (C j -C4Q)aikyl, more preferably a (C j -C ⁇ alkyl * still more preferably a (C2"Cg)alkyl, and even more preferably a (C4-Cg)alkyl.
  • each of R 7c and R 7d independently is bromo; cyano; ethyl; isopropyl; 1 -butyl; tertiary-butyl; 1,1- dimethylpropan-l-yl; 1,1-dimethylbutan-l-yl; 1,1-dimethylpentan-l-yl; 1,1-dimethylhexan-l-yl; or 2,4,4-trimethylpentan-2yl, and still more preferably methyl, tertiary-butyl, or 2,4,4-trimethylpentan-2yl
  • R 7c and R 7d are the same as each other.
  • each of R 7c and R 7d is 2,4,4-trimethylpentan-2yl.
  • R 7c and R 7d are different from each other. More preferably R 7c and R 7d are defined as in any one of the Examples described later in the EXAMPLES OF THE PRESENT INVENTION section.
  • R ⁇ c and R ⁇ d are preferred. In some embodiments R ⁇ c and R ⁇ d are the same as each other. In some embodiments R ⁇ c and R ⁇ d are different from each other.
  • At least one, and more preferably each of R ⁇ c and R ⁇ d independently is
  • the (Cg-C4Q)aryl is a (Cg-C j g)aryl and more preferably (Cg-C ⁇ aryl-
  • the (Cg-C4Q)aryl is a substituted phenyl and preferably a 2,4-disubstituted phenyl wherein each substituent is R s , 2,5-disubstituted phenyl wherein each substituent is R s ; or 2,6- disubstituted phenyl wherein each substituent is R s ; and more preferably wherein each R s independently is phenyl, methyl, ethyl, isopropyl, or tertiary-butyl, and still more preferably 2,6-dimethylphenyl or 2,6-diisopropylphenyl.
  • the (Cg-C4Q)aryl is a 3,5-disubstituted phenyl wherein each substituent is R s , and more preferably wherein each R s independently is phenyl, methyl, ethyl isopropyl, or tertiary-butyl, and still more preferably 3,5-di(tertiary-butyl)phenyl or 3,5-diphenylphenyl.
  • the (Cg-C4Q)aryl is a 2,4,6-trisubstituted phenyl wherein each substituent is R s , and more preferably wherein each R s independently is phenyl, methyl, isopropyl, or tertiary-butyl; In some embodiments the (Cg-C4g)aryl is a naphthyl or substituted naphthyl wherein each substituent is
  • each R s independently is phenyl, methyl, ethyl, isopropyl, or tertiary- butyl, and still more preferably 1 -naphthyl, 2-methyl-l -naphthyl, or 2-naphthyl.
  • the (Cg-C4g)aryl is a 1 ,2,3,4-tetrahydronaphthyl, and more preferably l ,2,3,4-tetrahydronaphth-5-yl or l ,2,3,4-tetrahydronaphth-6-yl.
  • the (Cg-C4g)aryl is an anthracenyl, and more preferably anthracen-9-yl.
  • the (Cg-C4Q)aryl is a 1 ,2,3,4-tetrahydroanthracenyl, and more preferably l ,2,3,4-tetrahydroanthracen-9-yl.
  • the (Cg-C4g)aryl is a 1 ,2,3,4,5, 6,7, 8-octahydroanthracenyl, and more preferably 1 ,2,3,4,5, 6,7, 8-octahydroanthracen-9-yl, In some embodiments the (Cg-C4g)aryl is a phenanthrenyl, and more preferably a phenanthren-9-yl. In some embodiments the (Cg-C4Q)aryl is a 1 , 2,3,4,5,6,7, 8-octahydrophenanthrenyl, and more preferably
  • (Cg-C4o)aryl independently is unsubstituted or substituted by one or more substituents R s .
  • the (Cg-C4g)aryl is unsubstituted.
  • Preferred unsubstituted (Cg-C4g)aryl is unsubstituted inden-6-yl; 2,3-dihydro-lH-inden-6-yl; naphthalene-2-yl; or l ,2,3,4-tetrahydronaphthalen-6-yl; and more preferably unsubstituted naphthalen-l -yl; l ,2,3,4-tetrahydronaphthalen-5-yl; anthracen-9-yl; l ,2,3,4-tetrahydroanthracen-9-yl; or 1 ,2,3,4,5,6,7, 8-octahydroanthracen-9-yl.
  • each of the aforementioned (Cg-C4g)aryl independently is unsubstituted or substituted by one or more substituents R s .
  • the (Cg-C4g)aryl is substituted by from 1 to 4 R s , wherein R s is as described previously.
  • R s is as described previously.
  • R s of the substituted (Cg-C4g)aryl of R ⁇ c and independently is an unsubstituted
  • Cg-C ⁇ hydrocarbyl more preferably an unsubstituted (C4-Cg)hydrocarbyl, still more preferably phenyl or an unsubstituted (T ⁇ -C ⁇ alkyl, and even more preferably an unsubstituted tertiary (C4-Cg)alkyl (e.g., tertiary-butyl or tertiary-octyl (i.e., 1 , 1-dimethylhexyl)).
  • tertiary (C4-Cg)alkyl e.g., tertiary-butyl or tertiary-octyl (i.e., 1 , 1-dimethylhexyl)
  • Examples of preferred substituted (Cg-C4g)aryl are a 2,6-disubstituted-phenyl having same substituent R s (e.g., 2,6- dimethylphenyl; 2,6-diethylphenyl; 2,6-bis(l-methylethyl)phenyl; and 2,6-diphenyl-phenyl); a 3,5- disubstituted-phenyl having same substituent R s (e.g., 3,5-dimethylphenyl; 3,5- bis(trifluoromethyl)phenyl; 3,5-bis(l-methylethyl)phenyl; and 3,5-bis(l ,l-dimethylethyl)phenyl; and
  • At least one, and more preferably each of R ⁇ c and independently is
  • (Cj-C4Q)heteroaryl Preferably the (Cj-C4o)heteroaryl has at least one nitrogen atom-containing aromatic ring. More preferably the (Cj-C4Q)heteroaryl is a pyridinyl, indolyl, indolinyl, quinolinyl,
  • (Cj-C4o)heteroaryl is carbazolyl or a substituted carbazolyl, preferably a 2,7-disubstituted carbazolyl or
  • each substituent is R s , more preferably wherein each R s independently is phenyl, methyl, ethyl, isopropyl, or tertiary-butyl, still more preferably 3,6-di(tertiary- butyl)-carbazolyl, 3,6-di(tertiary-octyl)-carbazolyl, 3,6-diphenylcarbazolyl, or 3,6-bis(2,4,6- trimethylphenyl)-carbazolyl, and more preferably 3,6-di(tertiary-butyl)-carbazol-9-yl, 3,6-di(tertiary- octyl)-carbazol-9-yl, 3,6-diphenylcarbazol-9-yl, or 3,6-bis(2,4,6-trimethylphenyl)-carbazol-9-yl.
  • Examples of 2,7-disubstituted carbazolyl are the foregoing 3,6-disubstituted carbazolyl where the 3,6- substituents are moved to 2,7-positions, respectively.
  • Tertiary-octyl is 1 ,1-dimethylhexyl.
  • the (Cj-C4o)heteroaryl is 1 ,2,3,4-tetrahydrocarbazolyl, preferably a 1 ,2,3,4- tetrahydrocarbazol-9-yl.
  • each of the aforementioned (Cj-C4Q)heteroaryl independently is unsubstituted or substituted by one or more substituents R s .
  • each of the indolyl, indolinyl, and tetrahydro- and octahydro-containing (Cj-C4Q)heteroaryl is bonded via its ring nitrogen atom to the phenyl rings bearing R ⁇ c or in formula (I).
  • the (Cj-C4o)heteroaryl is unsubstituted.
  • Preferred unsubstituted (Cj-C4o)heteroaryl is unsubstituted quinolin-4-yl, quinolin-5-yl, or quinolin-8-yl, (the quinolinyl N being at position 1); 1 ,2,3,4-tetrahydroquinolin-l-yl (the tetrahydroquinolinyl N being at position 1); isoquinolin-l-yl, isoquinolin-4-yl, isoquinolin-5-yl, or isoquinolin-8-yl (the isoquinolinyl N being at position 2); l ,2,3,4-tetrahydroisoquinolin-2-yl (the tetrahydroisoquinolinyl N being at position 2); lH-indol-l-yl (the indolyl N being at position 1); lH-indolin-l-yl (the indolinyl N being at position 1
  • the (Cj-C4Q)heteroaryl is substituted by from 1 to 4 R s .
  • R s there are 1 or 2 R s substituents in each substituted (Cj-C4Q)heteroaryl.
  • R ⁇ independently is an unsubstituted (Cg-C ⁇ hydrocarbyl, more preferably an unsubstituted
  • (C4-Cg)hydrocarbyl still more preferably phenyl or an unsubstituted (C4-Cjo)alkyl, and even more preferably an unsubstituted tertiary (C4-Cg)alkyl (e.g., tertiary-butyl or tertiary-octyl (i.e., 1 ,1- dimethylhexyl)).
  • tertiary (C4-Cg)alkyl e.g., tertiary-butyl or tertiary-octyl (i.e., 1 ,1- dimethylhexyl)
  • the substituted (Cj-C4o)heteroaryl is a 2,7-disubstituted quinolin-4-yl, 2,7- disubstituted quinolin-5-yl, or 3,6-disubstituted quinolin-8-yl; 3,6-disubstituted
  • Examples of preferred substituted (Cj-C4o)heteroaryl are 4.6-bis(l ,l-dimethylethyl)pyridine-2-yl; 4,6- diphenylpyridin-2-yl; 3 -phenyl- lH-indol-l -yl; 3-(l , l-dimethylethyl)-lH-indol-l -yl; 3,6-diphenyl-9H- carbazol-9-yl; 3,6-bis[2',4',6'-tris(l ,l-dimethylphenyl)]-9H-carbazol-9-yl; and more preferably each of R ⁇ c and is 3,6-bis(l , l-dimethylethyl)-9H-carbazol-9-yl.
