WO2009064452A2 - Ethylene polymers - Google Patents

Ethylene polymers Download PDF

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WO2009064452A2
WO2009064452A2 PCT/US2008/012768 US2008012768W WO2009064452A2 WO 2009064452 A2 WO2009064452 A2 WO 2009064452A2 US 2008012768 W US2008012768 W US 2008012768W WO 2009064452 A2 WO2009064452 A2 WO 2009064452A2
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polymer
group
molecular weight
catalyst
substituted
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PCT/US2008/012768
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WO2009064452A3 (en
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Rainer Kolb
Dongming Li
Francis C. Rix
Cesar A. Garcia-Franco
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Univation Technologies, Llc.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C07F17/00—Metallocenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • An ethylene polymer including units derived from ethylene, at least one other alpha-olefin comonomer, and at least one diene, and having at least one of certain properties discuseed in more detail below.
  • metallocene compounds in polymerization catalysts, and the use of metallocene catalysts for polymerization are known.
  • metallocene catalysts there remains an ongoing effort to develop metallocene catalysts, polymerization processes using such catalysts, and polyolefin resins and products made therewith, each having advantageous properties and performance.
  • metallocene catalyst systems comprising at least two catalyst components, wherein at least one component is a metallocene catalyst. See, for example, U.S. Patent Nos. 4,530,914,. 4,937,299, 5,470,811, 5,516,848, 5,696,045, 6, 492,472, 7,141,632, 7,163,906, 7,172,987, and EP-A2-0 743 327, EP-B 1-0 310 734, EP-B 1-516 018.
  • FIG. 4 provides a comparison of the shear thinning characteristics of a non-limiting example resin of the disclosure and a control resin.
  • FIG. 5 provides a comparison of non-limiting example resins of the disclosure and conventional resins.
  • FIG. 6 provides a comparison of Van Gurp-Palmen plots of non-limiting example resins of the disclosure and a control resin.
  • FIG. 7 provides a comparison of Van Gurp-Palmen plots of non-limiting example resins of the disclosure and conventional resins.
  • a halogen atom as in a moiety "substituted with a halogen atom” includes more than one halogen atom, such that the moiety may be substituted with two or more halogen atoms
  • reference to "a substituent” includes one or more substituents
  • reference to "a ligand” includes one or more ligands, and the like.
  • R 1 , R 2 , R 3 , R 4 , and R 5 can be identical or different (e.g. R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyls or R 1 and R 2 may be a substituted alkyl and R 3 may be an aryl, etc.).
  • Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes).
  • a named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name.
  • precatalyst "catalyst”, “precatalyst metal compound”, “catalyst metal compound”, “catalyst component” are generally used interchangeably in this specification, but those of skill in the art may recognize certain precatalysts as catalysts and vice versa.
  • monomer and “comonomer” are generally used interchangeably in this specification, but those of skill in the art may recognize certain monomers as comonomers and vice versa.
  • alkyl refers to a branched or unbranched saturated hydrocarbon group typically although not necessarily containing 1 to about 50 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein may contain 1 to about 12 carbon atoms.
  • heteroatom-containing When the term “heteroatom-containing” appears prior to a list of possible heteroatom- containing groups, it is intended that the term apply to every member of that group. That is, the phrase “heteroatom-containing alkyl, alkenyl and alkynyl” is to be interpreted as “heteroatom-containing alkyl, heteroatom-containing alkenyl and heteroatom-containing alkynyl.”
  • Hydrocarbyl refers to hydrocarbyl radicals containing 1 to about 50 carbon atoms, specifically 1 to about 24 carbon atoms, most specifically 1 to about 16 carbon atoms, including branched or unbranched, saturated or unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like.
  • lower hydrocarbyl intends a hydrocarbyl group of one to six carbon atoms, specifically one to four carbon atoms.
  • Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups
  • heteroatom-containing hydrocarbyl and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom.
  • substituted as in “substituted hydrocarbyl,” “substituted aryl,” “substituted alkyl,” “substituted alkenyl” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, hydrocarbylene, alkyl, alkenyl, aryl or other moiety, at least one hydrogen atom bound to a carbon atom is replaced with one or more substituents that are functional groups such as hydroxyl, alkoxy, alkylthio, phosphino, amino, halo, silyl, and the like.
  • substituted When the term "substituted" appears prior to a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase “substituted alkyl, alkenyl and alkynyl” is to be interpreted as “substituted alkyl, substituted alkenyl and substituted alkynyl.” Similarly, “optionally substituted alkyl, alkenyl and alkynyl” is to be interpreted as “optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl.”
