WO2012134615A1 - Complexes de pyridyldiamido et de métal de transition, production et utilisation de ceux-ci - Google Patents

Complexes de pyridyldiamido et de métal de transition, production et utilisation de ceux-ci Download PDF

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WO2012134615A1
WO2012134615A1 PCT/US2012/022476 US2012022476W WO2012134615A1 WO 2012134615 A1 WO2012134615 A1 WO 2012134615A1 US 2012022476 W US2012022476 W US 2012022476W WO 2012134615 A1 WO2012134615 A1 WO 2012134615A1
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group
complex
substituted
ring
hydrocarbyls
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PCT/US2012/022476
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John R. Hagadorn
Matthew S. Bedoya
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Exxonmobil Chemical Patents Inc.
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Priority claimed from US13/071,738 external-priority patent/US8394902B2/en
Priority claimed from US13/114,307 external-priority patent/US8674040B2/en
Priority claimed from US13/207,847 external-priority patent/US8710163B2/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to CN201280020007.9A priority Critical patent/CN103492397B/zh
Priority to EP12764279.1A priority patent/EP2688895A4/fr
Publication of WO2012134615A1 publication Critical patent/WO2012134615A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages

Definitions

  • the invention relates to pyridyldiamido transition metal complexes and intermediates and processes for use in making such pyridyldiamido 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 for use 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 2004/0220050A1 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 five-membered and a seven- membered chelate rings.
  • WO 2010/037059 discloses pyridine containing amines for use in pharmaceutical applications.
  • the performance may be varied in respect of 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 the placement of higher alpha-olefins in terms of the degree of stereoregular placement.
  • This invention relates to novel transition metal complexes having tridentate N ligands.
  • the ligand may be derived from a neutral ligand precursor or be created in situ in a complex, as will be described.
  • This invention also relates to a pyridyldiamido transition metal complex having the general formula (I), (II), or (III):
  • M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 1 1, or 12 metal
  • R1 is selected from the group consisting of hydrocarbyls (such as alkyls, aryls), substituted hydrocarbyls (such as heteroaryls), and silyl groups;
  • R 1 1 is selected from the group consisting of substituted 5 or 6 membered aromatic rings;
  • RlO is -E*(Rl2)(Rl3)- ;
  • E and E* are independently, carbon, silicon, or germanium
  • each Rl2 and Rl 3 is independently selected from the group consisting of hydrogen, hydrocarbyls (e.g., alkyl and aryl), substituted hydrocarbyls (e.g., heteroaryl), alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and Rl 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 12 and Rl 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;
  • each Rl2* and Rl 3 * is independently selected from the group consisting of hydrogen, CI to C5 hydrocarbyls, and substituted CI to C5 hydrocarbyls;
  • R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls (e.g., alkyls and aryls), substituted hydrocarbyls (e.g., heteroaryl), alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 and /or R 4 & R 5 ) 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;
  • R 6 , R 7 R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 15 , and/or R 16 & R 15 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or 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;
  • L is an anionic leaving group, where the L groups may be the same or different and any two
  • L groups may be linked to form a dianionic leaving group
  • n 0, 1, 2, 3, or 4;
  • L' is neutral Lewis base
  • w 0, 1, 2, 3, or 4;
  • Z is -(Rl4*) p Q-J(Rl5*) q-;
  • Q is C, O, N, or Si
  • J is C or Si
  • R 14 * and R 15 * are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, (preferably hydrogen and alkyls), and wherein adjacent R 14 * and R 15 * groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl 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;
  • p 1 or 2;
  • q 1 or 2.
  • This invention further relates to process to make the above complex, process to make intermediates for the above complex and methods to polymerize olefins using the above complex.
  • 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
  • Ph is phenyl
  • Et is ethyl
  • Pr is propyl
  • iPr is isopropyl
  • n-Pr normal propyl
  • Bu is butyl
  • iBu is isobutyl
  • tBu is tertiary butyl
  • p-tBu is para-tertiary butyl
  • nBu is normal butyl
  • TMS is trimethylsilyl
  • TIBAL is triisobutylaluminum
  • TNOAL is triisobutyl n-octylaluminum
  • MAO is methylalumoxane
  • pMe is para-methyl
  • Ar* is 2,6-diisopropylaryl
  • Ph is phenyl
  • Bn is benzyl (i.e., CH 2 Ph)
  • THF also referred to as thf
  • RT room temperature
  • tol is toluen
  • substituted means that a hydrogen has been replaced with a heteroatom or a hydrocarbyl group.
  • methyl-cyclopentadiene is substituted with a methyl group.
  • hydrocarbyl radical is defined to be C C ⁇ o radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one functional group such as 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, or where at least one heteroatom has been inserted within a hydrocarbyl ring.
  • at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one functional group such as 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, or where at least one heteroatom has been inserted within a hydrocarbyl
  • catalyst system is defined to mean a complex/activator pair.
  • catalyst system is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a co-activator.
  • 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 as used herein, is also often 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.
  • Noncoordinating 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.
  • a stoichiometric activator can be either neutral or ionic. The terms ionic activator, and stoichiometric ionic activator can be used interchangeably.
  • neutral stoichiometric activator and Lewis acid activator can be used interchangeably.
  • non-coordinating anion includes neutral stoichiometric activators, ionic stoichiometric activators, ionic activators, and Lewis acid activators.
