WO2018005201A1 - Complexes quinolinyldiamido de métaux de transition, leur production et leur utilisation - Google Patents

Complexes quinolinyldiamido de métaux de transition, leur production et leur utilisation Download PDF

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WO2018005201A1
WO2018005201A1 PCT/US2017/038606 US2017038606W WO2018005201A1 WO 2018005201 A1 WO2018005201 A1 WO 2018005201A1 US 2017038606 W US2017038606 W US 2017038606W WO 2018005201 A1 WO2018005201 A1 WO 2018005201A1
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complex
group
ring
methylphenyl
phenyl
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PCT/US2017/038606
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WO2018005201A8 (fr
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John R. Hagadorn
Patrick J. PALAFOX
Peijun Jiang
Yaohua GAO
Xin Chen
Georgy P. GORYUNOV
Mikhaill SHARIKOV
Dmitry V. Uborsky
Alexander Z. Voskoboynikov
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Exxonmobil Chemical Patents Inc.
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Priority to SG11201811335UA priority Critical patent/SG11201811335UA/en
Priority to EP17820955.7A priority patent/EP3478694B9/fr
Priority to CA3029544A priority patent/CA3029544C/fr
Priority to KR1020187038128A priority patent/KR20190003835A/ko
Priority to JP2018568410A priority patent/JP2019527679A/ja
Priority to CN201780046978.3A priority patent/CN109563110B/zh
Priority to BR112018077480-4A priority patent/BR112018077480A2/pt
Publication of WO2018005201A1 publication Critical patent/WO2018005201A1/fr
Publication of WO2018005201A8 publication Critical patent/WO2018005201A8/fr

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    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • 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
    • C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/64082—Tridentate ligand
    • C08F4/64086—Neutral ligand
    • C08F4/64089—NNN
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    • 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
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    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
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    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
    • C—CHEMISTRY; METALLURGY
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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    • C—CHEMISTRY; METALLURGY
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    • 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+

Definitions

  • TITLE Quinolinyldiamido Transition Metal Complexes, Production and Use Thereof
  • the invention relates to quinolinyldiamido transition metal complexes and intermediates and processes for use in making such quinolinyldiamido complexes.
  • the transition metal complexes may be used as catalysts for alkene polymerization processes.
  • Pyridyl amines have been used to prepare Group 4 complexes which are useful transition metal components in the polymerization of alkenes, see, for example, US 2002/0142912; US 6,900,321; and US 6,103,657; where the ligands have been used in complexes in which the ligands are coordinated in a bidentate fashion to the transition metal atom.
  • WO 2005/095469 shows catalyst compounds that use tridentate ligands through two nitrogen atoms (one amido and one pyridyl) and one oxygen atom.
  • US 2004/0220050 A 1 and WO 2007/067965 disclose complexes in which the ligand is coordinated in a tridentate fashion through two nitrogen (one amido and one pyridyl) and one carbon (aryl anion) donors.
  • a key step in the activation of these complexes is the insertion of an alkene into the metal-aryl bond of the catalyst precursor (Froese, R.D.J, et al., J. Am. Chem. Soc, 2007, 129, pp. 7831-7840) to form an active catalyst that has both a five-membered and a seven- membered chelate ring.
  • WO 2010/037059 discloses pyridine containing amines for use in pharmaceutical applications.
  • US 8,158,733 describes catalyst compositions featuring 2-(2-aryloxy)-8- anilinoquinoline, 2,8-bis(2-aryloxy)quinoline, and 2,8-bis(2-aryloxy)dihydroquinoline ligands that do not feature a tridentate NNN donor ligand.
  • US 2012/0016092 describes catalyst compositions containing 2-imino-8- anilinoquinoline and 2-aminoalkyl-8-anilinoquinoline ligands having a one-atom linker between the quinoline and the nitrogen donor at the 2-position of the quinoline ring.
  • the performance may be varied with respect to the amount of polymer produced per amount of catalyst (generally referred to as the "activity") under the prevailing polymerization conditions; the molecular weight and molecular weight distribution achieved at a given temperature; and/or the placement of higher alpha-olefins in terms of the degree of stereoregular placement.
  • This invention relates to novel transition metal complexes having tridentate NNN ligands. This invention also relates to quinolinyldiamido and related transition metal complexes represented by the formula (I) or (II):
  • M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal
  • J is a three-atom-length bridge between the quinoline and the amido nitrogen
  • E is selected from carbon, silicon, or germanium
  • X is an anionic leaving group
  • L is a neutral Lewis base
  • R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
  • R 2 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
  • n 1 or 2;
  • n 0, 1, or 2
  • n+m is not greater than 4.
  • any two adjacent R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
  • any two X groups may be joined together to form a dianionic group
  • any two L groups may be joined together to form a bidentate Lewis base
  • an X group may be joined to an L group to form a monoanionic bidentate group.
  • This invention further relates to process to make the above complexes, process to make intermediates for the above complexes, and methods to polymerize olefins using the above complexes.
  • FIG. 1 shows line drawings of eight quinolinyldiamide complexes prepared in the Experimental section.
  • Figure 2 shows examples of quinolinyldiamine ligands prepared in the Experimental section.
  • Figure 3 shows drawings of quinolinyldiamide ligand and metal complex that contains a fused dihydronaphthalene linker group.
  • Figure 4 shows the solid-state structure of (Q5)HfMe2 as determined by single crystal X-ray diffraction.
  • transition metal complexes The term complex is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom.
  • the ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization.
  • the ligand may be coordinated to the transition metal by covalent bond and/or electron donation coordination or intermediate bonds.
  • the transition metal complexes are generally subjected to activation to perform their polymerization or oligomerization function using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.
  • Me is methyl
  • Et is ethyl
  • Bu is butyl
  • t-Bu and t-Bu are tertiary butyl
  • Pr is propyl
  • iPr and iPr are isopropyl
  • Cy is cyclohexyl
  • THF also referred to as thf
  • Bn is benzyl
  • Ph is phenyl. Room temperature is 23 °C, unless otherwise stated.
  • substituted generally means that a hydrogen of the substituted species has been replaced with a different atom or group of atoms.
  • methyl-cyclopentadiene is cyclopentadiene that has been substituted with a methyl group.
  • picric acid can be described as phenol that has been substituted with three nitro groups, or, alternatively, as benzene that has been substituted with one hydroxy and three nitro groups.
  • hydrocarbyl radical is defined to be C C 100 radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • a substituted hydrocarbyl radical is a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one functional group such as F, CI, Br, I, C(0)R*, C(0)NR* 2 , C(0)OR*, NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SiR* 3 , GeR* 3 , SnR* 3 , PbR* 3 , and the like (where R* is independently a hydrogen or hydrocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.
  • R* is independently a hydrogen or hydrocarbyl radical, and two or more R* may join together to form a substituted or un
  • catalyst system is defined to mean a complex/activator pair.