  • divalent as in “divalent hydrocarbyl”, “divalent alkyl”, “divalent aryl” and the like, is meant that the hydrocarbyl, alkyl, aryl or other moiety is bonded at two points to atoms, molecules or moieties with the two bonding points being covalent bonds.
  • aromatic is used in its usual sense, including unsaturation that is essentially delocalized across multiple bonds, such as around a ring.
  • sil refers to the -SiZ 1 Z 2 Z 3 radical, where each
  • X of SiZ Z Z is independently selected from the group consisting of hydride and optionally substituted alkyl, alkenyl, alkynyl, heteroatom-containing alkyl, heteroatom-containing alkenyl, heteroatom-containing alkynyl, aryl, heteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.
  • boryl refers to the -BZ 1 Z 2 group, where each of Z 1 and Z 2 is as defined above.
  • phosphino refers to the group -PZ 1 Z 2 , where each of Z 1 and Z 2 is as defined above.
  • phosphine refers to the group: PZ 1 Z 2 Z 3 , where each of Z 1 , Z 2 , Z 3 as defined above.
  • amino is used herein to refer to the group -NZ 1 Z 2 , where each of Z 1 and Z 2 is as defined above.
  • amine is used herein to refer to the group: NZ 1 Z 2 Z 3 , where each of Z 1 , Z 2 , Z 3 is as defined above.
  • saturated refers to lack of double and triple bonds between atoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, and the like.
  • unsaturated refers to the presence of one or more double and triple bonds between atoms of a radical group such as vinyl, acetylide, oxazolinyl, cyclohexenyl, acetyl and the like.
  • any suitable polymerization catalyst may be practiced with embodiments of the invention, or any combination of polymerization catalysts may be practiced with embodiments of the invention. Illustrative embodiments are listed below.
  • Conventional catalysts are those traditional Ziegler-Natta catalysts and Phillips-type chromium catalyst well known in the art.
  • Examples of conventional- type transition metal catalysts are disclosed in U.S. Pat. Nos. 4,115,639, 4,077,904 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741.
  • the conventional- type transition metal catalyst compounds that may be used in the present invention include, but are not limited to transition metal compounds from Groups III to VIII of the Periodic Table of the Elements. All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by the International Union of Pure and Applied Chemistry, Inc., 2004. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
  • Examples of conventional- type vanadium catalyst compounds are VOC13, VC14 and VOC12— OR where R is a hydrocarbon radical, preferably a Cl to ClO aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-biityl, tertiary- butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates.
  • R is a hydrocarbon radical, preferably a Cl to ClO aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-biityl, tertiary- butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetyl acet
  • Conventional-type chromium catalyst compounds may include CrC ⁇ , chromocene, silyl chromate, chromyl chloride (CrO2C12), chromium-2-ethyl- hexanoate, chromium acetylacetonate (Cr(AcAc)3), and the like.
  • CrC ⁇ CrC ⁇
  • CrO2C12 chromium-2-ethyl- hexanoate
  • Cr(AcAc)3 chromium acetylacetonate
  • the conventional-type transition metal catalysts of the invention may also have the general formula M'lM"X2t Yu E, where M' is Mg, Mn and/or Ca; t is a number from 0.5 to 2; M" is a transition metal Ti, V and/or Zr; X is a halogen, preferably Cl, Br or I; Y may be the same or different and is halogen, alone or in combination with oxygen, — NR.sub.2, —OR, -SR, — COOR, or — OSOOR, where R is a hydrocarbyl radical, in particular an alkyl, aryl, cycloalkyl or arylalkyl radical, acetylacetonate anion in an amount that satisfies the valence state of M'; u is a number from 0.5 to 20; E is an electron donor compound selected from the following classes of compounds: (a) esters of organic carboxylic acids; (b) alcohols; (c) ethers; (d
  • Mg3Ti2C1127CH3COOC2H5 MgTiC15.6C2H5OH, MgTiC15.100CH3OH, MgTiC15 tetrahydrofuran, MgTi2C1127C6H5CN, MgTi2 C1126C6H5COOC2H5, MgTiC162CH3COOC2H5, MgTiC166C5H5N, MgTiC15(OCH3)2CH3COOC2H5, MgTiC15N(C6H5)23CH3COOC2H5, MgTiBr2C142(C2H5)O,
  • catalysts may include cationic catalysts such as A1C13, and other cobalt and iron catalysts well known in the art.
  • the conventional-type transition metal catalyst compounds disclosed herein may be activated with one or more of the conventional-type cocatalysts described below.
  • Cocatalysts And Other Components are described below.