  • the term "tertiary butyl" means 1 ,1- dimethylethyl. More preferably R ⁇ c and are defined as in any one of
  • the aforementioned steric interactions are those between R ⁇ c and R ⁇ a and between R ⁇ and wherein each of R ⁇ a and R ⁇ is not a hydrogen atom and is otherwise as described in any one of the preferred embodiments.
  • the aforementioned valuable steric interactions are those between R ⁇ c and R ⁇ a and between R ⁇ and R ⁇ wherein each of R ⁇ a and
  • R ⁇ 5 is not a hydrogen atom and is otherwise as described in any one of the preferred embodiments.
  • each of R ⁇ a and R ⁇ 5 independently has a sufficiently high degree of steric bulk such that volumes of R ⁇ a and R ⁇ independently are equal to or greater than volume of ethyl; more preferably equal to or greater than volume of 2-propyl; and still more preferably equal to or greater than volume of 1,1-dimethylethyl.
  • each of R and R is a hydrogen atom
  • at least one and preferably both of R ⁇ a and R ⁇ 5 independently is (C2"C4 Q )hydrocarbyl or a chlorine atom.
  • each Z is O
  • each of R ⁇ a and R ⁇ 5 is a hydrogen atom
  • each of R ⁇ c and R ⁇ independently is the (C j -C4 Q )heteroaryl. More preferred in such embodiments is a metal-ligand complex of any one of formulas (la) to (Ie):
  • each R ⁇ and R ⁇ independently is a hydrogen atom or an unsubstituted (C j -C ⁇ alkyl-
  • each R ⁇ and R ⁇ independently is a hydrogen atom or an unsubstituted (C j -C ⁇ alkyl-
  • each Z is O, each of R ⁇ a and is a hydrogen atom, and each of R ⁇ c and independently is the (Cg-C4g)aryl. More preferred in such e formulas (Ik) to (Io):
  • each R and R independently is a hydrogen atom or an unsubstituted (C j -C ⁇ alkyl-
  • the M, X, L, R l a , R 2a , R 3a , R lb , R 2b , R 3b , R 7c , and R 7d are as defined for the same of formula (I) (i.e., as M, X, L, R l a , R 2a , R 3a , R lb , R 2b , R 3b , R 7c , and R 7d of formula (I)).
  • M is hafnium or zirconium, and more preferably hafnium.
  • each X is a monodentate ligand.
  • 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.
  • L is -CH2CH2-, -CH2CH2CH2-,
  • each of R l a , R 2a , R 3a , R lb , R 2b , R 3b independently is hydrogen atom, methyl; ethyl; 2-propyl; 1,1 -dime thylethyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom; cyano; nitro; dimethylamino; aziridin-l-yl; or cyclopropyl, wherein at least one of R ⁇ a , R ⁇ a , and R ⁇ a independently is not the hydrogen atom and at least one of R ⁇ , R ⁇ and R- ⁇ independently is not the hydrogen atom.
  • each of R ⁇ c and R ⁇ independently is (C4-Cg)alkyl.
  • the metal-ligand complex of formula (I) is the metal-ligand complex of any one of the formulas (la) to (Io) except each Z that is O is replaced by a Z that is S. In some embodiments the metal-ligand complex of formula (I) is the metal-ligand complex of any one of the formulas (la) to (Io) except each Z that is O is replaced by a Z that is N(C j -C4o)hydrocarbyl. In some embodiments the metal-ligand complex of formula (I) is the metal-ligand complex of any one of the formulas (la) to (Io) except each Z that is O is replaced by a Z that is P(C j -C4o)hydrocarbyl.
  • the ligand of formula (Q) corresponds to a didehydro analog of the metal- ligand complex of formulas (la) to (Io) (i.e., is a ligand of formula (Qa) to (Qo), respectively, wherein M and X and n have been deleted and H has been added to each phenolate oxygen, wherein there are two phenolate oxygen atoms in formula (I), each phenolate oxygen being bonded to M via a bond depicted by a straight line "— ").
  • the invention is the ligand of formula (Q).
  • the invention is the Group 1 or 2 metal salt of the ligand of formula (Q).
  • the Group 1 or 2 metal salt includes monometal salts, bimetal salts, and hemimetal salts.
  • the monometal salt are Na(Q-H) and [CaOH](Q-H), wherein "Q-H” means a monodeprotonated ligand of formula (Q) having a formal charge of -1.
  • the bimetal salts are Na2(Q-2H) and K2(Q-2H), wherein "Q-2H” means a doubly deprotonated (i.e., didehydro) ligand of formula (Q) having a formal charge of -2.
  • the hemimetal salts are Ca(Q-H)2 and Mg(Q-H)2.
  • the Group 1 or 2 metal salt of the ligand of formula (Q) can be prepared by conventional means.
  • the Group 1 or 2 metal salt of the ligand of formula (Q) can be prepared by contacting the ligand of formula (Q) with from one to two mole equivalents of a corresponding metal base such as, for example, a metal alkoxide, metal hydroxide, metal bicarbonate, or metal carbonate, wherein the metal of the metal base is the cation of the metal of Group 1 or 2.
  • the contacting is performed in a polar aprotic solvent (e.g., dimethylformamide, dimethylsulfoxide, acetone, or a mixture thereof), polar protic solvent (e.g., methanol, water, or a mixture thereof), or a mixture thereof.
  • a polar aprotic solvent e.g., dimethylformamide, dimethylsulfoxide, acetone, or a mixture thereof
  • polar protic solvent e.g., methanol, water, or a mixture thereof
  • the Group 1 or 2 metal salt can be directly prepared in situ without going through the conjugate acid that is the ligand of formula (Q).
  • the Group 1 or 2 metal salt of the ligand of formula (Q) can be converted back to the ligand of formula (Q) (i.e., back to its conjugate acid form) by conventional means such as, for example, acidifying with an acid (e.g., acetic acid or hydrochloric acid) a solution or mixture of the Group 1 or 2 metal salt of the ligand of formula (Q) in a polar solvent.
  • an acid e.g., acetic acid or hydrochloric acid
  • Syntheses of some of the ligands (e.g., the ligand of formula (Q)) employed to prepare the metal-ligand complexes of formula (I) may utilize starting materials, intermediates, or reaction products that contain more than one reactive functional group.
  • a reactive functional group may be protected from unwanted side reactions by a protecting group that renders the reactive functional group substantially inert to the reaction conditions employed.
  • a protecting group is selectively introduced onto a starting material or intermediate prior to carrying out the reaction step for which the protecting group is needed. Once the protecting group is no longer needed, the protecting group can be removed. It is well within the ordinary skill in the art to introduce protecting groups during a synthesis and then later remove them.
  • protecting groups that may be utilized to protect amino, hydroxy), or other functional groups: carboxylic acyl groups such as, for example, formyl, acetyl, and trifluoroacetyl; alkoxycarbonyl groups such as, for example, ethoxycarbonyl, tert-butoxycarbonyl (BOC), ⁇ , ⁇ , ⁇ -trichloroethoxycarbonyl (TCEC), and ⁇ - iodoethoxycarbonyl; aralkyloxycarbonyl groups such as, for example, benzyloxycarbonyl (CBZ), para- methoxybenzyloxycarbonyl, and 9-fiuorenylmethyloxycarbonyl (FMOC); trialkyloxycarbonyl groups such as, for example, benzyloxycarbonyl (CBZ), para- methoxybenzyloxycarbonyl, and 9-fiuorenylmethyloxycarbonyl (FMOC); trialkyloxycarbonyl groups such as, for
  • Examples of procedures for removing protecting groups include hydrogenolysis of CBZ groups using, for example, hydrogen gas at about 3.4 atmospheres in the presence of a hydrogenation catalyst such as 10% palladium on carbon, acidolysis of BOC or MOM groups using, for example, hydrogen chloride in dichloromethane or trifluoroacetic acid (TFA) in dichloromethane, reaction of silyl groups with fluoride ions, and reductive cleavage of TCEC groups with zinc metal.
  • a hydrogenation catalyst such as 10% palladium on carbon
  • the invention contemplates preparing the metal-ligand complex of formula (I) and ligands of formula (Q) by any suitable method.
  • the method of preparation is not critical.
  • the method employs a convergent synthesis approach involving coupling together of two primary intermediates. Preferred illustrative procedures are described below and shown in Figs. 1 to 4.
  • the first primary intermediate is of formula (a5).
  • the preparation of the first primary intermediate of formula (a5) starts with an electrophilic aromatic substitution reaction of phenol (al) with a source of a leaving group LG, wherein LG is, for example, Br or I, to give functionalized phenol (a2).
  • LG is, for example, Br or I
  • phenol (al) is available from commercial suppliers or can be readily prepared by a person of ordinary skill in the art.
  • the source of the leaving group LG-Y can be, for example, B ⁇ , N- bromosuccinimide (NBS), or L ⁇ .
  • the B ⁇ and I2 can be prepared in situ such as by a procedure described later in certain Preparations.
  • the oxygen of functionalized phenol (a2) can then be protected with a hydroxyl protecting group, PG, such as, for example, a methoxymethyl or tetrahydropyran-2- ylmethyl so as to form protected phenol (a3), which also has the leaving group LG.
  • PG hydroxyl protecting group
  • (a3) can be coupled with a source of R ⁇ (e.g., source of the (C j -C4o)hydrocarbyl or
  • aryl coupling reactions are known for a variety of types of source of R ⁇ and include copper-mediated nitrogen arylation reactions where the H in R ⁇ -H (a4) is bonded to a nitrogen atom of R- ⁇ especially a nitrogen atom of a heteroaryl group; and palladium- mediated carbon arylation reactions where the H in R ⁇ -H (a4) is bonded to an aromatic, alkenyl, or alkynyl carbon atom of R ⁇
  • the reactions described in Scheme 1 preferably are carried out under a substantially inert gas atmosphere in an anhydrous aprotic solvent such as, for example, diethyl ether, toluene, xylenes, tetrahydrofuran, diethylene glycol dimethyl ether, or a combination thereof and at a temperature in a range of from
  • the second primary intermediate is of formula (b4).