  • Catalyst system means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a co-activator.
  • it means the activated complex and the activator or other charge-balancing moiety.
  • the transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system.
  • complex may also be referred to as catalyst precursor, precatalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. These words are used interchangeably. Activator and cocatalyst are also used interchangeably.
  • a scavenger is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments, a co- activator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.
  • an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have a "propylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from propylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a higher cc-olefin is defined to be an cc-olefin having 4 or more carbon atoms.
  • ethylene is considered an alpha-olefin.
  • a "polymer” has two or more of the same or different “mer” units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other. "Different” in reference to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • ethylene polymer or "ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol% propylene derived units, and so on.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight
  • wt% is weight percent
  • mol% is mole percent.
  • Molecular weight distribution also referred to as polydispersity index (PDI)
  • PDI polydispersity index
  • melting points (T m ) are DSC second melt.
  • a "ring carbon atom” is a carbon atom that is part of a cyclic ring structure.
  • a benzyl group has six ring carbon atoms and para-methylstyrene also has six ring carbon atoms.
  • aryl or "aryl group” means a six carbon aromatic ring and the substituted variants thereof, including but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl.
  • heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, preferably N, O, or S.
  • ring atom means an atom that is part of a cyclic ring structure.
  • a benzyl group has six ring atoms and tetrahydrofuran has five ring atoms.
  • a heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom.
  • tetrahydrofuran is a heterocyclic ring
  • 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring.
  • a substituted heterocyclic ring is a heterocyclic ring in which at least one hydrogen atom of the heterocyclic ring has been substituted with a hydrocarbyl group, a substituted hydrocarbyl group or a functional group such as F, CI, Br, I, C(0)R*, C(0)NR*2, C(0)OR*, NR* 2 , OR*, SeR*, TeR*, PR* 2 , AsR* 2 , SbR* 2 , SR*, BR* 2 , SiR* 3 , GeR* 3 , SnR* 3 , PbR* 3 , and the like (where R* is independently a hydrogen or hydrocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure).
  • aromatic also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatics.
  • This invention relates to quinolinyldiamido transition metal complexes where a three- atom linker is used between the quinoline and the nitrogen donor in the 2-position of the quinoline ring.
  • the resulting complex is thought to be effectively chiral (Ci symmetry), even when there are no permanent stereocenters present. This is a desirable catalyst feature, for example, for the production of isotactic polyolefins.
  • This invention further relates to a quinolinyldiamido transition metal complex represented by Formula (I), preferably by Formula (II), preferably by Formula (III):
  • M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal (preferably a group 4 metal);
  • J is group comprising a three-atom-length bridge between the quinoline and the amido nitrogen, preferably a group containing up to 50 non-hydrogen atoms;
  • E is carbon, silicon, or germanium
  • X is an anionic leaving group, (such as a hydrocarbyl group or a halogen);
  • L is a neutral Lewis base
  • R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 10' , R 11 , R 11' , R 12 , and R 14 are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, or phosphino; n is 1 or 2;
  • n 0, 1, or 2
  • n+m is not greater than 4.
  • any two R groups may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic, saturated or unsaturated ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
  • any two X groups may be joined together to form a dianionic group
  • any two L groups may be joined together to form a bidentate Lewis base
  • any X group may be joined to an L group to form a monoanionic bidentate group.
  • M is a Group 4 metal, such as zirconium or hafnium.
  • J is an aromatic substituted or unsubstituted hydrocarbyl (preferably a hydrocarbyl) having from 3 to 30 non-hydrogen atoms, preferably J is represented by the formula:
  • R 7 , R 8 , R 9 , R 10 , R 10' , R 11 , R 11 , R 12 , R 14 and E are as defined above, and any two R groups (e.g., R 7 & R 8 , R 8 & R 9 , R 9 & R 10 , R 10 & R 11 , etc.) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms (preferably 5 or 6 atoms), and said ring may be saturated or unsaturated (such as partially unsaturated or aromatic), preferably J is an arylalkyl (such as arylmethyl, etc.) or dihydro-lH- indenyl, or tetrahydronaphthalenyl group.
  • R 7 , R 8 , R 9 , R 10 , R 10' , R 11 , R 11 , R 12 , R 14 and E are as defined above, and
  • E is carbon
  • X is alkyl (such as alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, amido (such as NMe2), or alkylsulfonate.
  • alkyl such as alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof
  • aryl hydride
  • alkylsilane fluoride
  • chloride bromide
  • iodide triflate
  • carboxylate
  • L is an ether, amine or thioether.
  • R 10 and R 11 are joined to form a five-membered ring with the joined R 10 R n group being -CH 2 CH 2 -. In embodiments of the invention, R 10 and R 11 are joined to form a six-membered ring with the joined R 10 R n group being -CH 2 CH 2 CH 2 -.
  • R 1 and R 13 may be independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF 3 , N0 2 , alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • M is a Group 4 metal (preferably hafnium);
  • E is selected from carbon, silicon, or germanium (preferably carbon);
  • X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;
  • L is an ether, amine, or thioether
  • R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups (preferably aryl);
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
  • n 1 or 2;
  • n 0, 1, or 2;
  • n+m is from 1 to 4.
  • two X groups may be joined together to form a dianionic group
  • an X group may be joined to an L group to form a monoanionic bidentate group
  • R 10 and R 11 may be joined to form a ring (preferably a five-membered ring with the joined R 10 R n group being -CH2CH2-, a six-membered ring with the joined R 10 R n group being -
  • R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 4 and R 5 and/or R 5 and R 6 ) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.
  • R 7 , R 8 , R 9 , and R 10 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 7 and R 8 and/or R 9 and R 10 ) may be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • R 2 and R 3 are each, independently, selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 2 and R 3 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 2 and R 3 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings.
  • R 11 and R 12 are each, independently, selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 11 and R 12 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 11 and R 12 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings, or R 11 and R 10 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings.
  • R 1 and R 13 may be independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF 3 , NO2, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • preferred R 12 -E-R n groups include CH 2 , CMe 2 ,
  • alkyl is a C l to C 40 alkyl group (preferably C l to C 20 alkyl, preferably one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is a C 5 to C 40 aryl group (preferably a C 6 to C 20 aryl group, preferably phenyl or substituted phenyl, preferably phenyl, 2- isopropylphenyl, or 2-tertbutylphenyl).
  • alkyl is a C l to C 40 alkyl group (preferably C l to C 20 alkyl, preferably one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, de
  • R 11 , R 12 R 9 , R 14 , and R 10 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 10 and R 14 , and/or R 11 and R 14 , and/or R 9 and R 10 ) may be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings.
  • the R groups above (i.e., any of R 2 to R 14 ) and other R groups mentioned hereafter contain from 1 to 30, preferably 2 to 20 carbon atoms, especially from 6 to 20 carbon atoms.