  • the olefin present in the polymer or oligomer is the polymerized or oligomerized form of the olefin (for example polyethylene is made of units derived from ethylene).
  • An oligomer is defined to be compositions having 2-50 monomer units.
  • a polymer is defined to be compositions having 51 or more monomer units.
  • a higher a-olefin is defined to be an a-olefin having 4 or more carbon atoms.
  • a "ring carbon atom” is a carbon atom that is part of a cyclic ring structure. By this definition, 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 thee 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 5 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.
  • 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.
  • continuous 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 is dissolved in a liquid polymerization medium, 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, 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%.
  • a pyridyldiamido transition metal complex (optionally, for use in alkene polymerization) having the general formula: (I) or (II):
  • M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal (preferably a Group 4 metal, preferably Ti, Zr or Hf, preferably Hf or Zr, preferably Hf);
  • R 1 is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups (preferably alkyl, aryl, heteroaryl, and silyl groups);
  • R 1 1 is selected from the group consisting of substituted 5 or 6 (preferably 6) membered aromatic rings, (such as substituted 5 or 6 membered rings where the ring atoms are carbon or heterocyclic rings having 1, 2 or 3 heteroatoms in the ring (such as N, O or S)) where the substitution is a hydrocarbyl group, a heteroatom, or a heteroatom containing group, preferably R 1 1 is a substituted aryl group, preferably a 2,6 or 2,4,6 substituted aryl group; R 10 is -E*(R 12 )(R 13 )- (preferably R 10 is CH 2 , preferably R 12 and R 13 are the same);
  • E and E* are, independently, carbon, silicon, or germanium (preferably carbon or silicon, preferably carbon);
  • each R 12 and R 13 is independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino (preferably hydrogen, alkyl, aryl, alkoxy, silyl, amino, aryloxy, heteroaryl, halogen, and phosphino), R 12 and R 13 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 12 and R 13 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;
  • each R 12 * and R 13 * is independently selected from the group consisting of hydrogen, CI to C5 hydrocarbyls, substituted CI to C5 hydrocarbyls, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl;
  • R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, (preferably hydrogen, alkyl, alkoxy, aryloxy, halogen, amino, silyl, and aryl), and wherein adjacent R groups (R 3 & R 4 and/or R 4 & R 5 ) 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;
  • R 6 R 7 R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and the pairs of positions, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 15 , and/or R 16 & R 15 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or 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;
  • L is an anionic leaving group, where the L groups may be the same or different and any two
  • L groups may be linked to form a dianionic leaving group
  • n 0, 1, 2, 3, or 4;
  • L' is neutral Lewis base
  • w 0, 1, 2, 3, or 4;
  • Z is -(R 14 *) p Q-J(R 15 *) q - where Q or J is bonded to R 10 ;
  • J is C or Si, preferably C
  • Q is C, O, N, or Si, preferably C (preferably both J and Q are C);
  • R 14 * and R 15 * are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, (preferably hydrogen and alkyls), and wherein adjacent R 14 * and R 15 * groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl 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;
  • p 1 or 2;
  • q 1 or 2.
  • the R groups above and other R groups mentioned hereafter contain up to 30 carbon atoms, preferably no more than 30 carbon atoms, especially from 2 to 20 carbon atoms.
  • M is Ti, Zr, or Hf and/or E and/or E* is carbon, with Zr or Hf based complexes being especially preferred.
  • R 1 is selected from phenyl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF 3 , ⁇ (3 ⁇ 4, alkoxy, dialkylamino, aryl, and alkyl groups with between one to ten carbons.
  • R 1 1 is selected from aryl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF 3 , ⁇ (3 ⁇ 4, alkoxy, dialkylamino, aryl, and alkyl groups with between one to ten carbons, preferably R 1 1 is 2,6 or 2,4,6 substituted aryl, preferably where the substituents are methyl, ethyl, methoxy, propyl, tert-butyl, butyl, isopropyl, pentyl, hexyl, isobutyl, chloro, fluoro, bromo, iodo, trimethylsilyl, or triethylsilyl.
  • R 1 1 is 2,4,6-trimethylphenyl, 2,6- dimethylphenyl, 2,6-diethylphenyl, 2,6-diisobutylphenyl, 2,5-dimethylphenyl, 2,4,5- trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2,6-diisopropylphenyl, or 2,4,6- triisopropylphenyl.
  • each L may be independently selected from halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, triflate, alkylsulfonate, arylsulfonate, and alkynyl.
  • the selection of the leaving groups depends on the synthesis route adopted for arriving at the complex and may be changed by additional reactions to suit the later activation method in polymerization.
  • alkyl is preferred when using non-coordinating anions such as ⁇ , ⁇ -dimethylanilinium tetrakis(pentafluorophenyl)-borate or tris(pentafluorophenyl)borane.
  • two L groups may be linked to form a dianionic leaving group, for example, oxalate.
  • each L' is independently selected from the group consisting of ethers, thio-ethers, amines, nitriles, imines, pyridines, and phosphines, preferably ethers.
  • M is preferably a Group 4 metal, preferably Zr or Hf.
  • E and or E* is preferably carbon.
  • one of R 12 * and R 13 * is preferably hydrogen. In any embodiment described herein, R 12 * and R 13 * are not benzyl.
  • R 10 is CH2.
  • R 12 and R 13 are the same.