  • the preparation of the second primary intermediate of formula (b4) starts with an electrophilic aromatic substitution reaction of phenol (bl) with a source of a leaving group LG, wherein LG is, for example, Br or I, to give functionalized phenol (b2).
  • the source of the leaving group LG-Y can be the same as described previously for Scheme 1.
  • phenol (bl) is available from commercial suppliers or can be readily prepared by a person of ordinary skill in the art.
  • LG L are leaving groups suitable for be displaced in a nucleophilic substitution reaction by a phenol or phenolate anion. Examples of suitable LG L are bromide, iodide, trifluoromethanesulfonate, tosylate, and trifluoroacetate.
  • the reactions described in Scheme 2 preferably are carried out under a substantially inert gas atmosphere in an anhydrous aprotic solvent such as, for example, diethyl ether, toluene, xylenes, tetrahydrofuran, diethylene glycol dimethyl ether, or a combination thereof and at a temperature in a range of from about -78 °C to about 200 °C.
  • anhydrous aprotic solvent such as, for example, diethyl ether, toluene, xylenes, tetrahydrofuran, diethylene glycol dimethyl ether, or a combination thereof and at a temperature in a range of from about -78 °C to about 200 °C.
  • Preparation of second primary intermediate (b4) can also be carried out in polar organic solvents such as, for example, acetone, ethyl acetate, acetonitrile, ethanol, a mixture thereof, and water-containing mixtures thereof.
  • the reactions described in Scheme 3 preferably are carried out under a substantially inert gas atmosphere in an anhydrous aprotic solvent such as, for example, diethyl ether, toluene, xylenes, tetrahydrofuran, diethylene glycol dimethyl ether, or a combination thereof and at a temperature in a range of from about -78 °C to about 200 °C.
  • anhydrous aprotic solvent such as, for example, diethyl ether, toluene, xylenes, tetrahydrofuran, diethylene glycol dimethyl ether, or a combination thereof
  • the double-deprotection reaction can also be carried out in polar organic solvents such as, for example, acetic acid, acetone, ethyl acetate, acetonitrile, ethanol, a mixture thereof, and water-containing mixtures thereof and preferably further employs a deprotecting agent such as, for example, an acid (e.g., HC1 in ethanol or trifluoroacetic acid in methylene chloride), a hydrogenolysis reaction (e.g., when PG is, for example, benzyl or CBZ) employing hydrogen gas and a palladium catalyst.
  • the reactions are carried out at atmospheric pressure.
  • Scheme 4 An illustrative procedure for preparing the metal-ligand complex of formula (I) from the ligand of formula (Q) is shown in Scheme 4 in Fig. 4.
  • the preparation of the metal-ligand complex of formula (I) involves reacting the ligand of formula (Q) (prepared as shown in Scheme 3) with a source or sources of M and X as shown, for example, in Options A to D.
  • the compound of formula (Q) is doubly deprotonated with a non-nucleophilic base to give bisphenolate in situ (not shown), which is then allowed to react with a metal halide such as M(C1)4, wherein M is Zr,
  • organometallic compound such as, for example, an organolithium (X-Li) or Grignard reagent (X-MgBr) (or organosodium (X-Na) or organopotassium (X-K)), wherein X is as defined above to give the compound of formula (I).
  • organolithium X-Li
  • Grignard reagent X-MgBr
  • organosodium X-Na
  • organopotassium X-K
  • the compound of formula (Q) reacts with an organometallic compound M(X)4 to give the compound of formula (I).
  • the compound of formula (Q) reacts with the metal halide such as M(C1)4, followed by reaction of the resulting metal-ligand complex with 4 mole equivalents of an organometallic compound X-Li or X-MgBr (e.g., organolithium or Grignard reagent) to give the compound of formula (I).
  • the compound of formula (Q) reacts with an organometallic compound M(X)4 to give the compound of formula (I).
  • the compound of formula (Q) reacts with the metal halide such as M(C1)4, followed by reaction of the resulting metal-ligand complex with 4 mole equivalents of an organometallic compound X-Li or X-MgBr (e.g., organolithium or Grignard reagent) to give the compound of formula (I).
  • the compound of formula (Q) reacts with an organ
  • organometallic compound X-Li or X-MgBr such as, for example, methyl lithium or methyl magnesium bromide to give the compound of formula (I).
  • the reactions described in Scheme 4 preferably are carried out under a substantially inert gas atmosphere in an anhydrous aprotic solvent such as, for example, toluene, xylenes, tetrahydrofuran, diethylene glycol dimethyl ether, or a combination thereof and at a temperature in a range of from about -78 °C to about 200 °C.
  • the reactions are carried out at atmospheric pressure.
  • the invention contemplates procedures for preparing the metal-ligand complex of formula (I) and ligands of formula (Q) other than the previously described procedures illustrated in Figs. 1 to 4. Such other procedures would be readily known to one of ordinary skill in the art in view of the teachings described herein. Examples of such other procedures are those readily adapted from procedures in US 7,060,848 B2.
  • the invention process employs catalytic amounts of the invention catalyst.
  • each catalyst independently will be employed in a catalytic amount.
  • catalytic amount means less than a stoichiometric quantity based on number of moles of a product-limiting stoichiometric reactant employed in the invention process.
  • the catalytic amount is also equal to or greater than a minimum amount of the metal-ligand complex of formula (I) that is necessary for at least some product of the catalyzed reaction to be formed and detected (e.g., by mass spectrometry).
  • the minimum catalytic amount preferably is 0.0001 mole percent of the number of moles of a product- limiting stoichiometric reactant.
  • the product-limiting stoichiometric reactant for the invention catalyst typically will be ethylene.
  • the catalytic amount of the metal-ligand complex of formula (I) used to prepare the invention catalyst is from 0.001 mol % to 50 mol % of the moles of ethylene or (C3-C4Q)alpha-olefin, whichever is lower. More preferably, the catalytic amount of the metal-ligand complex of formula (I) is at least 0.01 mol , still more preferably at least 0.05 mol %, and even more preferably at least 0.1 mol . Also more preferably, the catalytic amount of the metal- ligand complex of formula (I) is 40 mol % or less, and still more preferably 35 mol % or less.
  • a particularly preferred invention catalyst is one that can achieve a high selectivity for polymerizing ethylene in the presence of the (C3-C4g)alpha-olefin in the invention process, wherein the high selectivity is characterized by the reactivity ratio r ⁇ described previously.
  • the reactivity ratio r ⁇ is greater than 30, more preferably greater than 40, still more preferably greater than 50, even more preferably greater than 60, and yet more preferably greater than 100.
  • the rich polyethylene or rich polyethylene segment of the poly(ethylene alpha- olefin) copolymer is characterized as having 6 mol or less, more preferably less than 3 mol , and still more preferably 2.3 mol or less of the residual of the alpha-olefin covalently incorporated therein.
  • the mol is characterized as having at least 0.01 mol , in other embodiments at least 0.1 mol , and in still other embodiments at least 1.0 mol of the residual of the (C3-C4Q) alpha-olefin covalently
  • Said mol are preferably determined by nuclear magnetic spectroscopy (NMR) spectroscopy as described later, but in some embodiments may alternatively be determined by the FT-IR spectroscopy as described later.
  • NMR nuclear magnetic spectroscopy
  • the residuals of the alpha-olefin and ethylene are approximately randomly distributed in the soft segment of the poly(ethylene alpha-olefin) block copolymer.
  • the invention catalyst is characterized as having a minimum catalyst efficiency or higher.
  • the catalyst efficiency is determined employing ethylene and 1-octene as described later at a polymerization reaction temperature of 170 °C and 0.10 micromole ( ⁇ ) of the metal-ligand complex of formula (I), 0.12 ⁇ of the activating co- catalyst, bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate
  • the catalyst efficiency is greater than 740,000, more preferably greater than 960,000, still more preferably greater than 1 ,480,000, and even more preferably greater than 1 ,900,000.
  • the catalyst efficiency is determined employing ethylene and 1-octene as described later at a polymerization reaction temperature of 170 °C and 0.08 ⁇ of the metal-ligand complex of formula (I), 0.096 ⁇ of the BOMATPB, and 0.8 ⁇ of MMAO-3A, the catalyst efficiency is greater than 1,1, 480,000.
  • the catalyst efficiency is determined employing ethylene and 1- octene as described later at a polymerization reaction temperature of 170 °C and 0.075 ⁇ of the metal-ligand complex of formula (I), 0.09 ⁇ of the BOMATPB, and 0.75 ⁇ of MMAO-3A, the catalyst efficiency is greater than 970,000, more preferably greater than 1 ,060,000, and still more preferably greater than 1 ,090,000.
  • the catalyst efficiency is determined employing ethylene and 1-octene as described later at a polymerization reaction temperature of 170 °C and 0.05 ⁇ of the metal-ligand complex of formula (I), 0.06 ⁇ of the BOMATPB, and 0.5 ⁇ of MMAO-3A
  • the catalyst efficiency is greater than 920,000, more preferably greater than 940,000, and still more preferably greater than 2,900,000. More preferably the catalyst efficiency is as defined as in any one of the Examples described later in the EXAMPLES OF THE PRESENT INVENTION section.
  • the invention catalyst, invention catalyst system or composition, or both further comprises one or more solvents (e.g., as in a solvated form of the invention catalyst), diluents (described later), or a combination thereof, as described herein.
  • the invention catalyst still further comprises a dispersant, e.g., an elastomer, preferably dissolved in the diluent.
  • the invention catalyst preferably comprises a homogeneous catalyst.
  • the metal-ligand complex of formula (I) is rendered catalytically active by contacting it to, or combining it with, the activating co-catalyst or by using an activating technique such as those that are known in the art for use with metal-based olefin polymerization reactions.