  • the R groups above (i.e., any of R 2 to R 14 ) and other R groups mentioned hereafter are independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, trimethylsilyl, and -CH2-Si(Me)3.
  • the quinolinyldiamide complex is linked to one or more additional transition metal complex, such as a quinolinyldiamide complex or a metallocene, through an R group in such a fashion as to make a bimetallic, trimetallic, or multimetallic complex that may be used as a catalyst component for olefin polymerization.
  • the linker R- group in such a complex preferably contains 1 to 30 carbon atoms.
  • M is Ti, Zr, or Hf
  • E is carbon, with Zr or Hf based complexes being especially preferred.
  • E is carbon and R 12 and R 11 are independently selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, CI, Br, I, CF 3 , N0 2 , alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyl groups with from one to ten carbons.
  • R 11 and R 12 are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH2- Si(Me)3, and trimethylsilyl.
  • R 7 , R 8 , R 9 , and R 10 are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, -CH2-Si(Me)3, and trimethylsilyl.
  • R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.
  • R 10 , R 11 and R 14 are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH2- Si(Me)3, and trimethylsilyl.
  • each L is independently selected from Et20, MeOtBu, Et 3 N, PhNMe2, MePh2N, tetrahydrofuran, and dimethylsulfide.
  • each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamide, dipropylamido, and diisopropylamido.
  • R 1 is 2,6- diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6- diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.
  • R 13 is phenyl, 2- methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4- methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.
  • J is dihydro-lH-indenyl and R 1 is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.
  • R 1 is 2,6- diisopropylphenyl and R 13 is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.
  • the quinolinyldiamine ligands described herein are generally prepared in multiple steps.
  • the main step in the synthesis of the quinolinyldiamine ligand is the carbon-carbon bond coupling step shown below in Scheme 1, wherein fragment 1 and fragment 2 are joined together in a transition metal mediated reaction.
  • the coupling step involves the use of Pd(PPh 3 )4, but other transition metal catalysts (e.g., Ni or Cu containing complexes) are also useful for this type of coupling reaction.
  • the W* and Y* groups used were a boronic acid ester and a halide, respectively.
  • W* and Y* groups of interest include alkali metal (e.g., Li), alkaline earth metal halide (e.g., MgBr), zinc halide (e.g., ZnCl), zincate, halide, and triflate.
  • alkali metal e.g., Li
  • alkaline earth metal halide e.g., MgBr
  • zinc halide e.g., ZnCl
  • zincate halide
  • triflate triflate.
  • transition metal quinolinyldiamide complexes is by reaction of the quinolinyldiamine ligand with a metal reactant containing anionic basic leaving groups.
  • anionic basic leaving groups include dialkylamido, benzyl, phenyl, hydrido, and methyl.
  • the role of the basic leaving group is to deprotonate the quinolinyldiamine ligand.
  • Hf(NMe2)4 is reacted with a quinolinyldiamine ligand at elevated temperatures to form the quinolinyldiamide complex with the formation of two molar equivalents of dimethylamine, which is lost or removed before the quinolinyldiamide complex is isolated.
  • a second method for the preparation of transition metal quinolinyldiamide complexes is by reaction of the quinolinyldiamine ligand with an alkali metal or alkaline earth metal base (e.g., BuLi, EtMgBr) to deprotonate the ligand, followed by reaction with a metal halide (e.g., HfCl 4 , ZrCl 4 ).
  • an alkali metal or alkaline earth metal base e.g., BuLi, EtMgBr
  • a metal halide e.g., HfCl 4 , ZrCl 4
  • Quinolinyldiamide (QDA) metal complexes that contain metal-halide, alkoxide, or amido leaving groups may be alkylated by reaction with organolithium, Grignard, and organoaluminum reagents as shown in Scheme 2.
  • organolithium, Grignard, and organoaluminum reagents as shown in Scheme 2.
  • the alkyl groups are transferred to the QDA metal center and the leaving groups are removed.
  • R 1 through R 13 and E are as described above and X* is a halide, alkoxide, or dialkylamido leaving group.
  • Reagents typically used for the alkylation reaction include, but are not limited to, MeLi, MeMgBr, AlMe 3 , AliBu 3 , A10ct 3 , and PhCH 2 MgCl.
  • alkylating reagent typically 2 to 20 molar equivalents of the alkylating reagent are added to the QDA complex.
  • the alkylations are generally performed in etherial or hydrocarbon solvents or solvent mixtures at temperatures typically ranging from -80°C to 70°C.
  • X* dialkylamido, alkoxo, F, CI, Br
  • catalyst systems may be formed by combining the complexes with activators in any manner known from the literature including by supporting them for use in slurry or gas phase polymerization.
  • the catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer).
  • the catalyst system typically comprises a complex as described above and an activator such as alumoxane or a non-coordinating anion. Activation may be performed using alumoxane solution including methyl alumoxane, referred to as MAO, as well as modified MAO, referred to herein as MMAO, containing some higher alkyl groups to improve the solubility.
  • MAO methyl alumoxane
  • MMAO modified MAO
  • the catalyst system employed in the present invention preferably uses an activator selected from alumoxanes, such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, ⁇ -butyl alumoxane, and the like. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane.
  • alumoxanes such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, ⁇ -butyl alumoxane, and the like. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • a useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3 A, covered under patent number US 5,041,584).
  • MMAO modified methyl alumoxane
  • the catalyst complex-to-activator molar ratio is from about 1:3000 to 10:1; alternatively, 1:2000 to 10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1: 1; alternatively 1:200 to 1:1; alternatively 1:100 to 1: 1; alternatively 1:50 to 1:1; alternatively 1: 10 to 1: 1.
  • the activator is an alumoxane (modified or unmodified)
  • some embodiments select the maximum amount of activator at a 5000-fold molar excess over the catalyst precursor (per metal catalytic site).
  • the preferred minimum activator-to-complex ratio is 1:1 molar ratio.
  • NCA non-coordinating anions
  • NCA's non-coordinating anions
  • NCA may be added in the form of an ion pair using, for example, [DMAHJ+ [NCA]- in which the N,N- dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]-.
  • the cation in the precursor may, alternatively, be trityl.
  • the transition metal complex may be reacted with a neutral NCA precursor, such as B(C 6 F 5 ) 3 , which abstracts an anionic group from the complex to form an activated species.
  • Useful activators include N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate (i.e., [PhNMe 2 H]B(C 6 F 5 ) 4 ) and N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.
  • Non-coordinating anion is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly.
  • NCA is also defined to include multicomponent NCA-containing activators, such as ⁇ , ⁇ -dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion.
  • NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group.
  • NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • a neutral Lewis base such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
  • the term non-coordinating anion includes ionic activators and Lewis acid activators.
  • preferred activators useful herein include those described in US 7,247,687 at column 169, line 50 to column 174, line 43, particularly column 172, line 24 to column 173, line 53.
  • boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in US 8,658,556 and or US 6,211,105, which are incorporated by reference herein.