  • R 10 is represented by the formula:
  • R 12 " is hydrogen, alkyl, aryl, or halogen
  • R 13 " is hydrogen, alkyl, aryl, or halogen, preferably R 12 " and R 13 " are the same.
  • R 12 * and R 13 * are the same.
  • R 6 ; R 7 R 8 , R 9 R 15 , and R 16 may be, independently, selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl.
  • R 1 , R 3 , R 4 , R 5 ; and R 1 1 may each contain no more than 30 carbon atoms, preferably R 1 , R 3 , R 4 , R 5 ; R 6 , R 7 , R 8 , R 9 , and R 15 each contain no more than 30 carbon atoms.
  • E is carbon and R 1 is 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 , ⁇ (3 ⁇ 4, alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyls groups with from one to ten carbons.
  • the pyridyldiamido transition metal complex is represented by the Formula (I) or (II) above and at least one of R 12 * and R 13 * is a group containing from 1 to 5 (preferably 1 to 4, preferably 1 to 3) carbons.
  • the pyridyldiamido transition metal complex is represented by the Formula (I) or (II) above, R 12 is H, R 13 is a group containing between 1 to 100 (preferably 6 to 40, preferably 7 to 30) carbons, M is a Group 4 metal, preferably Zr or Hf, E is carbon, R 12 " and R 13 " are the same, preferably R 10 is CH ).
  • the pyridyldiamido transition metal complex is represented by the Formula (I) above, and M is a Group 4 metal preferably Zr or Hf, preferably Hf.
  • the pyridyldiamido transition metal complex is represented by the Formula (II) above, and M is a Group 4 metal preferably Zr or Hf, preferably Hf.
  • the pyridyldiamido transition metal complex is represented by the Formula (II) above, and R 10 is CH2.
  • the pyridyldiamido transition metal complex is represented by the Formula (I) or (II) and both R 12 * and R 13 * are a to C5 alkyl group, alternately methyl, ethyl, propyl, butyl, pentyl or an isomer thereof.
  • the pyridyldiamido transition metal complex is represented by the Formula (I) or (II) and R 12 * and R 13 * are hydrogen, E is C, and E* is C or Si.
  • the pyridyl diamine ligands described herein are generally prepared in multiple steps.
  • One step involves the preparation of an amine-containing "linker" group where the linker is typically a boronic acid ester of an aryl methyl amine or substituted amine.
  • This amine- containing linker may be prepared from an aryl-methyl boronic ester in two steps, the first of which involves the conversion of the methyl group to a halo-methyl group by free radical halogenation in unreactive solvents (e.g., CC1 4 , benzene).
  • the second step then involves reaction of this halo-methyl group containing species with an amine or protected amine or deprotonated protected amine to yield an amine-containing linker.
  • This amine-containing linker is then coupled with a suitable pyridine containing species, such as 6-bromo-2- pyridinecarboxaldehyde.
  • This coupling step typically uses a metal catalyst (e.g., Pd(PPh 3 ) 4 ) in less than 5 mol% loading.
  • the new derivative which can be described as amine-linker-pyridine-aldehyde, is then reacted with a second amine to produce the imine derivative amine-linker-pyridine-imine in a condensation reaction.
  • This reaction is generally performed in etherial solvents at temperatures between -100°C and 50°C when aryllithium or alkyllithium reagents are employed.
  • This reaction is generally performed in methanol at reflux when sodium cyanoborohydride is employed.
  • pyridyl diamide metal complexes from pyridyl diamines may be accomplished using typical protonolysis and methylation reactions.
  • the protonolysis reaction the pyridyl diamine is reacted with a suitable metal reactant to produce a pyridyldiamide metal complex.
  • a suitable metal reactant will feature a basic leaving group that will accept a proton from the pyridiyl diamine and then generally depart and be removed from the product.
  • PDA dichloride complex in Scheme 1 below can be alkylated by reaction with an appropriate organometallic reagent.
  • Suitable reagents include organolithium and organomagnesium, and Grignard reagents.
  • the alkylations are generally performed in etherial or hydrocarbon solvents or solvent mixtures at temperatures typically ranging from -100°C to 50°C.
  • R, R 1 , R 2 , R 3 , R 4 are independently selected from the group consisting of H, hydrocarbyls (such as alkyls, aryls), substituted hydrocarbyls (such as heteroaryls), and silyl groups, and R n indicates hydrogen, hydrocarbyls, or substituted hydrocarbyls, which may be joined to form polycyclic aromatic ring and n is 1, 2, 3, or 4.
  • Another route to pyridyl diamide and other complexes of interest as catalysts involves the insertion of an unsaturated molecule into a covalent metal-carbon bond where the covalently bonded group is part of a multidentate ligand structure, such as that described by Boussie et al. in US 6,750,345.
  • the unsaturated molecule will generally have a carbon-X double or triple bond where X is a group 14 or group 15 or group 16 element.
  • Examples of unsaturated molecules include alkenes, alkynes, imines, nitriles, ketones, aldehydes, amides, formamides, carbon dioxide, isocyanates, thioisocyanates, and carbodiimides. Examples showing the insertion reactions involving benzophenone and ⁇ , ⁇ -dimethylformamide are below.