  • Suitable activating co- catalysts for use herein 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 activating technique is bulk electrolysis (explained in more detail hereinafter).
  • alkyl aluminum means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum.
  • Aluminoxanes and their preparations are known at, 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.
  • Preferred Lewis acid activating co-catalysts are Group 13 metal compounds containing from 1 to 3 hydrocarbyl substituents as described herein. More preferred Group 13 metal compounds are tri(hydrocarbyl)-substituted-aluminum or tri(hydrocarbyl)-boron compounds, still more preferred are tri ⁇ C j -C ⁇ alky ⁇ aluminum or tri((Cg-C j g)aryl)boron compounds and halogenated (including perhalogenated) derivatives thereof, even more especially tris(fluoro-substituted phenyl)boranes, still even more especially tris(pentafluorophenyl)borane.
  • the activating co-catalyst is a tris((C j -C2o)hydrocarbyl) borate (e.g., trityl tetrafluoroborate) or a
  • ammonium means a nitrogen cation that is a ((C j -C2())hydrocarbyl)4N + , a
  • Preferred combinations of neutral Lewis acid activating co-catalysts include mixtures comprising a combination of a tri ⁇ C j -C ⁇ alky ⁇ alurninum and a halogenated tri((Cg-C j g)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Also preferred are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane.
  • (alumoxane) [e.g., (Group 4 metal-ligand complex) :(tris(pentafluoro-phenylborane):(alumoxane)] are from 1 : 1 : 1 to 1: 10:30, more preferably from 1 : 1 : 1.5 to 1 :5: 10.
  • hydrocarbyloxides are disclosed in US 5,296,433.
  • suitable Bronsted acid salts for addition polymerization catalysts are disclosed in US 5,064,802; US 5,919,983; US 5,783,512.
  • suitable salts of a cationic oxidizing agent and a non-coordinating, compatible anion as activating co- catalysts for addition polymerization catalysts are disclosed in US 5,321,106.
  • suitable carbenium salts as activating co-catalysts for addition polymerization catalysts are disclosed in US 5,350,723.
  • suitable silylium salts as activating co-catalysts for addition polymerization catalysts are disclosed in US 5,625,087.
  • one or more of the foregoing activating co-catalysts are used in combination with each other.
  • An especially preferred combination is a mixture of a tri((C j -
  • the ratio of total number of moles of one or more metal-ligand complexes of formula (I) to total number of moles of one or more of the activating co-catalysts is from 1 : 10,000 to 100: 1. Preferably, the ratio is at least 1 :5000, more preferably at least 1: 1000; and 10: 1 or less, more preferably 1 : 1 or less.
  • the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metal-ligand complex of formula (I).
  • the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of formula (I) form 0.5: 1 to 10: 1, more preferably from 1 : 1 to 6:1, still more preferably from 1 : 1 to 5: 1.
  • the remaining activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal- ligand complexes of formula (I).
  • the invention catalyst further is employed in the invention process with the molecular weight control agent.
  • the molecular weight control agent is an ingredient (e) and give the molecular weight-controlled rich polyethylene.
  • molecular weight control agents are trialkyl aluminum compounds or other chain shuttling agents, or, preferably hydrogen (3 ⁇ 4).
  • the invention catalyst is employed with the combination of the chain shuttling agent and the promiscuous olefin polymerization catalyst.
  • the chain shuttling agent (CSA) is an ingredient (e) and the promiscuous olefin polymerization catalyst is an ingredient (f).
  • the molecular weight control agent can also be employed as another ingredient (e).
  • the chain shuttling embodiments of the invention process give a poly(ethylene alpha-olefin) block copolymer.
  • the invention catalyst where it is employed in the chain shuttling embodiments of the invention process, gives at least one polyethylene hard segment of the poly(ethylene alpha-olefin) block copolymer in the presence of the alpha-olefin and the promiscuous olefin polymerization catalyst gives at least one soft segment of the poly(ethylene alpha-olefin) block copolymer, the soft segment comprising residuals of ethylene and the alpha-olefin.
  • the contacting step comprises a continuous polymerization process that is performed under olefin polymerizing conditions and prepares a poly(ethylene alpha-olefin) block copolymer in one polymerization reactor, the poly(ethylene alpha- olefin) block copolymer comprising a segment rich in polyethylene (a hard segment) characterizable by a high melting temperature (T m > 100 degrees Celsius) and a segment rich in residuals from the alpha- olefin and ethylene (a soft segment).
  • T m > 100 degrees Celsius a high melting temperature
  • the alpha-olefin employed in the chain shuttling embodiments of the invention process is a (C3-C4Q)alpha-olefin.
  • Chain shuttling agents are known.
  • chain shuttling agent means a molecule characterizable, without limitation, as functioning in the chain shuttling embodiments of the invention process in such a way that polymer chains are transferred between two distinct catalysts with different monomer selectivities in a single polymerization reactor. That is, the chain shuttling agent (CSA) is a molecule characterizable, without limitation, as functioning in such a way that during the continuous process polymer chains are transferred between the catalyst comprising a mixture or reaction product of ingredients (a) and (b) and the promiscuous olefin polymerization catalyst.
  • CSA chain shuttling agent
  • chain shuttling agents comprise a first metal that is Al, B, or Ga, the first metal being in a formal oxidation state of +3; or a second metal that is Zn or Mg, the second metal being in a formal oxidation state of +2.
  • first metal that is Al, B, or Ga
  • second metal that is Zn or Mg
  • chain shuttling agents are described in U.S. Patent Application Publication Number US 2007/0167315.
  • Chain shuttling agents suitable for use with the catalyst system in the chain shuttling embodiments of the invention process include diethylzinc, di(i-butyl)zinc, di(n-hexyl)zinc,
  • the process when preparing the poly (ethylene alpha-olefin) block copolymer according to the immediately aforementioned embodiments of the invention process, the process employs a catalyst system comprising a mixture or reaction product of:
  • a first olefin polymerization catalyst (A) a first olefin polymerization catalyst, the first olefin polymerization catalyst being characterized as having a high comonomer incorporation index (described later, e.g., a comonomer incorporation index of 15 mole percent of comonomer or higher);
  • the second olefin polymerization catalyst comprising the invention catalyst as described in the first embodiment.
  • the "first olefin polymerization catalyst” is interchangeably referred to herein as “Catalyst (A).”
  • the first olefin polymerization catalyst (Catalyst (A)) means the aforementioned "promiscuous olefin polymerization catalyst.”
  • the “second olefin polymerization catalyst” is interchangeably referred to herein as “Catalyst (B).”
  • the first and second olefin polymerization catalysts i.e., Catalyst (A)_and Catalyst (B) have different ethylene and (C3-
  • the invention catalyst that comprises a mixture or reaction product of the ingredients (a) and (b) as described in the first embodiment is a Catalyst (B), but not Catalyst (A).
  • the comonomer incorporation index of Catalyst (B) is less than 50 percent and more preferably less than 5 percent of the comonomer incorporation index of Catalyst (A).
  • the comonomer incorporation index for Catalyst (A) is greater than 20 mol , more preferably greater than 30 mol , and still more preferably greater than 40 mol incorporation of comonomer.
  • the invention catalyst is employed in the invention process to selectively polymerize ethylene.
  • Other catalysts e.g., the promiscuous olefin polymerization catalyst
  • Promiscuous olefin polymerization catalysts are known.
  • the promiscuous olefin polymerization catalyst (ingredient (f)) is a catalyst useful for copolymerizing ethylene and the (C3-C4Q)alpha-olefin and is characterizable as having a reactivity ratio r ⁇ of less than 20 (r ⁇ ⁇ 20), wherein reactivity ratio r ⁇ is as defined previously.
  • Catalyst (A) of the catalyst system and the promiscuous olefin polymerization catalyst independently is a non-invention Catalyst (A) described in US 2006/0199930 Al ; US
  • the catalyst system further comprises a non-invention Catalyst (B) (i.e., a Catalyst (B) that is other than the invention catalyst that comprises a mixture or reaction product of the ingredients (a) and (b), wherein ingredients (a) and (b) are as described previously for the first embodiment), the non-invention Catalyst (B) being a Catalyst (B) described in US 2006/0199930 Al ; US 2007/0167578 Al; US 2008/0311812 Al ; US 7,355,089 B2; or WO 2009/012215 A2.
  • B non-invention Catalyst
  • Catalyst (Al) is [N-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2- diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03/40195, 2003US and WO 04/24740, and having the structure:
  • Catalyst (A2) is [N-(2,6-di(l-methylethyl)phenyl)amido)(2-methylphenyl)(l,2-phenylene-(6- pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03/40195, 2003US 2, 2003, and WO 04/24740, and having the structure:
  • Catalyst (A3) is bis[N,N' ' '-(2,4,6 ri(methylphenyl)amido)ethylenediamine]hafnium dibenzyl, and having the structure:
  • Catalyst (A4) is bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2- phenoxymethyl)cyclohexane-l,2-diyl zirconium (IV) dibenzyl, prepared substantially according to the teachin structure:
  • Catalyst (A5) is [q z -2,6-diisopropyl-N-(2-methyl-3-(octylimino)butan-2- yl)benzeneamide]trimethylhafnium, prepared substantially according to the teachings of WO
  • Catalyst (Bl) is l,2-bis-(3,5-di-t-butylphenylene)(l-(N-(l-methylethyl)imino)methyl)(2-oxoyl) zirconium dibenzyl, and having the structure:
  • Catalyst (B2) is l,2-bis-(3,5-di-t-butylphenylene)(l-(N-(2-methylcyclohexyl)-imino)methyl)(2- z
  • Catalyst (CI) is (t-butylamido)dimethyl(3-N-pyrrolyl-l,2,3,3a,7a-q-inden-l-yl)silanetitanium dimethyl, prepared substantially according to the techniques of USP 6,268,444, and having the structur
  • Catalyst (C2) is (t-butylarnido)di(4-methylphenyl)(2-methyl-l,2,3,3a,7a ⁇ -inden-l- yl)silanetitanium dimethyl, prepared substantially according to the teachings of US-A -2003/004286, and having the structure
  • Catalyst (C3) is (t-butylamido)di(4-methylphenyl)(2-methyl-l,2,3,3a,8a ⁇ -s-indacen-l- yl)silanetitanium dimethyl, prepared substantially according to the teachings of US-A -2003/004286, and having
  • Catalyst (Dl) is bis(dimethyldisiloxane)(indene-l-yl)zirconium dichloride, available from -Aldrich and having the structure:
  • the amount of the (C3-C40) alpha-olefin comonomer incorporated into a polyolefin such as the rich polyethylene or a segment of a polyolefin copolymer such as the rich polyethylene segment of the of the poly(ethylene alpha-olefin) copolymer (e.g., the hard and soft segments of the poly(ethylene alpha-olefin) block copolymer) is characterized by the aforementioned comonomer incorporation index.