  • the NCA containing activator is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N- dimethylanilinium tetrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, methyl bis(hydrogenated
  • Preferred activators include ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph 3 C + ][B(C 6 F
  • the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3 ,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).
  • a triaryl carbonium such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3 ,4,6
  • the activator comprises one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, ⁇ , ⁇ -dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, ⁇ , ⁇ -dialkylanilinium tetrakis- (2,3,4, 6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N- dialkylanilinium tetrakis (perfluoronaphthyl)borate , trialkylammonium tetrakis(perfluorobiphenyl
  • the catalyst complex-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to 10: 1; 1: 10 to 2:1; 1: 10 to 3: 1; 1:10 to 5: 1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to
  • a co-activator may also be used in the catalyst system herein.
  • the complex-to-co-activator molar ratio is from 1:100 to 100: 1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to 25: 1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5: 1, 1:2 to 2: 1; 1:100 to 1: 1; 1:75 to 1:1; 1:50 to 1:1;
  • the complexes described herein may be supported (with or without an activator) by any method effective to support other coordination catalyst systems, effective meaning that the catalyst so prepared can be used for oligomerizing or polymerizing olefin in a heterogeneous process.
  • the catalyst precursor, activator, co-activator if needed, suitable solvent, and support may be added in any order or simultaneously.
  • the complex and activator may be combined in solvent to form a solution. Then the support is added, and the mixture is stirred for 1 minute to 10 hours.
  • the total solution volume may be greater than the pore volume of the support, but some embodiments limit the total solution volume below that needed to form a gel or slurry (about 90% to 400%, preferably about 100- 200% of the pore volume).
  • the residual solvent is removed under vacuum, typically at ambient temperature and over 10-16 hours. But greater or lesser times and temperatures are possible.
  • the complex may also be supported absent the activator; in that case, the activator (and co-activator if needed) is added to a polymerization process's liquid phase. Additionally, two or more different complexes may be placed on the same support. Likewise, two or more activators or an activator and co-activator may be placed on the same support.
  • Suitable solid particle supports are typically comprised of polymeric or refractory oxide materials, each being preferably porous.
  • any support material that has an average particle size greater than 10 ⁇ is suitable for use in this invention.
  • a porous support material such as for example, talc, inorganic oxides, inorganic chlorides, for example, magnesium chloride and resinous support materials such as polystyrene polyolefin or polymeric compounds or any other organic support material and the like.
  • Some embodiments select inorganic oxide materials as the support material including Group-2, -3, -4, -5, -13, or -14 metal or metalloid oxides.
  • Some embodiments select the catalyst support materials to include silica, alumina, silica-alumina, and their mixtures.
  • inorganic oxides may serve either alone or in combination with the silica, alumina, or silica- alumina. These are magnesia, titania, zirconia, and the like.
  • Lewis acidic materials such as montmorillonite and similar clays may also serve as a support. In this case, the support can optionally double as the activator component, however, an additional activator may also be used.
  • the support material may be pretreated by any number of methods.
  • inorganic oxides may be calcined, chemically treated with dehydroxylating agents, such as, aluminum alkyls and the like, or both.
  • polymeric carriers will also be suitable in accordance with the invention, see, for example, the descriptions in WO 95/15815 and US 5,427,991.
  • the methods disclosed may be used with the catalyst complexes, activators, or catalyst systems of this invention to adsorb or absorb them on the polymeric supports, particularly if made up of porous particles, or may be chemically bound through functional groups bound to or in the polymer chains.
  • Useful supports typically have a surface area of from 10-700 m 2 /g, a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 ⁇ .
  • Some embodiments select a surface area of 50-500 m 2 /g, a pore volume of 0.5-3.5 cc/g, or an average particle size of 20-200 ⁇ . Other embodiments select a surface area of 100-400 m 2 /g, a pore volume of 0.8-3.0 cc/g, and an average particle size of 30-100 ⁇ .
  • Useful supports typically have a pore size of 10-1000 Angstroms, alternatively 50-500 Angstroms, or 75-350 Angstroms.
  • the catalyst complexes described herein are generally deposited on the support at a loading level of 10-100 micromoles of complex per gram of solid support; alternately 20-80 micromoles of complex per gram of solid support; or 40-60 micromoles of complex per gram of support. But greater or lesser values may be used provided that the total amount of solid complex does not exceed the support's pore volume.
  • continuous process means a system that operates without interruption or cessation.
  • a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • a solution polymerization means a polymerization process in which the polymer produced is dissolved in a liquid polymerization medium at polymerization condition, such as an inert solvent or monomer(s) or their blends.
  • a solution polymerization is typically homogeneous.
  • a homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium.
  • Such systems are preferably not turbid as described in J. Vladimir Oliveira, C. Dariva, and J. C. Pinto, Ind. Eng, Chem. Res., 29, 2000, p. 4627.
  • a bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent.
  • a small faction of inert solvent might be used as a carrier for catalyst and scavenger.
  • a bulk polymerization system contains less than 25 wt% of inert solvent or diluent, preferably less than 10 wt%, preferably less than 1 wt%, preferably 0 wt%.
  • Catalyst activity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W mmol of transition metal (M), over a period of time of T hours; and may be expressed by the following formula: P/(T x W).
  • inventive catalyst complexes described herein are useful in polymerizing unsaturated monomers conventionally known to undergo coordination catalyst-catalyzed polymerization such as solution, slurry, gas-phase, and high-pressure polymerization.
  • unsaturated monomers conventionally known to undergo coordination catalyst-catalyzed polymerization
  • one or more of the complexes described herein, one or more activators, and one or more monomers are contacted to produce polymer.
  • the complexes may be supported and, as such, will be particularly useful in the known, fixed-bed, moving- bed, fluid-bed, slurry, solution, or bulk operating modes conducted in single, series, or parallel reactors.
  • One or more reactors in series or in parallel may be used in the present invention.
  • the complexes, activator and when required, co-activator may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or preactivated and pumped as an activated solution or slurry to the reactor.
  • Polymerizations are carried out in either single reactor operation, in which monomer, comonomers, catalyst/activator/co-activator, optional scavenger, and optional modifiers are added continuously to a single reactor or in series reactor operation, in which the above components are added to each of two or more reactors connected in series.
  • the catalyst components can be added to the first reactor in the series.
  • the catalyst component may also be added to both reactors, with one component being added to first reaction and another component to other reactors.
  • the complex is activated in the reactor in the presence of olefin.
  • the polymerization process is a continuous process.
  • Polymerization processes used herein typically comprise contacting one or more alkene monomers with the complexes (and, optionally, activator) described herein.
  • alkenes are defined to include multi-alkenes (such as dialkenes) and alkenes having just one double bond.
  • Polymerization may be homogeneous (solution or bulk polymerization) or heterogeneous (slurry -in a liquid diluent, or gas phase -in a gaseous diluent).
  • the complex and activator may be supported.