  • Pyridyl diamide complexes may have fluxional structures in solution. Shown in Figure 24 are NMR spectra acquired for a pyridyl dimide complex that displays a complete lack of symmetry (Q symmetry) at -22°C, but higher symmetry (C s symmetry) at
  • One method for controlling the fluxionalty in these systems would be to use a sub-stoichiometric amount of activator to form a mixture of activated and unactivated species. Of the two, the unactivated species would be expected to undergo relatively fast fluxionality. Thus this would provide a mechanism to produce blocky polyolefins when this system is employed in the presence of, or in the absence of, Group 12 or 13 organometallics (e.g., ZnEt2, AlEt3) that can facilitate polymeryl chain transfer.
  • Activators e.g., ZnEt2, AlEt3
  • catalyst systems may be formed by combining them 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, z ' so-butyl alumoxane, and the like.
  • alumoxanes such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane, z ' so-butyl alumoxane, and the like.
  • the 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, [DMAH] + [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(C6F 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., [PhNMe2H]B(C6F 5 )4) and N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.
  • 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.
  • the 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 1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.
  • a co-activator such as a group 1, 2, or 13 organometallic species (e.g., an alkyl aluminum compound such as tri-n-octyl aluminum), 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; 1:25 to 1:1; 1:15 to 1:1; l:10to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.
  • boron containing NCA activators represented by the formula below can be used:
  • Z is (L-H) or a reducible Lewis acid
  • L is a neutral Lewis base
  • H is hydrogen
  • (L-H) is a Bronsted acid
  • a d" is a boron containing non-coordinating anion having the charge d-
  • d is 1, 2, or 3.
  • the cation component, Z d + may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation ⁇ + may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums.
  • Preferred reducible Lewis acids can be any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a Q to C40 hydrocarbyl, or a substituted CI to C40 hydrocarbyl), preferably the reducible Lewis acids in formula (14) above as "Z" include those represented by the formula: (Ph 3 C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with C ⁇ to C40 hydrocarbyls or substituted a Q to C40 hydrocarbyls, preferably C ⁇ to C20 alkyls or aromatics or substituted C ⁇ to C20 alkyls or aromatics, preferably Z is a triphenylcarbonium.
  • Z d + is the activating cation (L-H) d + , it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo ⁇ , ⁇ -dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, te
  • the anion component A d" includes those having the formula [M k+ Q n ] d_ wherein k is
  • each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • suitable A d also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in USSN 61/494,730, filed June 8, 2011, which is incorporated by reference herein.
  • the ionic stoichiometric activator ⁇ + (A d_ ) is one or more of N,N- dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -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, or triphenylcarbenium tetra(perflufluoroph
  • Bulky activator refers to anionic activators represented by the formula: each R 1 is, independently, a halide, preferably a fluoride;
  • Ar is substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl), preferably substituted with to C 4Q hydrocarbyls, preferably to C20 alkyls or aromatics;
  • each R 2 is, independently, a halide, a to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R2 is a fluoride or a perfluorinated phenyl group);
  • each R 3 is a halide, to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a to C20 hydrocarbyl or hydrocarbylsilyl group (preferably
  • R3 is a fluoride or a perfluorinated aromatic hydrocarbyl group); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2 and R3 form a perfluorinated phenyl ring); and
  • L is a neutral Lewis base
  • (L-H) + is a Bronsted acid
  • d is 1, 2, or 3 ;
  • anion has a molecular weight of greater than 1020 g/mol
  • ( ⁇ 3 (3 ⁇ 4 + is (Ph 3 C) c i + , where Ph is a substituted or unsubstituted phenyl, preferably substituted with Q to C 4 Q hydrocarbyls or substituted Q to C 4 Q hydrocarbyls, preferably Q to C20 alkyls or aromatics or substituted Q to C20 alkyls or aromatics.
  • Molecular volume is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume. Molecular volume may be calculated as reported in "A Simple "Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964.
  • MV Molecular volume
  • V s the scaled volume.
  • V s the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V s is decreased by 7.5% per fused ring.
  • one or more of the NCAs is chosen from the activators described in U.S. Patent No. 6,211, 105.
  • 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.
  • 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% to 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.
  • Invention catalyst complexes are useful in polymerizing unsaturated monomers conventionally known to undergo metallocene-catalyzed polymerization such as solution, slurry, gas-phase, and high-pressure polymerization.
  • metallocene-catalyzed polymerization such as solution, slurry, gas-phase, and high-pressure 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 process used herein typically comprises 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.
  • Chain transfer agents (such as hydrogen or diethyl zinc) 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.
  • the process may be conducted at a pressure of from 0.05 to 1500 MPa. In a preferred embodiment, the pressure is between 1.7 MPa and 30 MPa, or in another embodiment, especially under supercritical conditions, the pressure is between 15 MPa and 1500 MPa.
  • Monomers useful herein include olefins having from 2 to 40 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 C2 to 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 C3 to C20 a-olefin, and particularly a C3 to 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 C4 to C20 a-olefin, and particularly a C4 to C20 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- 1.
  • 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, and 9-methyl- 1,9-decadiene.
  • the catalyst systems may, under appropriate conditions, generate stereoregular polymers or polymers having stereoregular sequences in the polymer chains.
  • the catalyst complexes described herein are used in any polymerization process described above to produce ethylene homopolymers or copolymers, propylene homopolymers or copolymers.