  • the term, "comonomer incorporation index” refers to the mole percent of residuals of comonomer incorporated into an ethylene/comonomer copolymer, or ethylene-derived hard segment thereof, prepared under representative olefin polymerization conditions (described later herein), ideally under steady-state, continuous solution polymerization conditions in a hydrocarbon diluent at 100 °C, 4.5 megapascals (MPa) ethylene pressure (reactor pressure), greater than 92 percent (more preferably greater than 95 percent) ethylene conversion, and greater than 0.01 percent comonomer conversion.
  • MPa megapascals
  • ethylene pressure reactor pressure
  • the selection of metal-ligand complexes or catalyst compositions having the greatest difference in comonomer incorporation indices results in copolymers from two or more monomers having the largest difference in block or segment properties, such as density.
  • Monomer and comonomer content of the polyolefins prepared by the invention process may be measured using any suitable technique such as, for example, infrared (IR) spectroscopy, especially the aforementioned FT-IR spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy, with techniques based on NMR spectroscopy being preferred and carbon-13 NMR spectroscopy being more preferred.
  • IR infrared
  • NMR nuclear magnetic resonance
  • the comonomer incorporation index may be determined directly, for example by the use of NMR spectroscopic techniques described previously or by IR spectroscopy. If
  • any difference in comonomer incorporation is indirectly determined.
  • this indirect determination may be accomplished by various techniques based on monomer reactivities.
  • the relative amounts of comonomer and monomer in the copolymer and hence the copolymer composition is determined by relative rates of reaction of comonomer and monomer.
  • Mathematically the molar ratio of comonomer to monomer is given by
  • R p2 andR pl are the rates of polymerization of comonomer and monomer respectively.
  • the ratio of comonomer to monomer in the reactor largely determines polymer composition as determined according to either the Terminal Copolymerization Model or the Penultimate Copolymerization Model.
  • the terminal copolymerization model is employed. In this model insertion reactions of the type
  • C represents the catalyst, M ; represents monomer i , and ky is the rate constant having the rate equation
  • the mole fraction of comonomer in the polymer is solely dependent on the mole fraction of comonomer in the reaction media and two temperature dependent reactivity ratios defined in terms of the insertion rate constants as:
  • the identities of the last two monomers inserted in the growing polymer chain dictate the rate of subsequent monomer insertion.
  • the polymerization reactions are of the form
  • the comonomer content can be calculated (again as disclosed in George Odian, Supra.) as:
  • the polymer composition is a function only of temperature dependent reactivity ratios and comonomer mole fraction in the reactor. The same is also true when reverse comonomer or monomer insertion may occur or in the case of the interpolymerization of more than two monomers.
  • Reactivity ratios for use in the foregoing models may be predicted using well known theoretical techniques or empirically derived from actual polymerization data. Suitable theoretical techniques are disclosed, for example, in B. G. Kyle, Chemical and Process Thermodynamics, Third Addition, Prentice-Hall, 1999 and in Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pp 1197-1203.
  • RKS Redlich-Kwong-Soave
  • the invention process employs olefin polymerizing conditions.
  • the olefin polymerizing conditions independently produce the invention catalyst in situ that is formed by combination or reaction of the metal-ligand complex of formula (I) and the one or more activating co-catalysts of ingredient (b).
  • the invention catalyst system comprises the invention catalyst and at least one other ingredient of the invention process.
  • Such other ingredients include, but are not limited to, (i) olefin monomer(s); (ii) another metal-ligand complex of formula (I); (iii) one or more of non-invention Catalysts (A); (iv) one or more of non-invention Catalysts (B); (v) chain shuttling agent; (vi) a catalyst stabilizer (if any); (vii) a solvent (if any); and (viii) a mixture of any two or more thereof.
  • Olefin polymerizing conditions independently refer to reaction conditions such as solvent(s), atmosphere(s), temperature(s), pressure(s), time(s), and the like that are preferred for giving, after 15 minutes reaction time, at least a 10 percent (%), more preferably at least 20%, and still more preferably at least 30% reaction yield of the rich polyethylene or rich polyethylene segment of the poly(ethylene alpha-olefin) copolymer, from the invention process.
  • the rich polyethylene segment of the poly(ethylene alpha-olefin) copolymer is the polyethylene hard segment of a poly(ethylene alpha-olefin) block copolymer .
  • the invention process is independently are run under an inert atmosphere (e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof).
  • an inert atmosphere e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof.
  • Other atmospheres are contemplated, however, and these include sacrificial olefin in the form of a gas and hydrogen gas (e.g., as a polymerization termination agent).
  • the invention process independently is run without any solvent, i.e., is a neat process that is run in a neat mixture of ingredients (a) to (d).
  • the neat mixture further contains additional ingredients (e.g., catalyst stabilizer such as
  • the invention process is run with a solvent or mixture of two or more solvents, i.e., is a solvent-based process that is run as a solvent- containing mixture of ingredients (a) to (d), and at least one solvent, e.g., an aprotic solvent.
  • the neat process or solvent-based process is run at a temperature of the neat mixture or solvent- containing mixture of from -20 °C to about 300 °C. In some embodiments, the temperature is at least 30 °C, and more preferably at least 40 °C.
  • the temperature is at least 100 °C. In some embodiments, the temperature is at least 120 °C. In some embodiments, the temperature is at least 130 °C. In some embodiments, the temperature is at least 150 °C. In some embodiments, the temperature is 200 °C or lower. In some embodiments, the temperature is 180 °C or lower. In some embodiments, the temperature is 160 °C or lower.
  • a convenient temperature is from about 130 °C to about 190 °C (e.g., 150 °C or 170 °C or 190 °C).
  • the invention process independently is run under a pressure of from about 0.9 atmospheres (atm) to about 10 atm (i.e., from about 91 kiloPascals (kPa) to about 1010 kPa). More preferably, the pressure is about 1 atm (i.e., about 101 kPa).
  • polymerizable olefins useful in the invention process are (C2-
  • C4o)hydrocarbons consisting of carbon and hydrogen atoms and containing at least 1 , and preferably no more than 3, and more preferably no more than 2, carbon-carbon double bonds.
  • from 1 to 4 hydrogen atoms of the (C2-C4g)hydrocarbons are replaced, each by a halogen atom, preferably fluoro or chloro to give halogen atom-substituted (C2-C4g)hydrocarbons as the useful polymerizable olefins.
  • the (C2-C4g)hydrocarbons (not halogen atom-substituted) are preferred.
  • Preferred polymerizable olefins i.e., olefin monomers
  • Preferred polymerizable olefins are ethylene and polymerizable (C3-C4Q)olefins.
  • the (C3-C4Q)olefins include an alpha-olefin, a cyclic olefin, styrene, and a cyclic or acyclic diene.
  • at least one of the other polymerizable olefin is the alpha-olefin, and more preferably a (C3-C4g)alpha-olefin.
  • the (C3-C4Q)olefins include an alpha-olefin, a cyclic olefin, styrene, and a cyclic or acyclic diene.
  • at least one of the other polymerizable olefin is the alpha-olefin
  • C4Q)alpha-olefin is a (C4-C4Q)alpha-olefin, more preferably a (Cg-C4g)alpha-olefin, still more preferably a (C7-C4Q)alpha-olefin, and even more preferably a (Cg-C4Q)alpha-olefin.
  • the alpha-olefin comprises the (C3-C4Q)alpha-olefin, more preferably a branched chain (C3-C4Q)alpha- olefin, still more preferably a linear-chain (C3-C4Q)alpha-olefin, even more preferably a linear chain
  • linear-chain (C3-C4Q)alpha-olefin that is 1-propene, 1-butene, 1- pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1- tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, or a linear-chain (C2Q-)alpha-olefin that is 1-propene, 1-butene, 1- pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1- tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadec
  • the cyclic olefin is a (C3-C4Q)cyclic olefin.
  • the cyclic or acyclic diene is a (C4-C4g)diene, preferably an acyclic diene, more preferably an acyclic conjugated
  • (C4-C4o)diene more preferably an acyclic 1,3 -conjugated (C4-C4g)diene, and still more preferably 1,3- butadiene.
  • Polyolefins that can be made by an invention process include, for example, rich polyethylene and interpolymers that comprise residuals of ethylene and one or more polymerizable (C3-C4Q)olefins.
  • Preferred homopolymers are high density polyethylene.
  • Preferred interpolymers are those prepared by co-polymerizing a mixture of two or more polymerizable olefins such as, for example,
  • ethylene/propylene ethylene/1 -butene, ethylene/ 1-pentene, ethylene/ 1-hexene, ethylene/4-methyl-l- pentene, ethylene/1 -octene, ethylene/styrene, ethylene/propylene/butadiene and other EPDM terpolymers.
  • the polyolefin is an ethylene homopolymer (e.g., a high density polyethylene), an ethylene/alpha-olefin interpolymer (i.e., poly(ethylene alpha-olefin) copolymer such as, for example, a poly(ethylene 1-octene)), or an ethylene/alpha-olefin/diene inte olymer (i.e., a poly(ethylene alpha- olefin diene) terpolymer such as, for example, a poly(ethylene 1-octene 1,3-butadiene).