  • Silica is useful as a support herein. Hydrogen may be used in the practice of this invention.
  • the present polymerization processes may be conducted under conditions preferably including a temperature of about 30°C to about 200°C, preferably from 60°C to 195°C, preferably from 75°C to 190°C, preferably from 80°C to 130°C, preferably 85°C to 105°C.
  • the present polymerization processes may be conducted at a pressure of from 0.05 MPa to 1500 MPa.
  • the pressure is between 1.7 MPa and 30 MPa, or in another embodiment, especially under supercritical conditions, the pressure is between
  • Monomers useful herein include olefins having from 2 to 20 carbon atoms, alternately 2 to 12 carbon atoms (preferably ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, and dodecene) and optionally also polyenes (such as dienes).
  • Particularly preferred monomers include ethylene, and mixtures of C 2 to C 10 alpha olefins, such as ethylene-propylene, ethylene-hexene, ethylene-octene, propylene -hexene, and the like.
  • the complexes described herein are also particularly effective for the polymerization of ethylene, either alone or in combination with at least one other olefinically unsaturated monomer, such as a C 3 to C 20 a-olefin, and particularly a C 3 to C 12 a-olefin.
  • the present complexes are also particularly effective for the polymerization of propylene, either alone or in combination with at least one other olefinically unsaturated monomer, such as ethylene or a C 4 to C 20 a-olefin, and particularly a C 4 to C 20 a-olefin.
  • Examples of preferred a-olefins include ethylene, propylene, butene-1, pentene- 1, hexene- 1, heptene- 1, octene- 1, nonene-1, decene-1, dodecene-1, 4-methylpentene-l, 3-methylpentene-l,3,5,5- trimethylhexene-1, and 5-ethylnonene-l.
  • the monomer mixture may also comprise one or more dienes at up to 10 wt%, such as from 0.00001 to 1.0 wt%, for example, from 0.002 to 0.5 wt%, such as from 0.003 to 0.2 wt%, based upon the monomer mixture.
  • Non-limiting examples of useful dienes include, cyclopentadiene, norbornadiene, dicyclopentadiene, 5-ethylidene-2- norbornene, 5-vinyl-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6- heptadiene, 6-methyl-l,6-heptadiene, 1 ,7-octadiene, 7-methyl-l,7-octadiene, 1,9-decadiene, 1,9-dimethyl- 1,9-decadiene.
  • the polymerization of propylene or propylene -rich copolymers with ethylene is expected to produce polymer with crystalline isotactic polypropylene runs. This is expected because the catalyst family has a seven-membered chelate ring, which effectively makes the catalyst Ci symmetric (i.e., no symmetry) in use.
  • the catalyst system when using the complexes described herein, particularly when they are immobilized on a support, the catalyst system will additionally comprise one or more scavenging compounds.
  • scavenging compound means a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability.
  • the scavenging compound will be an organometallic compound such as the Group-13 organometallic compounds of US 5,153,157; US 5,241,025; WO-A-91/09882; WO-A-94/03506; WO-A-93/14132; and that of WO 95/07941.
  • Exemplary compounds include triethyl aluminum, triethyl borane, tri-z ' so-butyl aluminum, methyl alumoxane, ⁇ -butyl alumoxane, and tri-n-octyl aluminum.
  • Those scavenging compounds having bulky or C 6 -C 20 linear hydrocarbyl substituents connected to the metal or metalloid center usually minimize adverse interaction with the active catalyst.
  • Examples include triethylaluminum, but more preferably, bulky compounds such as tri-z ' so-butyl aluminum, tri- ⁇ -prenyl aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum.
  • bulky compounds such as tri-z ' so-butyl aluminum, tri- ⁇ -prenyl aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum.
  • the molecular weight of the polymers produced herein can be influenced by reactor conditions including temperature, monomer concentration and pressure, the presence of chain-terminating or chain-transfer agents and the like
  • the homopolymer and copolymer products produced by the present process may have an Mw of about 1,000 to about 2,000,000 g/mol, alternately of about 30,000 to about 600,000 g/mol, or alternately of about 100,000 to about 500,000 g/mol, as determined by GPC (as described below).
  • the polymers produced herein may have a melt flow rate (MFR) of at least 0.01 dg/min (preferably 0.1 to 50 dg/min, preferably 0.2 to 300 dg/min, preferably 0.1 to 1.5 dg/min, preferably 0.15 to 1.0 dg/min, preferably 0.15 to 0.8 dg/min) (ASTM 1238, 2.16 kg, 230 °C).
  • MFR melt flow rate
  • the polymers produced herein may have a melt flow rate (MFR) of at least 0.01 dg/min (preferably 0.1 to 50 dg/min, preferably 1 to 10 dg/min).
  • Preferred polymers produced herein may be homopolymers or copolymers.
  • the comonomer(s) are present at up to 50 mol%, preferably from 0.01 to 40 mol%, preferably 1 to 30 mol%, preferably from 5 to 20 mol%.
  • the polymers produced are propylene-ethylene copolymers having from 1 to 35 wt% ethylene (preferably 5 to 30, preferably 5 to 25) and 99 to 65 wt% propylene (preferably 95 to 70, preferably 95 to 75), with optional one or more diene present at up to 10 wt% (preferably from 0.00001 to 6.0 wt%, preferably from 0.002 to 5.0 wt%, preferably from 0.003 to 0.2 wt %), based upon weight of the copolymer.
  • Non-limiting examples of useful dienes include, cyclopentadiene, norbornadiene, dicyclopentadiene, 5- ethylidene-2-norbornene (“ENB”), 5-vinyl-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 1,5- heptadiene, 1,6-heptadiene, 6-methyl-l,6-heptadiene, 1,7-octadiene, 7-methyl-l,7-octadiene, 1,9-decadiene, 1 and 9-methyl-l,9-decadiene.
  • ENB ethylidene-2-norbornene
  • a multimodal polyolefin composition comprising a first polyolefin component and at least another polyolefin component, different from the first polyolefin component by molecular weight, preferably such that the GPC trace has more than one peak or inflection point.
  • multimodal when used to describe a polymer or polymer composition, means “multimodal molecular weight distribution,” which is understood to mean that the Gel Permeation Chromatography (GPC) trace, plotted as Absorbance versus Retention Time (seconds), has more than one peak or at least one inflection points.
  • An “inflection point” is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versa).
  • a polyolefin composition that includes a first lower molecular weight polymer component (such as a polymer having an Mw of 100,000 g/mol) and a second higher molecular weight polymer component (such as a polymer having an Mw of 300,000 g/mol) is considered to be a "bimodal" polyolefin composition.
  • the Mw's of the polymer or polymer composition differ by at least 10%, relative to each other, preferably by at least 20%, preferably at least 50%, preferably by at least 100%, preferably by a least 200%.