  • the catalyst complexes described herein are used in any polymerization process described above to produce polyalphaolefins (PAO's), e.g., polymers of C3 to C40 alphaolefins, having low number average molecular weight (e.g., 30,000 g/mol or less (as determined as described in US 2008/0045638, pg 36-38), such as dimers, trimers, tetramers, pentamers) of C 4 to C24 (preferably C 5 to (3 ⁇ 4, preferably to C 14 , even preferably Cg to C ⁇ , most preferably QQ) branched or linear alpha-olefins, provided that C3 and C 4 alpha-olefins are present at 10 wt% or less.
  • PAO's polyalphaolefins
  • C3 to C40 alphaolefins having low number average molecular weight (e.g., 30,000 g/mol or less (as determined as described in US 2008/
  • Suitable olefins include propylene, 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, and blends thereof.
  • Polymers of linear alpha olefins (LAO's) with only even carbon numbers between 6 and 18 (inclusive) are particularly preferred. In one embodiment, a single LAO is used to prepare the oligomers.
  • a preferred embodiment involves the oligomerization of 1 -decene
  • the PAO is a mixture of oligomers (including, for example, dimers, trimers, tetramers, pentamers, and higher) of 1-decene.
  • the PAO comprises oligomers of two or more C3 to LAOs (preferably C5 to C g LAOs), to make 'bipolymer' or 'terpolymer' or higher-order copolymer combinations, provided that C3 and C 4 LAOs are present at 10 wt% or less.
  • a preferred embodiment involves the polymerization of a mixture of 1 -octene, 1-decene, and 1 - dodecene
  • the PAO is a mixture of oligomers (for example, dimers, trimers, tetramers, pentamers, and higher) of 1 -octene, 1 -decene, and 1 -dodecene.
  • the PAO has a viscosity index (ASTM D 2270) of 120 or more, preferably 150 or more, preferably 200 or more and a pour point (ASTM D 97) of -20°C or less, preferably -25°C or less, preferably -30°C or less and a flash point (ASM D 92) of 200°C or more, preferably 220°C or more, preferably 250°C or more.
  • ASTM D 2270 a viscosity index
  • ASTM D 97 pour point
  • ASM D 92 flash point
  • 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 Patents 5,153, 157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132, and that of WO 95/07941.
  • Exemplary compounds include tri ethyl aluminum, triethyl borane, tri-z ' so-butyl aluminum, methyl alumoxane, z ' so-butyl alumoxane, and tri-n-octyl aluminum.
  • Those scavenging compounds having bulky or C6-C20 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-iso- butyl aluminum, tri-z ' so-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-iso- butyl aluminum, tri-z ' so-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.
  • two or more complexes are combined with diethyl zinc in the same reactor with monomer.
  • one or more complexes are combined with another catalyst (such as a metallocene) and diethyl zinc in the same reactor with monomer.
  • 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 Gel Permeation Chromatography.
  • Preferred polymers produced here 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%.
  • 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, and storageware, toys, sheets, pipes, 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.
  • this invention relates to:
  • a pyridyldiamido transition metal complex for use in alkene polymerization represented by the formula: (I) or (II):
  • M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal (preferably a Group 4 metal, preferably Ti, Zr or Hf);
  • R 1 is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups (preferably alkyl, aryl, heteroaryl, and silyl groups);
  • R 1 1 is selected from the group consisting of substituted 5 or 6 (preferably 6) membered aromatic rings, (such as substituted 5 or 6 membered rings where the ring atoms are carbon or heterocyclic rings having 1, 2 or 3 heteroatoms in the ring (such as N, O or S)) where the substitution is a hydrocarbyl group, a heteroatom, or a heteroatom containing group, preferably R 1 1 is a substituted aryl group, preferably a 2,6 or 2,4,6 substituted aryl group; R 10 is -E*(R 12 )(R 13 )- (preferably R 12 and R 13 are the same, preferably R 10 is CH 2 ;
  • E and E* are independently carbon, silicon, or germanium (preferably carbon);
  • each R 12 and R 13 are independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino (preferably hydrogen, alkyl, aryl, alkoxy, silyl, amino, aryloxy, heteroaryl, halogen, and phosphino), R 12 and R 13 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 12 and R 13 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; each R 12 * and R 13 * is independently selected from the group consisting of hydrogen, CI to C5 hydrocarbyls, substituted CI to C5 hydrocarbyls, preferably hydrogen, methyl,
  • R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, (preferably hydrogen, alkyl, alkoxy, aryloxy, halogen, amino, silyl, and aryl), and wherein adjacent R groups (R 3 & R 4 and/or R 4 & R 5 ) 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;
  • R 6 ; R 7 R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and the pairs of positions, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 15 , and/or R 16 & R 15 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or 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;
  • L is an anionic leaving group, where the L groups may be the same or different and any two
  • L groups may be linked to form a dianionic leaving group
  • n 0, 1, 2, 3, or 4;
  • L' is neutral Lewis base
  • w 0, 1, 2, 3, or 4;
  • Z is -(R 14 *) P Q-J(R 15 *) Q - where Q or J is bonded to R 10 ;
  • J is C or Si, preferably C
  • Q is C, O, N, or Si, preferably C
  • R 14 * and R 15 * are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, (preferably hydrogen and alkyls), and wherein adjacent R 14 * and R 15 * groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl 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;
  • p 1 or 2;
  • q 1 or 2.
  • E is carbon and Ri is selected from phenyl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF 3 , ⁇ (3 ⁇ 4, alkoxy, dialkylamino, hydrocarbyl (such as alkyl and aryl), and substituted hydrocarbyls (such as heteroaryl), groups with from one to ten carbons.