  • ethylene homopolymer e.g., a high density polyethylene
  • an ethylene/alpha-olefin interpolymer i.e., poly(ethylene alpha-olefin) copolymer such as, for example, a poly(ethylene 1-octene)
  • an ethylene/alpha-olefin/diene inte olymer i.
  • the mole ratio of (moles of (C3-C4Q)alpha-olefin)/(moles of ethylene) is 0.1 or higher, more preferably 0.30 or higher, still more preferably 0.50 or higher, and even more preferably 0.75 or higher (e.g., 1.0 or higher).
  • the present invention is a polyolefin, preferably the rich polyethylene (e.g., in an isolated form or as part of an intermediate mixture with the alpha-olefin) prepared by the invention process.
  • the invention olefin polymerization reactions can be run in one reactor or multiple reactors, the multiple reactors being two reactors, or more than two reactors.
  • multiple catalyst processes are useful in the present invention.
  • two or more catalysts are introduced into a single reactor under the olefin polymerization conditions, wherein at least the first one of the catalysts is an invention catalyst and each catalyst inherently produces a mixture or blend of different polyolefin copolymers.
  • the terms "mixture” and "blend" as applied to the polyolefin copolymers are synonymous.
  • a relatively high molecular weight product (M w from 100,000 to over 1,000,000, more preferably 200,000 to 500,000) polyolefin is formed from one of the catalysts while a product of a relatively low molecular weight (M w 2,000 to 300,000) polyolefin is formed from another of the catalysts.
  • the two or more catalysts can have similar or different comonomer incorporation ability, different molecular weight capability, or a combination thereof.
  • the resulting mixture or blend of different polyolefin copolymers will have properties dependent on the ratio of the two or more catalysts that are employed in the single reactor.
  • Suitable combinations of polyolefin molecular weight, comonomer incorporation ability, processes, and ratios of catalysts for such products are disclosed in U.S. Pat. No. 6,924,342.
  • the invention catalysts are compatible with other olefin polymerization catalysts, including Ziegler/Natta catalysts.
  • the second catalyst composition may comprise another invention catalyst, a metallocene or other ⁇ -bonded ligand group containing metal-ligand complex (including constrained geometry metal-ligand complexes), or a polyvalent heteroatom ligand group containing metal-ligand complex, especially polyvalent pyridylamine or imidizolylamine based complexes and tetradentate oxygen-ligated biphenylphenol based Group 4 metal-ligand complexes.
  • the invention catalyst is prepared from and the invention process employs three or fewer, more preferably two, and still more preferably one metal- ligand complex of formula (I) per reactor. Examples of suitable processes and systems employing multiple reactors include such processes and systems as are disclosed in U.S.
  • the multiple reactors preferably two reactors, can be operated in series or in parallel, with at least one invention catalyst being employed in at least one of the reactors.
  • at least one invention catalyst being employed in at least one of the reactors.
  • one, two, or, when employing more than two reactors three or more of the multiple reactors contain the two or more catalysts described in the immediately preceding paragraph (single reactor paragraph).
  • Polyolefin products from these reactors can have similar or different densities.
  • the final polymer product is a mixture or blend of effluents of different polyolefin copolymers from the two or more, preferably two, reactors.
  • the effluents of different polyolefin copolymers are combined by mixing or blending prior to being subjected to de volatilization so as to result in a uniform mixing or blending of the different polyolefin copolymers.
  • the molecular weight of the different polyolefin copolymers from the two or more reactors is nearly the same but the densities vary to the extent that one of the reactors produces a first polyolefin copolymer with density in the range of 0.865-0.895, while another reactor produces a second polyolefin copolymer with a different density in the range of 0.885-0.950.
  • dual reactor/dual catalyst invention process allows for the preparation of a mixture or blend polyolefin copolymers with tailored properties.
  • two reactors are connected in series, that is, the effluent from a first reactor is charged to a second reactor and, optionally, fresh monomer, solvent and hydrogen is added to the second reactor.
  • Olefin polymerization conditions are adjusted in the second reactor so that they are different from the olefin polymerization conditions that were employed in the first reactor such that a weight ratio of weight of the polyolefin copolymer produced in the first reactor to weight of the polyolefin copolymer produced in the second reactor is ideally in the range of from 20:80 to 80:20.
  • This embodiment of a dual reactor process is capable of producing a mixture or blend of different polyolefin copolymers having broadened molecular weight distribution or polydispersity index (PDI).
  • the invention process produces a mixture or blend of different polyolefin copolymers that comprises high and low molecular weight polyolefin copolymer components, wherein the high molecular weight polyolefin copolymer component contains higher quantities of comonomer (lower density) incorporated therein than quantities of comonomer that are contained in the low molecular weight polyolefin copolymer component.
  • one of the two reactors of the dual reactor embodiment contains a heterogeneous Ziegler-Natta catalyst or a chromium containing catalyst, such as one of the numerous such catalysts known in the art.
  • Ziegler- Natta catalysts include, but are not limited to, titanium-based catalysts supported on MgCl 2 , and additionally comprise compounds of aluminum containing at least one aluminum-alkyl bond.
  • Suitable Ziegler-Natta catalysts and their preparation include, but are not limited to, those disclosed in U.S. Pat. Nos. 4,612,300, 4,330,646, and 5,869,575.
  • Suitable chromium based catalysts are those disclosed in U.S. Pat. Nos. 4,981,927, 4,835,219, 4,564,660, 4,173,548, 3,953,413, and elsewhere.
  • the invention catalyst is contained in the same or different one of the two reactors.
  • the mixture or blend of different polyolefin copolymers and invention process for preparing same are preferred. Especially preferred is such a mixture or blend containing the rich polyethylene or rich polyethylene segment -containing poly(ethylene alpha-olefin) copolymer produced by the invention process.
  • the present invention is the poly(ethylene alpha-olefin) copolymer prepared by certain embodiments of the invention process.
  • a particularly valuable type of poly(ethylene alpha-olefin) copolymer is the aforementioned poly(ethylene alpha-olefin) block copolymer or, simply, an olefin block copolymer (OBC).
  • OBCs are characterized as having at least one so-called "hard segment” or block comprising residuals of ethylene monomer and at least one so-called "soft segment” or block comprising residuals of an alpha-olefin (also known as an alpha-olefin and 1 -olefin) monomer.
  • OBCs are available from The Dow Chemical Company, Midland, Michigan, USA under the trade name INFUSETM Olefin Block Copolymers. INFUSETM Olefin Block Copolymers are useful in a variety of forms and applications such as, for example, those listed at www.dow.com/infuse.
  • Part of a preparation of an OBC involves a process that, among other steps, selectively polymerizes ethylene in the presence of the alpha-olefin to form the one or more hard segments of the OBC. More preferably, the
  • poly(ethylene alpha-olefin) block copolymer is characterizable as having a melting temperature of greater than 100 degrees Celsius, and more preferably greater than 120 °C, as determined by Differential Scanning Calorimetry using the procedure described later.
  • the poly(ethylene alpha-olefin) block copolymers comprise ethylene residuals and one or more copolymerizable a-olefin comonomer residuals (i.e., ethylene and one or more copolymerizable a-olefin comonomer s in polymerized form).
  • the poly(ethylene alpha-olefin) block copolymers are characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/a-olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers.
  • the terms "interpolymer” and copolymer” are used interchangeably herein.
  • the multi-block copolymer can be represented by the following formula:
  • n' is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher
  • A represents a hard block or segment
  • B represents a soft block or segment.
  • As and Bs are linked in a linear fashion, not in a branched or a star fashion.
  • Hard segments refer to blocks of polymerized units in which ethylene residuals are present in an amount greater than 95 weight percent, and preferably greater than 98 weight percent in the poly(ethylene alpha-olefin) block copolymers.
  • the comonomer e.g., (C3-C4Q)alpha- olefin
  • the hard segments comprise all or substantially all ethylene residuals.
  • polyethylene hard segment and "ethylene -derived hard segment” are synonymous and mean the hard segment portion of a poly(ethylene alpha-olefin) block copolymer.
  • Soft segments refer to blocks of polymerized units in which the comonomer residuals content is greater than 5 weight percent, preferably greater than 8 weight percent, greater than 10 weight percent, or greater than 15 weight percent in the poly(ethylene alpha-olefin) block copolymers.
  • the comonomer residuals content in the soft segments can be greater than 20 weight percent, greater than 25 eight percent, greater than 30 weight percent, greater than 35 weight percent, greater than 40 weight percent, greater than 45 weight percent, greater than 50 weight percent, or greater than 60 weight percent.
  • a blocks and B blocks are randomly distributed along a polymer (backbone) chain of the poly(ethylene alpha-olefin) block copolymer.
  • the poly(ethylene alpha-olefin) block copolymers usually do not have a structure like:
  • the poly(ethylene alpha-olefin) block copolymers usually do not have a third type of block, i.e., do not have a "C" block that is not an A block and not a B block.
  • each of block A and block B of the poly(ethylene alpha-olefin) block copolymers has monomers or comonomer s randomly distributed within the block.
  • neither block A nor block B comprises two or more segments (or sub-blocks) of distinct composition, such as a tip segment, which has a different composition than the rest of the block.