  • the Mw's of the polymer or polymer composition differ by 10% to 10,000%, relative to each other, preferably by 20% to 1000%, preferably 50% to 500%, preferably by at least 100% to 400%, preferably 200% to 300%.
  • measurements of the moments of molecular weight i.e., weight average molecular weight (Mw), number average molecular weight (Mn), and z average molecular weight (Mz) are determined by Gel Permeation Chromatography (GPC) as described in Macromolecules, 2001, Vol. 34, No. 19, pg. 6812, which is fully incorporated herein by reference, including that, a High Temperature Size Exclusion Chromatograph (SEC, Waters Alliance 2000), equipped with a differential refractive index detector (DRI) equipped with three Polymer Laboratories PLgel 10 mm Mixed-B columns is used. The instrument is operated with a flow rate of 1.0 cm3 /min, and an injection volume of 300 ⁇ .
  • GPC Gel Permeation Chromatography
  • the various transfer lines, columns, and differential refractometer (the DRI detector) are housed in an oven maintained at 145°C.
  • Polymer solutions are prepared by heating 0.75 to 1.5 mg/mL of polymer in filtered 1 ,2,4-Trichlorobenzene (TCB) containing -1000 ppm of butylated hydroxy toluene (BHT) at 160°C for 2 hours with continuous agitation.
  • TCB filtered 1 ,2,4-Trichlorobenzene
  • BHT butylated hydroxy toluene
  • a sample of the polymer containing solution is injected into to the GPC and eluted using filtered 1,2,4- trichlorobenzene (TCB) containing -1000 ppm of BHT.
  • the separation efficiency of the column set is calibrated using a series of narrow MWD polystyrene standards reflecting the expected Mw range of the sample being analyzed and the exclusion limits of the column set. Seventeen individual polystyrene standards, obtained from Polymer Laboratories (Amherst, MA) and ranging from Peak Molecular Weight (Mp) -580 to 10,000,000, were used to generate the calibration curve. The flow rate is calibrated for each run to give a common peak position for a flow rate marker (taken to be the positive inject peak) before determining the retention volume for each polystyrene standard. The flow marker peak position is used to correct the flow rate when analyzing samples. A calibration curve (log(Mp) vs.
  • retention volume is generated by recording the retention volume at the peak in the DRI signal for each PS standard, and fitting this data set to a 2nd-order polynomial.
  • the equivalent polyethylene molecular weights are determined by using the Mark-Houwink coefficients shown in Table B.
  • the homopolymer and copolymer products produced by the present process may have an Mw of about 1,000 to about 2,000,000 g/mol, alternately of about 30,000 to about 600,000 g/mol, or alternately of about 100,000 to about 500,000 g/mol, as determined by GPC and have a multi-modal, preferably bimodal, Mw/Mn.
  • the polymer produced is an ethylene polymer or a propylene polymer.
  • the polymer produced is a tactic polymer, preferably an isotactic or highly isotactic polymer.
  • the polymer produced is isotactic polypropylene, such as highly isotactic polypropylene.
  • isotactic polypropylene (iPP) is defined as having at least 10% or more isotactic pentads.
  • highly isotactic polypropylene is defined as having 50% or more isotactic pentads.
  • sindiotactic polypropylene is defined as having 10% or more syndiotactic pentads.
  • random copolymer polypropylene (RCP), also called propylene random copolymer, is defined to be a copolymer of propylene and 1 to 10 wt% of an olefin chosen from ethylene and C 4 to C 8 alpha-olefins.
  • isotactic polymers such as iPP
  • a polyolefin is "atactic,” also referred to as “amorphous” if it has less than 10% isotactic pentads and syndiotactic pentads.
  • Polypropylene microstructure is determined by 13 C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]).
  • the designation "m” or “r” describes the stereochemistry of pairs of contiguous propylene groups, "m” referring to meso and “r” to racemic. Samples are dissolved in d2-l,l,2,2-tetrachloroethane, and spectra recorded at 125°C using a 100 MHz (or higher) NMR spectrometer.
  • Articles made using polymers produced herein may include, for example, molded articles (such as containers and bottles, e.g., household containers, industrial chemical containers, personal care bottles, medical containers, fuel tanks, storageware, toys, sheets, pipes, and tubing) films, non-wovens, and the like. It should be appreciated that the list of applications above is merely exemplary, and is not intended to be limiting.
  • ⁇ NMR spectroscopic data were acquired at 250, 400, or 500 MHz using solutions prepared by dissolving approximately 10 mg of a sample in either C 6 D 6 , CD 2 C1 2 , CDC1 3 , or D 8 -toluene.
  • the chemical shifts ( ⁇ ) presented are relative to the residual protium in the deuterated solvent at 7.15, 5.32, 7.24, and 2.09 for C 6 D 6 , CD 2 C1 2 , CDC1 3 , and D 8 -toluene, respectively.
  • 500Mz and CD 2 C1 2 are used.
  • Hafnium complexes of a series of 2-((aminomethyl)phenyl)-8-anilinoquinoline ligands have been prepared and characterized. These complexes form active olefin polymerization catalysts when combined with activators, such as N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate.
  • activators such as N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate.
  • the J group is a three-atom-length bridge between the quinoline and the amido nitrogen (preferred J groups include arylmethyl and dihydro-lH-indenyl, and tetrahydronaphthalenyl groups); M is Hf; R 2 to R 6 are H; X is NMe2, or Me; n is 2; y is 0 and L is not present; R 1 is 2,6- diisopropylphenyl; R 13 is 2-methyl phenyl, 2,6-dimethylphenyl, or phenyl; R 12 is H; R 11 is H or forms a ring with R 10 ; R 9 is H; R 10 is H or forms a ring with R 11 , and R 7 and R 8 are each H or are joined together to form a six-membered aromatic ring.
  • the obtained suspension was heated to 100°C and then cooled to room temperature.
  • To the reaction mixture 2.45 g (2.68 mmol) of Pd2(dba)3, 2.55 g (5.36 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos), and 45.2 g (134 mmol) of the protected 8-bromoquinolin-2(lH)-one were subsequently added.
  • the dark brown suspension obtained was stirred at 60°C till the lithium salt precipitate disappeared (approx. 30 minutes).
  • the resulting dark red solution was quenched by 100 mL of water; the organic layer was separated, dried over Na2S0 4 , and then evaporated to dryness.
  • the obtained oil was dissolved in a mixture of 1000 mL of dichloromethane and 500 mL of methanol followed by an addition of 50 mL of 12 M hydrochloric acid.
  • the reaction mixture was stirred at room temperature for 3 hours, then poured into 2000 mL of 5% aqueous K2CO3.
  • the product was extracted with 3 x 700 mL of dichloromethane.
  • the combined extract was dried over Na2S0 4 and then evaporated to dryness.
  • the resulting solid was triturated with 300 mL of hexane and then filtered off on a glass frit (G3). Yield 34.1 g (79%) of a marsh-green solid.