  • each L is, independently, selected from halide, alkyl, aryl, alkoxy, ami do, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, triflate, alkylsulfonate, arylsulfonate, and alkynyl; and/or L' is, independently, selected from ethers, thio-ethers, amines, nitriles, imines, pyridines, and phosphines.
  • R 1 1 is selected from aryl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF 3 , ⁇ (3 ⁇ 4, alkoxy, dialkylamino, aryl, and alkyl groups with between one to ten carbons, preferably R 1 1 is 2,6 or 2,4,6 substituted aryl, preferably where the substituents are methyl, ethyl, methoxy, propyl, tert-butyl, butyl, isopropyl, pentyl, hexyl, isobutyl, chloro, fluoro, bromo, iodo, trimethylsilyl, or triethylsilyl.
  • R 1 1 is 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6- diisobutylphenyl, 2,5-dimethylphenyl, 2,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2,6-diisopropylphenyl, or 2,4,6-triisopropylphenyl.
  • a catalyst system comprising a complex according to any of paragraphs 1 to 9 and an activator or cocatalyst such as alumoxane or a non-coordinating anion.
  • a polymerization process comprising contacting alkene monomer with a complex according to any of paragraphs 1 to 9 or the catalyst system of paragraph 10.
  • Schemes 1 Outlined in Schemes 1 is the general synthetic routes that was used to prepare pyridyl diamines.
  • pinacolate (2,3 dimethyl butane 2,3 diolate)
  • Me is methyl
  • Mes is mesityl
  • Boc is t-butylcarbonate
  • Ph is phenyl
  • Dipp is 2,6-diisopropylphenyl
  • 2-iPrPh is 2-isopropylphenyl.
  • a suspension of 17.0 g (88.1 mmol) of tert-butyl phenylcarbamate in 150 ml of hexanes 35.2 ml (88.1 mmol) of 2.5 M wBuLi in hexanes was slowly added at gentle reflux for ca. 15 min. This mixture was stirred for additional 30 minutes and then evaporated to dryness.
  • the resulting white powder was added to a solution of 30.6 g (88.1 mmol) of 2-[2-(bromomethyl)-l-naphthyl]-4,4,5,5-tetramethyl-l,3,2- dioxaborolane in 300 ml of DMF. This mixture was stirred for 20 minutes at 75°C and then poured into 1200 cm 3 of cold water. The product was extracted with 3 x 200 ml of ethyl acetate. The combined organic extract was washed by 2 x 300 ml of water, dried over MgS04, and then evaporated to dryness.
  • N-((l-(6-((2,6-Diisopropylphenylimino)methyl)pyridin-2-yl)naphthalen-2- yl)methyl)-2,4,6-trimethylaniline (6b).
  • Benzene 200 mL was added to compound 5b (6.69 g, 17.6 mmol), and 2,6-diisopropylaniline (3.12 g, 17.6 mmol), and p-toluenesulfonic acid monohydrate (5 mg) in a 500 mL round-bottomed flask fitted with a Dean-Stark trap. The mixture was heated to reflux under nitrogen.
  • pyridyldiamide complexes Shown below in Table 1 are pyridyldiamide complexes. Details of their syntheses are given below. Complexes P-Cl, U-Cl, and V-Cl were prepared as intermediates to P, U, and V, respectively, and were not used directly as catalyst components for olefin polymerizations. Complexes H, P, and V are for comparative purposes. Table 1. Pyridyl diamide complexes used as precatalysts for olefin polymerizations.
  • 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 then closed and propylene (typically 1 mL) was introduced to each vessel as a condensed gas liquid. If ethylene was added as a comonomer, it was added before the propylene as a gas to a pre-determined pressure (typically 10-80 psi) while the reactor vessels were heated to a set temperature (typically 40°C).
  • solvent typically isohexane
  • scavenger and/or co-catalyst and/or a chain transfer agent such as tri-n-octylaluminum in toluene (typically 100-1000 nmol) was added.
  • the reaction was then allowed to proceed until a pre-determined amount of pressure had been taken up by the reaction. Alternatively, the reaction may be allowed to proceed for a set amount of time. At this point, the reaction was quenched by pressurizing the vessel with compressed air.
  • the glass vial insert containing the polymer product and solvent was removed from the pressure cell 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, by FT-IR (see below) to determine percent ethylene incorporation, and by DSC (see below) to determine melting point.
  • the system was operated at an eluent flow rate of 2.0 mL/minutes 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 uL 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 are relative to linear polystyrene standards and are uncorrected.
  • DSC Differential Scanning Calorimetry
  • Weight percent ethylene was obtained from the ratio of peak heights at 744-715 and 1 189-1 126 cm -1 . This method was calibrated using a set of ethylene/propylene copolymers with a range of known wt% ethylene content.
  • the X groups for U and H differ (methyl vs benzyl), but this change has a negligible effect on the polymer produced.
  • R 12 H because, inter alia: (i) it produced higher molecular weight ethylene-polypropylene copolymer; (ii) it has higher activity; and (iii) it enabled the production of ethylene-propylene copolymers containing low (i.e., less than 35%) amounts of ethylene.