  • the polyolefin comprises an ethylene/alpha-olefin interpolymer, such as those described in PCT International Patent Application Publication Number WO 2009/097560, which is herein incorporated by reference, preferably a block copolymer, which comprises a hard segment and a soft segment, and is characterized by a M w /M n in the range of from about 1.4 to about 2.8 and:
  • T m has at least one T m (°C), and a density (d) in grams/cubic centimeter, wherein the numerical values of T m and d correspond to the relationship:
  • T m > -6553.3 + 13735(d) - 7051.7(d) 2
  • (b) is characterized by a heat of fusion ( ⁇ , in J/g), and a delta temperature quantity ( ⁇ , in °C), defined as the temperature difference between the tallest differential scanning
  • the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 °C; or
  • (c) is characterized by an elastic recovery (R g ) in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/alpha-olefin interpolymer, and has a density d in grams/cubic centimeter, wherein the numerical values of R g and d satisfy the following relationship when ethylene/alpha-olefin interpolymer is substantially free of a cross- linked phase:
  • (d) has a molecular fraction which elutes between 40 °C and 130 °C when
  • fractionated using TREF characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/alpha-olefin interpolymer; or
  • (e) has a storage modulus at 25 °C (G'(25 °C)) and a storage modulus at 100°C (C (100 °C)) wherein the ratio of G'(25 °C) to G'(100 °C) is in the range of about 1 : 1 to about 9: 1 ; or
  • (f) is characterized by an average block index greater than zero (0) and up to about 1.0; or (g) has a molecular fraction which elutes between 40 °C and 130 °C when fractionated using TREF, characterized in that the fraction has a molar comonomer content greater than, or equal to, the quantity (- 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T+ 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction, measured in °C; and,
  • the polyolefin comprises an ethylene/alpha-olefin interpolymer, such as that described in U.S. Patent No. US 7,355,089 and U.S. Patent Application Publication No. US 2006- 0199930, wherein the interpolymer is preferably a block copolymer, and comprises a hard segment and a soft segment, and the ethylene/alpha-olefin interpolymer:
  • (a) has a M w /M n from about 1.7 to about 3.5, at least one T m ( °C), and a density d, in grams/cubic centimeter, wherein the numerical values of T m and d correspond to the relationship:
  • Tm > -2002.9 + 4538.5(d) - 2422.2(d)2;
  • (b) has a M w /M n from about 1.7 to about 3.5, and is characterized by a heat of fusion, ⁇ in J/g, and a delta quantity, ⁇ ( °C), defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ⁇ and ⁇ have the following
  • the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 °C; or
  • (c) is characterized by an R g in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/alpha-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of R g and d satisfy the following relationship when ethylene/alpha-olefin interpolymer is substantially free of a cross-linked phase:
  • (d) has a molecular fraction which elutes between 40 °C and 130 °C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/alpha-olefin interpolymer; or
  • (e) has a storage modulus at 25 °C (G'(25 °C)), and a storage modulus at 100 °C, (G'(100 °C)), wherein the ratio of G'(25 °C) to G'(100 °C) is in the range of about 1 : 1 to about 9: 1 or
  • (f) has a molecular fraction which elutes between 40 °C and 130 °C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 and a M w /M n greater than about 1.3; or
  • (g) has an average block index greater than zero (0) and up to about 1.0 and a M w /M n greater than about 1.3; or (h) has a molecular fraction which elutes between 40 °C and 130 °C when fractionated using TREF, characterized in that the fraction has a molar comonomer content greater than, or equal to, the quantity (- 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T+ 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction, measured in °C.
  • a preferred invention process can achieve a minimum molecular weight distribution or polydispersity index (PDI) of the polyolefin product produced thereby.
  • the PDI is greater than 2.4, in other embodiments the PDI is greater than 4.0, in other embodiments the PDI is greater than 6.0, and in still other embodiments the PDI is greater than 8.0. In some embodiments the PDI is less than 11. More preferably the PDI is as defined as in any one of the Examples described later in the EXAMPLES OF THE PRESENT INVENTION section.
  • a preferred invention process can achieve a productivity ratio of weight of polyolefin produced per weight of ethylene employed, as determined employing ethylene and 1- octene as described later at a polymerization reaction temperature of 170 °C, wherein the productivity ratio of the polyolefin produced to ethylene employed is greater than 1.00, preferably greater than 1.10, more preferably greater than 1.40, and still more preferably greater than 2.50. More preferably the productivity ratio is as defined as in any one of the Examples described later in the EXAMPLES OF THE PRESENT INVENTION section.
  • M w weight average molecular weight
  • polydispersity index M w and ratio of M w /M n (polydispersity index or PDI) using a Polymer LabsTM 210 high temperature gel permeation chromatograph. Prepare samples using 13 mg of polyethylene polymer that is diluted with 16 mL of 1 ,2,4-trichlorobenzene (stabilized with butylated hydroxy toluene (BHT)), heat and shake at 160 °C for 2 hours.
  • BHT butylated hydroxy toluene
  • Determining melting and crystallization temperatures and heat of fusion by Differential Scanning Calorimetry (DSC; DSC 2910, TA Instruments, Inc.): First heat samples from room temperature to 180 °C at a heating rate of 10 °C per minute. After being held at this temperature for 2 to 4 minutes, cool the samples to -40 °C at a cooling rate of 10 °C per minute; hold the sample at the cold temperature for 2 to 4 minutes, and then heat the sample to 160 °C.
  • r.t. room temperature
  • g gram(s)
  • mL milliliter(s)
  • °C degrees Celsius
  • mmol millimole(s)
  • MHz MegaHertz
  • Hz Hertz
  • Preparation 4 preparation of intermediate, 3,6-di-tert-butyl-9-(2-(methoxymethoxy)-5-(2,4,4 trimethylpentan-2-yl)phenyl)-9H-carbazole, (P4).
  • Preparation 6 preparation of intermediate, 3,6-di-tert-butyl-9-(2-(tetrahydro-2H-pyran-2-yloxy)-5- (2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole, (P6).
  • Preparations 13a to 13d preparation of intermediates, 2,4-dimethyl-6-iodophenol (P13a); 4-chloro-2- ethyl-6-iodophenol, (P13b); 4-fiuoro-6-iodo-2-methylphenol, (P13c), and 4-fiuoro-6-iodo-2- trifiuoromethylphenol, (PI 3d).
  • Preparations 14a to 14d preparation of intermediates, l,3-bis(2,4-dimethyl-6-iodophenoxy)propane, (P14a); l,3-bis(4-chloro-2-ethyl-6-iodophenoxy)propane, (P14b); l,3-bis(4-fluoro-6-iodo-2- methylphenoxy)propane, (PI 4c); and l,3-bis(4-fluoro-6-iodo-2-trifluoromethylphenoxy)propane, (P14d).
  • Non-limiting examples of the present invention are described below that illustrate some specific embodiments and aforementioned advantages of the present invention.
  • Preferred embodiments of the present invention incorporate one limitation, and more preferably any two, limitations of the Examples, which limitations thereby serve as a basis for amending claims.
  • Example Q2 preparation of ligand, 2',2"-(propane-l ,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H- carbazol-9-yl)-3',5'-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol, (Q2).
  • Example Q3 preparation of ligand, 2',2"-(propane-l,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl- -carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol, (Q3).
  • the ligands (Q4) to (Q9), (Q12), and (Q14) to (Q19) can be prepared and ligands (Q10), (Ql l), (Q13), and (Q20) to (Q22) are prepared.
  • ligand (Q10) in a manner similar to Example (Q3) except use (P14a) of Preparation P14a instead of (P12).
  • Prepare ligand (Ql 1) in a manner similar to Example (Q3) except use (P14b) of Preparation P14b instead of (P12).
  • Prepare ligand (Q13) in a manner similar to Example (Q3) except use (PI 4c) of Preparation PI 4c instead of (PI 2).
  • Prepare ligand (Q20) in a manner similar to Example (Q3) except use (P14d) of Preparation P14d instead of (P12).
  • Fig. 6 Structures of ligands (Q17) to (Q22) are shown in Fig. 7.
  • t-butyl is synonymous with tert-butyl, tertiary-butyl, and 1,1-dimethylethyl.
  • the "Me” means methyl.
  • the “Et” means ethyl.
  • t-octyl is synonymous with tert-octyl, tertiary-octyl, and 1,1-dimethylhexyl.
  • -CN is cyano.
  • the invention ligand is any one of ligands (Ql) to (Q3). In some embodiments the invention ligand is any one of ligands (Q10), (Ql l), (Q13), and (Q20) to (Q22). In some embodiments the invention ligand is any one of ligands (Q4) to (Q9), (Q12), and (Q14) to (Q19). In some embodiments the invention ligand is ligand (Q3). In some embodiments the invention ligand is ligand (Q13). In some embodiments the invention ligand is any one of ligands (Ql), (Q2), (Q10), (Ql l), and (Q20) to (Q22).
  • Example 1 preparation of (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)- 3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (1).
  • yl)biphenyl-2-ol) ligand (Ql), Preparation 9, and HfCL ⁇ add 4.1 mole equivalents of methyl magnesium bromide (MeMgBr) at room temperature. After stirring for 1.5 hours, remove solvent under reduced pressure. To the resulting residue add 10 mL of toluene and 25 mL of hexane. Filter the resulting mixture to give an off-white filtrate. Remove solvent to give an off-white solid. NMR of this solid shows formation of essentially pure (1) with small impurities in aliphatic region. Dissolve the solid in about 1.5 mL of toluene, and then add 3 mL of hexane. Filter the resulting solution, and place filtrate into freezer overnight. Decant resulting liquid, and wash the remaining white crystalline solid with 1 mL of hexane and then dry it under reduced pressure to yield 0.32g (55.5%) of (1).
  • MeMgBr methyl magnesium bromide
  • Fig. 8 shows an ORTEP depiction of a single crystal structure derived by x-ray analysis of invention metal-ligand complex (2) (Example 2).
  • invention metal-ligand complex (2) Example 2
  • hydrogen atoms are omitted for clarity.
  • . 9 shows an ORTEP depiction of a single crystal structure derived by x-ray analysis of invention metal-ligand complex (3) (Example 3). In Fig. 9 hydrogen atoms are omitted for clarity.
  • the metal-ligand complexes (4) to (9), (12), (14) to (19), (24), and (25) can be prepared, and metal-ligand complexes (10), (11), (13), and (20) to (23) are prepared.