  • Conventional-type cocatalyst compounds for the above conventional-type transition metal catalyst compounds may be represented by the formula M3M4v X2c R3b-c, wherein M3 is a metal from Group IA, IIA, HB and IIIA of the Periodic Table of Elements; M4 is a metal of Group IA of the Periodic Table of Elements; v is a number from 0 to 1; each X2 is any halogen; c is a number from 0 to 3; each R3 is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4; and wherein b minus c is at least 1.
  • M3R3k is a Group IA, IIA, HB or IIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3 depending upon the valency of M3 which valency in turn normally depends upon the particular Group to which M3 belongs; and each R3 may be any monovalent hydrocarbon radical.
  • Examples of conventional-type organometallic cocatalyst compounds of Group IA, IIA and IIIA useful with the conventional-type catalyst compounds described above include, but are not limited to, methyllithium, butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium, di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminum alkyls, such as tri-hexyl- aluminum, triethylaluminum, trimethylaluminum, and tri-isobutylaluminum.
  • Non-limiting examples of such conventional-type cocatalyst compounds may include di-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, ethylberyllium chloride, ethylcalcium bromide, di- isobutylaluminum hydride, methylcadmium hydride, diethylboron hydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminum hydride and bromocadmium hydride.
  • Conventional-type organometallic cocatalyst compounds are known to those in the
  • the catalyst system may include at least one metallocene catalyst component.
  • the metallocene catalyst component may include "half sandwich” and “full sandwich” compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one metal atom.
  • these compounds will be referred to as “metallocenes” or "metallocene catalyst components”.
  • the one or more metallocene catalyst components are represented by the formula (I):
  • the metal atom "M" of the metallocene catalyst compound may be selected from the group consisting of Groups 3 through 12 atoms and lanthanide Group atoms in one embodiment; and selected from the group consisting of Groups 3 through 10 atoms in a more particular embodiment, and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selected from the group consisting of Groups 4, 5 and 6 atoms in yet a more particular embodiment, and a Ti, Zr, Hf atoms in yet a more particular embodiment, and Zr in yet a more particular embodiment.
  • the oxidation state of the metal atom "M” may range from 0 to +7 in one embodiment; and in a more particular embodiment, is +1, +2, +3, +4 or +5; and in yet a more particular embodiment is +2, +3 or +4.
  • the groups bound the metal atom "M” is such that the compounds described below in the formulas and structures are neutral, unless otherwise indicated.
  • the Cp ligand(s) form at least one chemical bond with the metal atom M to form the "metallocene catalyst compound".
  • the Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.
  • M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; and n is 0 or an integer from 1 to 4, and either 1 or 2 in a particular embodiment.
  • the ligands represented by Cp A and Cp B in formula (I) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms and either or both of which may be substituted by a group R.
  • Cp A and Cp B are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
  • each Cp A and Cp B of formula (I) may be unsubstituted or substituted with any one or combination of substituent groups R.
  • substituent groups R as used in structure (I) include hydrogen radicals, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys, aryls, substituted aryls, heteroaryls, aralkyls, aralkyls, aralkyls
  • alkyl substituents R associated with formula (i) includes methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like.
  • substituents R include olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like.
  • at least two R groups, two adjacent R groups in one embodiment, are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof.
  • a substituent group R group such as 1-butanyl may form a bonding association to the element M.
  • Each X in formula (I) is independently selected from the group consisting of: any leaving group in one embodiment; halogen ions, hydrides, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys, aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides, haloalkyl
  • X is Ci to Ci 2 alkyls, C 2 to Ci 2 alkenyls, C 6 to Ci 2 aryls, C 7 to C 2 o alkylaryls, Ci to Ci 2 alkoxys, C 6 to Ci 6 aryloxys, C 7 to Ci 8 alkylaryloxys, Ci to Ci 2 fluoroalkyls, C 6 to Ci 2 fluoroaryls, and Ci to Ci 2 heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular embodiment; hydride, halogen ions, Ci to C 6 alkyls, C 2 to C 6 alkenyls, C 7 to Q 8 alkylaryls, Ci to C 6 alkoxys, C 6 to C )4 aryloxys, C 7 to Ci 6 alkylaryloxys, Ci to C 6 alkylcarboxylates, Ci to C 6 fluorinated alkylcarboxylates, C 6 to Ci 2 arylcarboxylates, C 7 to C C
  • X groups in formula (I) include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., -C 6 F 5 (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF 3 C(O)O " ), hydrides and halogen ions and combinations thereof.