  • !fi NMR data is collected at 120°C shall be used in a 5 mm probe using a spectrometer with a frequency of at least 400 MHz. Data is recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 120 transients. Spectral signals are integrated. Samples are dissolved in deuterated methylene chloride at concentrations between 10 wt% to 15 wt% prior to being inserted into the spectrometer magnet. Prior to data analysis, spectra are referenced by setting the residual CHDCI 2 resonance to 5.24 ppm.
  • 13 C NMR data is collected at 120°C using a spectrometer with a 13 C frequency of at least 75 MHz.
  • a 90 degree pulse, an acquisition time adjusted to give a digital resolution between 0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time with continuous broadband proton decoupling using swept square wave modulation without gating is employed during the entire acquisition period.
  • the spectra are acquired with time averaging to provide a signal to noise level adequate to measure the signals of interest.
  • Samples are dissolved in deuterated methylene chloride at concentrations between 10 wt% to 15 wt% prior to being inserted into the spectrometer magnet. Prior to data analysis, spectra are referenced by setting the chemical shift of the deuterated methylene chloride solvent signal to 54 ppm.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne des complexes de pyridyldiamido et de métal de transition pour l'utilisation dans la polymérisation d'alcène.
PCT/US2012/022476 2011-03-25 2012-01-25 Complexes de pyridyldiamido et de métal de transition, production et utilisation de ceux-ci WO2012134615A1 (fr)

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EP12764279.1A EP2688895A4 (fr) 2011-03-25 2012-01-25 Complexes de pyridyldiamido et de métal de transition, production et utilisation de ceux-ci

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US13/114,307 US8674040B2 (en) 2008-07-25 2011-05-24 Pyridyldiamido transition metal complexes, production and use thereof
US13/207,847 US8710163B2 (en) 2008-07-25 2011-08-11 Pyridyldiamido transition metal complexes, production and use thereof
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EP2688896A2 (fr) * 2011-03-25 2014-01-29 Exxonmobil Chemical Patents Inc. Complexes de métaux de transition pyridyldiamido, leurs production et utilisation
US9315526B2 (en) 2014-03-03 2016-04-19 Exxonmobil Chemical Patents Inc. Pyridyldiamido transition metal complexes, production and use thereof
EP3114130A4 (fr) * 2014-03-03 2017-05-10 ExxonMobil Chemical Patents Inc. Complexes de métaux de transition pyridyldiamido, production et utilisation associées
WO2018013284A2 (fr) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Compositions de copolymère de catalyseur métallocène double
WO2018013283A2 (fr) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Compositions copolymères à doubles catalyseurs métallocènes
WO2018013286A1 (fr) 2016-07-14 2018-01-18 Exxonmobil Chemical Patents Inc. Compositions d'huile lubrifiante comprenant des compositions de copolymères bimodaux, catalysés par un métallocène double, utiles en tant que modificateurs de viscosité
US9975973B2 (en) 2015-10-02 2018-05-22 Exxonmobil Chemical Patents Inc. Asymmetric fluorenyl-substituted salan catalysts
US9982076B2 (en) 2015-10-02 2018-05-29 Exxonmobil Chemical Patents Inc. Supported bis phenolate transition metals complexes, production and use thereof
US9982067B2 (en) 2015-09-24 2018-05-29 Exxonmobil Chemical Patents Inc. Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports
US9994658B2 (en) 2015-10-02 2018-06-12 Exxonmobil Chemical Patents Inc. Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports
US9994657B2 (en) 2015-10-02 2018-06-12 Exxonmobil Chemical Patents Inc. Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports
US10000593B2 (en) 2015-10-02 2018-06-19 Exxonmobil Chemical Patents Inc. Supported Salan catalysts
EP3353217A4 (fr) * 2015-09-24 2018-11-07 ExxonMobil Chemical Patents Inc. Procédé de polymérisation à l'aide de composés pyridyldiamido supportés sur des supports de silicate stratifié traité par un organoaluminium
WO2018231224A1 (fr) 2017-06-14 2018-12-20 Exxonmobil Chemical Patents Inc. Mélanges de copolymères d'éthylène pour applications de réticulation
EP3344666A4 (fr) * 2015-08-31 2019-07-31 ExxonMobil Chemical Patents Inc. Polymères produits au moyen d'agents de transfert vinyliques
US10414887B2 (en) 2015-10-02 2019-09-17 Exxonmobil Chemical Patents Inc. Supported catalyst systems and methods of using same
US10562987B2 (en) 2016-06-30 2020-02-18 Exxonmobil Chemical Patents Inc. Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents
WO2020046597A1 (fr) 2018-08-29 2020-03-05 Exxonmobil Chemical Patents Inc. Procédés de préparation de compositions polymères à élasticité améliorée à l'aide de systèmes catalytiques vtp et hmp dans des procédés parallèles
US10618988B2 (en) 2015-08-31 2020-04-14 Exxonmobil Chemical Patents Inc. Branched propylene polymers produced via use of vinyl transfer agents and processes for production thereof
US10626200B2 (en) 2017-02-28 2020-04-21 Exxonmobil Chemical Patents Inc. Branched EPDM polymers produced via use of vinyl transfer agents and processes for production thereof