  • the metal-ligand complexes (4) to (22), (23), (24), and (25) can be or are prepared from ligands (Q4) to (Q22), (Q3), (Q2), and (Q3), respectively.
  • metal-ligand complex (10), (11), (13), (20), (21), and (22) in a manner similar to Example (3) except respectively use ligand (QIO) of Example QIO, (Ql l) of Example Ql l, (Q 13) of Example Q 13 , (Q20) of Example Q20, (Q21 ) of Example Q21 , or (Q22) of Example Q22 instead of ligand (Q3).
  • QIO ligand
  • t-butyl is synonymous with tert-butyl, tertiary-butyl, and 1,1-dimethylethyl.
  • Me means methyl.
  • Et means ethyl.
  • t-octyl is synonymous with tert-octyl, tertiary-octyl, and 1,1-dimethylhexyl.
  • -CN is cyano.
  • At least one of the one or more metal-ligand complexes of formula (I) is any one of metal-ligand complexes (1) to (3). In some embodiments at least one of the one or more metal-ligand complexes of formula (I) is any one of metal-ligand complexes (10), (11), (13), and (20) to (23). In some embodiments at least one of the one or more metal-ligand complexes of formula (I) is any one of metal-ligand complexes (4) to (9), (12), (14) to (19), (24), and (25). In some embodiments at least one of the one or more metal-ligand complexes of formula (I) is metal-ligand complex (3).
  • At least one of the one or more metal-ligand complexes of formula (I) is metal-ligand complex (13). In some embodiments at least one of the one or more metal-ligand complexes of formula (I) is any one of metal-ligand complexes (1), (2), (10), (11), and (20) to (23).
  • a metal-ligand complex of formula (I) e.g., the metal ligand complex of Example Ql, Q2, or Q3
  • an activating co-catalyst that is either trityl borate or bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate ([HNMe ⁇ j gH- ⁇ l L EKCgF ⁇ ], abbreviated as BOMATPB)
  • another activating co-catalyst that is a triisobutylaluminum-modified methylalumoxane-3A (MMAO-3A).
  • Illustrative procedures are: Determine melting and crystallization temperatures of polyethylene polymer products by DSC using DSC 2910 instrument from TA Instruments, Inc. DSC samples are first heated from room temperature to 180 °C at a heating rate of 10 °C per minute. Hold at 180 °C for from 2 minutes to 4 minutes, then cool the sample to -40 °C at a cooling rate of 10 °C per minute. Hold at -40 °C for from 2 minutes to 4 minutes, and then heat the sample to 160 °C at a heating rate of 10 °C per minute. Determine M w and ratio of M w /M n (polydispersity index or PDI) using a Polymer LabsTM 210 high temperature gel permeation calorimeter.
  • M w and ratio of M w /M n polydispersity index or PDI
  • non-invention catalysts prepared from non-invention metal-ligand complexes that are of formula (I) except they lack R ⁇ a and in the general procedure prepare poly ethylenes having either greater than 14.0 mol , and in some cases greater than 17 mol , covalent incorporation of 1-octene; a density of less than 0.86 grams per milliliter (g/mL); a melting temperature of less than 50 °C, and in some cases less than 30 °C; or a combination thereof when prepared by the aforementioned process.
  • Examples A to N Selective polymerization of ethylene in the presence of 1-octene to give a high density polyethylene using the metal-ligand complex (1), (2), (3) (seven times), (11) (two times), (13) (two times), and (21) of Examples 1, 2, 3 (seven times), 11 (two times), 13 (two times), and 21, respectively.
  • Example A using 0.3 micromoles ( ⁇ ) of the metal-ligand complex (1) of Example 1 ; activating co-catalysts that are BOMATPB (0.36 ⁇ ) and MMAO-3A (3 ⁇ ); and a polymerization reaction temperature of 150 °C; and
  • Example B using 0.2 ⁇ of the metal-ligand complex of (2) of Example 2; activating co- catalysts that are BOMATPB (0.24 ⁇ ) and MMAO-3A (2 ⁇ ); and a polymerization reaction temperature of 150 °C.
  • Example C using 0.1 ⁇ of the metal-ligand complex (3) of Example 3; activating co- catalysts that are BOMATPB (0.12 ⁇ ) and MMAO-3A (1.2 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Examples D and E using 0.1 ⁇ of the metal-ligand complex (3) of Example 3; activating co-catalysts that are BOMATPB (0.12 ⁇ ) and MMAO-3A (1.0 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Examples F and G using 0.075 ⁇ of the metal-ligand complex (3) of Example 3; activating co-catalysts that are BOMATPB (0.09 ⁇ ) and MMAO-3A (0.75 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Examples H and I using 0.05 ⁇ of the metal-ligand complex (3) of Example 3; activating co-catalysts that are BOMATPB (0.06 ⁇ ) and MMAO-3A (0.5 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Example J using 0.05 ⁇ of the metal-ligand complex (11) of Example 11; activating co- catalysts that are BOMATPB (0.06 ⁇ ) and MMAO-3A (0.5 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Example K using 0.08 ⁇ of the metal-ligand complex (11) of Example 11 ; activating co- catalysts that are BOMATPB (0.096 ⁇ ) and MMAO-3A (0.8 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Example L using 0.1 ⁇ of the metal-ligand complex (13) of Example 13; activating co- catalysts that are BOMATPB (0.12 ⁇ ) and MMAO-3A (1.0 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Example M using 0.075 ⁇ of the metal-ligand complex (13) of Example 13; activating co- catalysts that are BOMATPB (0.09 ⁇ ) and MMAO-3A (0.75 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Example N using 0.08 ⁇ of the metal-ligand complex (21) of Example 21 ; activating co- catalysts that are BOMATPB (0.096 ⁇ ) and MMAO-3A (0.8 ⁇ ); and a polymerization reaction temperature of 170 °C.
  • Table 1 certain characterizations of processes of Examples A to N employing metal-ligand complexes (1) to (3) (seven times), (11) (two times), (13) (two times), and (21), respectively.
  • gPEO/gMLC catalyst efficiency calculated by dividing weight in grams of PEO product by weight in grams of metal in metal-ligand complex used.
  • Table 2 certain characterizations of high density polyethylenes of Examples A to N.
  • the invention catalysts prepared from the invention metal-ligand complexes selectively polymerize ethylene in presence of an alpha- olefin when used in the invention process.
  • This selective polymerization of the invention process desirably yields the rich polyethylene (also referred to herein as a rich polyethylene), or the rich polyethylene segment of a poly(ethylene alpha-olefin) copolymer, the rich polyethylene and rich polyethylene segment independently having low mole percent incorporation of alpha-olefin therein.
  • the invention process would selectively give an ethylene-derived hard segment of an OBC in the presence of a (C3-C4Q)alpha-olefin.
  • a particularly preferred metal-ligand complex(es) of formula (I) is one capable of preparing such a catalyst(s) that can achieve a high selectivity for polymerizing ethylene in the presence of the (C3-C4g)alpha-olefin, wherein the high selectivity is characterized in the preferred embodiments as described previously.
  • the invention process is also useful for preparing the aforementioned polymer blends with good catalyst efficiency.

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Abstract

La présente invention concerne généralement un procédé qui polymérise sélectivement l'éthylène en présence d'une alpha-oléfine, et un complexe métal-ligand (précatalyseur) et un catalyseur utile dans de tels procédés, et des compositions associées. La présente invention concerne généralement en outre des ligands et des intermédiaires utiles pour préparer le complexe métal-ligand et des procédés de leur préparation.
PCT/US2010/035096 2010-05-17 2010-05-17 Procédé pour polymériser sélectivement l'éthylène et catalyseur pour celui-ci WO2011146044A1 (fr)

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PCT/US2010/035096 WO2011146044A1 (fr) 2010-05-17 2010-05-17 Procédé pour polymériser sélectivement l'éthylène et catalyseur pour celui-ci
BR112012022591-0A BR112012022591B1 (pt) 2010-05-17 2011-05-11 Processo para seletivamente polimerizar etileno na presença de uma alfa-olefina, complexo metal-ligante, catalisador e ligante
MX2012007036A MX350592B (es) 2010-05-17 2011-05-11 Proceso para polimerizacion selectiva de etileno y un catalizador del mismo.
KR1020127018508A KR101788892B1 (ko) 2010-05-17 2011-05-11 에틸렌의 선택적 중합 방법 및 그를 위한 촉매
US13/105,018 US8609794B2 (en) 2010-05-17 2011-05-11 Process for selectively polymerizing ethylene and catalyst therefor
CN201180024264.5A CN102906129B (zh) 2010-05-17 2011-05-11 选择性聚合乙烯的方法及其催化剂
EP11724080.4A EP2491062B1 (fr) 2010-05-17 2011-05-11 Procédé de polymérisation sélective de l'éthylène et catalyseur utile à cet effet
PCT/US2011/036004 WO2011146291A1 (fr) 2010-05-17 2011-05-11 Procédé de polymérisation sélective de l'éthylène et catalyseur utile à cet effet
JP2013511220A JP5767318B2 (ja) 2010-05-17 2011-05-11 エチレンを選択的に重合させるための方法及びそのための触媒
US14/076,322 US9000108B2 (en) 2010-05-17 2013-11-11 Process for selectively polymerizing ethylene and catalyst therefor

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WO2021091959A1 (fr) * 2019-11-04 2021-05-14 Dow Global Technologies Llc Catalyseurs de polymérisation au biphénylphénol de titane
CN114616255A (zh) * 2019-11-04 2022-06-10 陶氏环球技术有限责任公司 联苯酚聚合催化剂
CN114729081A (zh) * 2019-11-04 2022-07-08 陶氏环球技术有限责任公司 联苯基苯酚钛聚合催化剂
CN114616255B (zh) * 2019-11-04 2024-09-13 陶氏环球技术有限责任公司 联苯酚聚合催化剂
CN113880977A (zh) * 2021-10-18 2022-01-04 万华化学集团股份有限公司 一种烯烃聚合催化剂、制备方法与应用

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