  • the formed mixture was diluted with 2 L of water, and the organic layer was separated. The aqueous layer was extracted with 3 x 400 mL of toluene. The combined organic extract was dried over Na2S0 4 and evaporated to dryness. The residue was distilled using a Kugelrohr apparatus at 120°C-140°C/1 mbar. The obtained yellow oil was dissolved in 50 mL of triethylamine, and the formed solution was added drop-wise to a stirred solution of 49.0 mL (519 mmol) of acetic anhydride and 4.21 g (34.5 mmol) of 4-(N,N-dimethylamino)pyridine (DMAP) in 70 mL of triethylamine.
  • DMAP 4-(N,N-dimethylamino)pyridine
  • the combined organic extract was separated, dried over Na2S0 4 , and evaporated to dryness.
  • the residue was re-crystallized from 30 mL of ethyl acetate at -30°C.
  • the formed crystalline solid was filtered off (G3) and then dried in vacuum. After that, it was dissolved in 500 mL of methanol, then 8.34 g (132 mmol) of NaBSbCN and 2.0 mL of glacial acetic acid were added. The resulting mixture was refluxed for 3 h, then cooled to room temperature, and evaporated to dryness.
  • the residue was diluted with 200 mL of water, and crude product was extracted with 3 x 100 mL of ethyl acetate.
  • Phenyl[7-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-2,3-dihydro-lH-inden-l- yl]amine To a solution of 2.50 g (8.70 mmol) of (7-bromo-2,3-dihydro-lH-inden-l- yl)phenylamine in 50 mL of THF 3.50 mL (8.70 mmol) of 2.5 M n-BuLi in hexanes was added at -80°C in argon atmosphere. The reaction mixture was then stirred for 1 hour at this temperature.
  • N-(2,6-Diisopropylphenyl)-2- ⁇ 2-[(2,6-dimethylphenylamino)methyl]naphthalen- l-yl ⁇ quinolin-8-amine Q2-H2
  • 2-chloro-N-(2,6- diisopropylphenyl)quinolin-8-amine was added 2.00 g (5.15 mmol) of 2,6-dimethyl-N- ⁇ [ 1 -(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl ⁇ aniline.
  • N-(2,6-Diisopropylphenyl)-2-[3-(phenylamino)-2,3-dihydro-lH-inden-4- yl]quinolin-8-amine Q3-H2.
  • 2-chloro-N-(2,6- diisopropylphenyl)quinolin-8-amine was added 4.10 g (12.3 mmol) of phenyl[7-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-2,3-dihydro-lH-inden-l-yl]amine.
  • N-(2,6-Diisopropylphenyl)-2-[3-(o-tolylamino)-2,3-dihydro-lH-inden-4- yl]quinolin-8-amine Q4-H2.
  • 1,2,3,4-tetrahydronaphthalen-l-ol 160 mL (1.06 mol) of ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethylethylenediamine, and 3000 mL of pentane cooled to -20 °C 435 mL (1.09 mol) of 2.5 M "BuLi in hexanes was added dropwise.
  • the obtained mixture was refluxed for 12 h, then cooled to -80°C, and 160 mL (1.33 mol) of 1 ,2-dibromotetrafluoroethane was added.
  • the obtained mixture was allowed to warm to room temperature and then stirred for 12 h at this temperature. Thereafter, 100 mL of water was added.
  • the resulting mixture was diluted with 2000 mL of water, and the organic layer was separated. The aqueous layer was extracted with 3 x 400 mL of toluene. The combined organic extract was dried over Na2S0 4 and then evaporated to dryness. The residue was distilled using the Kugelrohr apparatus, b.p. 150- 160°C/1 mbar. The obtained yellow oil was dissolved in 100 mL of triethylamine, and the formed solution was added dropwise to a stirred solution of 71.0 mL (750 mmol) of acetic anhydride and 3.00 g (25.0 mmol) of DMAP in 105 mL of triethylamine.
  • the product was extracted with 3 x 50 mL of ethyl acetate.
  • the combined organic extract was dried over Na2S0 4 , evaporated to dryness, and the residue was re-crystallized from 10 mL of ethyl acetate.
  • the obtained crystalline solid was dissolved in 200 mL of methanol, 7.43 g (118 mmol) of NaB3 ⁇ 4CN and 3 mL of acetic acid were added in argon atmosphere. This mixture was heated to reflux for 3 h, then cooled to room temperature, and evaporated to dryness.
  • the residue was diluted with 200 mL of water, and crude product was extracted with 3 x 100 mL of ethyl acetate.
  • the obtained mixture was purged with argon for 10 min followed by an addition of 2.48 g (2.15 mmol) of Pd(PPli3) 4 .
  • the formed mixture was stirred for 2 h at 90 °C, then cooled to room temperature.
  • To the obtained two-phase mixture 700 mL of n-hexane was added. The organic layer was separated, washed with brine, dried over Na2S0 4 , and then evaporated to dryness.
  • the solid was purified by recrystallization from Cl bCk-hexanes (20 mL - 20 mL) by slow evaporation to give pure product as orange crystals (1.33 g, 43.2% from ligand).
  • the mother liquor was further concentrated for a second crop (0.291 g, 9.5% from ligand).
  • Catalyst screening for olefin polymerizations was performed in a parallel, pressure reactor (PPR) as generally described in US 6,306,658; US 6,455,316; US 6,489,168; WO 00/09255; and J. Am. Chem. Soc, 2003, 125, pp. 4306-4317, each of which is fully incorporated herein by reference to the extent not inconsistent with this specification.
  • Catalysts are screened in the PPR for their ability to produce a variety of polymers, including homopolyethylene, homopolypropylene, ethylene-hexene copolymer, ethylene-octene copolymer, and ethylene-propylene copolymer.
  • a pre-weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels.
  • the reactor was purged with the gaseous monomer (typically ethylene or propylene) to be used for the polymerization.
  • gaseous monomer typically ethylene or propylene
  • liquid comonomer typically 1-octene or 1-hexene
  • solvent typically isohexane
  • a solution of scavenger (typically an organoaluminum reagent in isohexane or toluene) was then added along with a solvent chaser (typically 500 microliters).
  • a solvent chaser typically 500 microliters.
  • An activator solution in toluene (typically 1.1 molar equivalent relative to the pre-catalyst complex) was then injected into the reaction vessel along with a solvent chaser (typically 500 microliters). Then a toluene solution of the dissolved pre-catalyst complex was added along with a solvent chaser (typically 500 microliters).
  • a set amount of time typically 30 minutes.
  • the glass vial insert containing the polymer product and solvent was removed from the reactor and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure.
  • the vial was then weighed to determine the yield of the polymer product.
  • the resultant polymer was analyzed by Rapid GPC (see below) to determine the molecular weight.
  • the system was operated at an eluent flow rate of 2.0 niL/min and an oven temperature of 165°C. 1,2,4-trichlorobenzene was used as the eluent.