US10676547B2 (en) 2015-08-31 2020-06-09 Exxonmobil Chemical Patents Inc. Aluminum alkyls with pendant olefins on clays
US10676551B2 (en) 2017-03-01 2020-06-09 Exxonmobil Chemical Patents Inc. Branched ethylene copolymers produced via use of vinyl transfer agents and processes for production thereof
US11041029B2 (en) 2015-08-31 2021-06-22 Exxonmobil Chemical Patents Inc. Aluminum alkyls with pendant olefins for polyolefin reactions

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JP2023513582A (ja) * 2020-02-11 2023-03-31 エクソンモービル ケミカル パテンツ インコーポレイテッド 遷移金属ビス（フェノラート）触媒錯体を用いて得られるエチレン－アルファオレフィン－ジエンモノマーのコポリマー及びその生成のための均一プロセス

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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2688897A1 (fr) * 2011-03-25 2014-01-29 Exxon-Mobil Chemical Patents Inc. Complexes de métaux de transition pyridyldiamido pyridyldiamido, leurs production et utilisation
EP2688896A2 (fr) * 2011-03-25 2014-01-29 Exxonmobil Chemical Patents Inc. Complexes de métaux de transition pyridyldiamido, leurs production et utilisation
EP2688897A4 (fr) * 2011-03-25 2014-11-12 Exxonmobil Chem Patents Inc Complexes de métaux de transition pyridyldiamido pyridyldiamido, leurs production et utilisation
EP2688896A4 (fr) * 2011-03-25 2014-11-12 Exxonmobil Chem Patents Inc Complexes de métaux de transition pyridyldiamido, leurs production et utilisation
US9315526B2 (en) 2014-03-03 2016-04-19 Exxonmobil Chemical Patents Inc. Pyridyldiamido transition metal complexes, production and use thereof
EP3114130A4 (fr) * 2014-03-03 2017-05-10 ExxonMobil Chemical Patents Inc. Complexes de métaux de transition pyridyldiamido, production et utilisation associées
US11041029B2 (en) 2015-08-31 2021-06-22 Exxonmobil Chemical Patents Inc. Aluminum alkyls with pendant olefins for polyolefin reactions
US10829569B2 (en) 2015-08-31 2020-11-10 Exxonmobil Chemical Patents Inc. Polymers produced via use of vinyl transfer agents
US10676547B2 (en) 2015-08-31 2020-06-09 Exxonmobil Chemical Patents Inc. Aluminum alkyls with pendant olefins on clays
EP3344666A4 (fr) * 2015-08-31 2019-07-31 ExxonMobil Chemical Patents Inc. Polymères produits au moyen d'agents de transfert vinyliques
US10618988B2 (en) 2015-08-31 2020-04-14 Exxonmobil Chemical Patents Inc. Branched propylene polymers produced via use of vinyl transfer agents and processes for production thereof
EP3353217A4 (fr) * 2015-09-24 2018-11-07 ExxonMobil Chemical Patents Inc. Procédé de polymérisation à l'aide de composés pyridyldiamido supportés sur des supports de silicate stratifié traité par un organoaluminium
US9982067B2 (en) 2015-09-24 2018-05-29 Exxonmobil Chemical Patents Inc. Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports
US9975973B2 (en) 2015-10-02 2018-05-22 Exxonmobil Chemical Patents Inc. Asymmetric fluorenyl-substituted salan catalysts
US9994657B2 (en) 2015-10-02 2018-06-12 Exxonmobil Chemical Patents Inc. Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports
US10000593B2 (en) 2015-10-02 2018-06-19 Exxonmobil Chemical Patents Inc. Supported Salan catalysts
US9994658B2 (en) 2015-10-02 2018-06-12 Exxonmobil Chemical Patents Inc. Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports
US9982076B2 (en) 2015-10-02 2018-05-29 Exxonmobil Chemical Patents Inc. Supported bis phenolate transition metals complexes, production and use thereof
US10414887B2 (en) 2015-10-02 2019-09-17 Exxonmobil Chemical Patents Inc. Supported catalyst systems and methods of using same
US10562987B2 (en) 2016-06-30 2020-02-18 Exxonmobil Chemical Patents Inc. Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents
WO2018013283A2 (fr) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Compositions copolymères à doubles catalyseurs métallocènes
WO2018013284A2 (fr) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Compositions de copolymère de catalyseur métallocène double
WO2018013285A1 (fr) 2016-07-14 2018-01-18 Exxonmobil Chemical Patents Inc. Compositions de copolymère bimodal catalysé par métallocène double
WO2018013286A1 (fr) 2016-07-14 2018-01-18 Exxonmobil Chemical Patents Inc. Compositions d'huile lubrifiante comprenant des compositions de copolymères bimodaux, catalysés par un métallocène double, utiles en tant que modificateurs de viscosité
US10626200B2 (en) 2017-02-28 2020-04-21 Exxonmobil Chemical Patents Inc. Branched EPDM polymers produced via use of vinyl transfer agents and processes for production thereof
US10676551B2 (en) 2017-03-01 2020-06-09 Exxonmobil Chemical Patents Inc. Branched ethylene copolymers produced via use of vinyl transfer agents and processes for production thereof
WO2018231224A1 (fr) 2017-06-14 2018-12-20 Exxonmobil Chemical Patents Inc. Mélanges de copolymères d'éthylène pour applications de réticulation
WO2020046597A1 (fr) 2018-08-29 2020-03-05 Exxonmobil Chemical Patents Inc. Procédés de préparation de compositions polymères à élasticité améliorée à l'aide de systèmes catalytiques vtp et hmp dans des procédés parallèles

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CN103492397A (zh) 2014-01-01
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EP2688895A4 (fr) 2014-10-22

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