  • the polymer samples were dissolved in 1,2,4-trichlorobenzene at a concentration of 0.1 - 0.9 mg/mL. 250 of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using an evaporative light scattering detector.
  • the molecular weights presented in the examples are relative to linear polystyrene standards.
  • Octene comonomer content in ethylene-octene copolymer samples was determined by infrared spectroscopic analysis.
  • Samples for infrared analysis were prepared by depositing the stabilized polymer solution onto a silanized wafer (Part number S 10860, Symyx). By this method, approximately between 0.12 and 0.24 mg of polymer is deposited on the wafer cell. The samples were subsequently analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with Pikes's MappIR specular reflectance sample accessory. Spectra, covering a spectral range of 5000 cm 1 to 500 cm 1 , were collected at a 2 cm "1 resolution with 32 scans.
  • the wt% comonomer is determined via measurement of the methyl deformation band at -1375 cm 1 .
  • the peak height of this band is normalized by the combination and overtone band at -4321 cm 1 , which corrects for path length differences.
  • the normalized peak height is correlated to individual calibration curves from 3 ⁇ 4 NMR data to predict the wt% comonomer content within a concentration range of -2 to 35 wt% for octene. Typically, R 2 correlations of 0.98 or greater are achieved.
  • DSC Differential Scanning Calorimetry
  • temperature 100°C
  • pressure 100 psi
  • uptake 12 psi
  • activator 1.1 molar equivalents [PhNMe2H]B(C6Fs)4
  • solvent isohexane
  • volume 5 mL
  • scavenger 500 nmol trioctylaluminum.
  • the ligand also has a large effect on the stereoregularity of the polypropylene produced.
  • the complexes prepared using ligands Q2 and Q4 produced polypropylene with higher melting points than the complexes prepared using ligands Ql and Q3.
  • Increased polypropylene stereoregularity is thought to be due to the steric bulk of the groups in the R 13 position (e.g., Ph ⁇ ortho-tolyl ⁇ xylyl) and the dihydro-lH-indenyl J group instead of a phenylmethyl J group (R 13 + J refer to Formulas I and II).
  • Cat-1 was prepared as described in US 9,102,773.
  • Cat-2 was prepared using the general method described in US 9,315,526.
  • Cat-3 was synthesized according to the procedure described in US 9,290,519.
  • the following examples were produced using a solution process in a 1 liter continuous stirred-tank reactor (autoclave reactor).
  • Autoclave reactor A 1 -liter Autoclave reactor was equipped with a stirrer, a pressure controller, and a water cooling/steam heating element with a temperature controller. The reactor was operated in liquid fill condition at a reactor pressure in excess of the bubbling point pressure of the reactant mixture, keeping the reactants in liquid phase. Isohexane and propylene were pumped into the reactors by Pulsa feed pumps.
  • the polymer produced in the reactor exited through a back pressure control valve that reduced the pressure to atmospheric. This caused the unconverted monomers in the solution to flash into a vapor phase which was vented from the top of a vapor liquid separator.
  • the liquid phase comprising mainly polymer and solvent, was collected for polymer recovery.
  • the collected samples were first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90 °C for about 12 hours. The vacuum oven dried samples were weighed to obtain yields.
  • Catalysts used in these examples were Cat-1, Cat-2, Cat-3 and (Q5)HfMe2.
  • Activator used was ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorophenyl) borate (BF20). Both the catalyst and activator were first dissolved in toluene and the solutions were kept in an inert atmosphere. The solutions of catalyst and activator were premixed and fed into the reactor using an ISCOTM syringe pump. The catalyst to activator feed ratio (molar) was set at 0.98.
  • Tri-n-octylaluminum (TNOAL) solution (available from Sigma Aldrich, Milwaukee, Wis.) was further diluted in isohexane and used as a scavenger.
  • Runs 1 through 14 are presented as comparatives. Runs 15 through 28 are inventive. Specific polymerization process conditions and some characteristic properties are listed in Table A. The scavenger feed rate was adjusted to optimize the catalyst efficiency and the feed rate varied from 0 (no scavenger) to 15 ⁇ / ⁇ . The catalyst feed rates was adjusted according to the level of impurities in the system to reach the targeted conversions listed. All the reactions were carried out at a pressure of about 2.4 MPa/g unless otherwise mentioned. Additional processing conditions for the polymerization process of example 1 to 28, and the properties of the polymers produced are included below in Table A. Ethylene content was determined by FTIR, ASTM D3900. Melt Flow Rate (MFR) was determined according to ASTM 1238 (230°C, 2.16kg) and are presented as dg polymer/minute.
  • MFR Melt Flow Rate
  • Runs 15 through 22 demonstrate that the catalyst system (Q5)HfMe2/BF20 produces high molecular weight ethylene -propylene copolymer containing 7.0-16.4% ethylene at 85°C with productivities of 94 kg polymer/mmol Hf or greater. Under similar process conditions the comparative catalysts had productivities of 55 kg/mmol Hf or less (see runs 3 and 5 through 14).
  • Runs 25 and 28 demonstrate that (Q5)HfMe2/BF20 produces high molecular weight ethylene-propylene copolymer containing 10-16% ethylene at 100°C with productivities of 82 kg polymer/mmol Hf or greater. Under similar condition CAT-1/BF20 had a productivity of 19 kg/mmol Hf (see run 4).
  • compositions, an element, or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

Abstract

L'invention concerne des complexes de métaux de transition quinolinyldiamido, utilisables dans la polymérisation des alcènes pour produire des polyoléfines multimodales.
PCT/US2017/038606 2016-06-30 2017-06-21 Complexes quinolinyldiamido de métaux de transition, leur production et leur utilisation WO2018005201A1 (fr)

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SG11201811335UA SG11201811335UA (en) 2016-06-30 2017-06-21 Quinolinyldiamido transition metal complexes, production and use thereof
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CA3029544A CA3029544C (fr) 2016-06-30 2017-06-21 Complexes quinolinyldiamido de metaux de transition, leur production et leur utilisation
KR1020187038128A KR20190003835A (ko) 2016-06-30 2017-06-21 퀴놀리닐디아미도 전이 금속 착물, 제조 및 이의 용도
JP2018568410A JP2019527679A (ja) 2016-06-30 2017-06-21 キノリニルジアミド遷移金属錯体、生成物およびその使用
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WO2021173362A1 (fr) * 2020-02-24 2021-09-02 Exxonmobil Chemical Patents Inc. Catalyseurs bases de lewis et procédés associés
WO2021262842A1 (fr) 2020-06-26 2021-12-30 Exxonmobil Chemical Patents Inc. COPOLYMERS D'ÉTHYLÈNE, α-OLÉFINE, DIÈNE NON CONJUGUÉ, ET CYCLOALCÈNE ARYL-SUBSTITUÉ, PROCÉDÉ DE PRODUCTION, MÉLANGES ET ARTICLES OBTENUS À PARTIR DE CEUX-CI

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