  • Q 2 GZ forms a polydentate ligand unit (e.g., pivalate), wherein at least one of the Q groups form a bond with M, and is defined such that each Q is independently selected from the group consisting of -O-, -NR-, -CR 2 — and -S-; G is either carbon or silicon; and Z is selected from the group consisting of R, - OR, -NR 2 , -CR 3 , -SR, -SiR 3 , -PR 2 , and hydride, providing that when Q is -NR-, then Z is selected from the group consisting of -OR, -NR 2 , -SR, -SiR 3 , -PR 2 ; and provided that neutral valency for Q is satisfied by Z; and wherein each R is independently selected from the group consisting of hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted
  • Me5Phenyl))2ZrX' 2 (1-Me, 3-Bu-Cp)2ZrC12, (CpPr)(Me4Cp)HfC12, (CpBu)2ZrC12, (CpPr)2ZrC12, (CpBu)2HfC12, (CpPr)2HfC12, and any combinations thereof.
  • metallocene catalysts components described above include their structural or optical or enantiomeric isomers (racemic mixture), and may be a pure enantiomer in one embodiment.
  • a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.
  • the "metallocene catalyst component” may comprise any combination of any “embodiment” described herein.
  • Group 15-containing catalyst components include Group 3 to Group 12 metal complexes, wherein the metal is 2 to 4 coordinate, the coordinating moiety or moieties including at least two Group 15 atoms, and up to four Group 15 atoms.
  • the Group 15-containing catalyst component is a complex of a Group 4 metal and from one to four ligands such that the Group 4 metal is at least 2 coordinate, the coordinating moiety or moieties including at least two nitrogens.
  • Group 15-containing compounds are disclosed in, for example, WO 98/46651, WO 99/01460; EP Al 0 893,454; EP Al 0 894 005; US 5,318,935; US 5,889,128 US 6,333,389 B2 and US 6,271,325 Bl.
  • Phenoxide transition metal catalyst compositions are heteroatom substituted phenoxide ligated Group 3 to 10 transition metal or lanthanide metal compounds wherein the metal is bound to the oxygen of the phenoxide group.
  • Phenoxide transition metal catalyst compounds may be represented by Formula XIV or XV:
  • a heteroatom containing group may be any heteroatom or a heteroatom bound to carbon, silicon or another heteroatom.
  • Preferred heteroatoms include boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, and tellurium.
  • Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus, and sulfur. Even more particularly preferred heteroatoms include nitrogen and oxygen.
  • one or more catalyst compounds or catalyst systems may be used in combination with one or more conventional- type catalyst compounds or catalyst systems.
  • suitable catalysts and catalyst systems are described in U.S. Patent Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031, and PCT Publication No. WO 96/23010 published Aug. 1, 1996, all of which are herein fully incorporated by reference.
  • the compound is a biphenyl phenol catalyst (BPP) compound.
  • BPP catalyst compounds are known in the art and any are suitable for use herein such as, but not limited to those disclosed in U.S. Patent Nos. 7,091,282, 7,030,256, 7,060,848, 7,126,031, 6,841,502, U. S. Patent Application publication numbers 2006/0025548, 2006/020588, 2006/00211892, and published PCT application numbers WO 2006/020624, WO 2005/108406, and WO 2003/091262, all incorporated herein by reference.
  • R 1 of formula 1 is hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl,
  • R 40 is selected from the group consisting of hydride, halide, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thioxy, alkyl thio, arylthio, and combinations thereof.
  • Specific R 1 groups within these embodiments include ⁇ (CH 2 ) 2 --, -(CH 2 ) 3 ⁇ , -(CH 2 ) 4 ⁇ and -(CH 2 HC 6 H 4 )- (CH 2 )-.
  • Other specific bridging moieties are set forth in the example ligands and complexes herein.
  • R 2 - R 9 of formula (XVI) are optionally hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino,
  • X groups in formula (XVI) include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., -C 6 F 5 (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF 3 C(O)O " ), hydrides and halogen ions and combinations thereof.
  • X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.
  • two or more X's form a part of a fused ring or ring system.
  • M may be Ti, Zr, or Hf.
  • R 1 , R 3 , R 5 through R 9 are H; each R 2 may be any of alkyl, aryl, or heteroaryl; each R 4 may be any of H, alkyl, aryl; and each X may be any of F, Cl, Br, I, Me, Bnz, CH 2 SiMe 3 , or Cl to C5 alkyls.
  • M may be Ti, Zr, or Hf;
  • R 1 may be any of CH 2 CH 2 , (CH 2 ) 3 , (CH 2 ) 4 , CH 2 CHMeCH 2 , CH 2 CMe 2 CH 2 , Me 2 Si, CH 2 SiMe 2 CH 2 , each R 2 may be any of an aryl group, defined here to bind through the 1 -position to the BPP ring, with substituents in the 2-position or substituents in the 2 and 6 positions such as 2,4-Me 2 Ph, 2,5-Me 2 Ph, 2,6-Me 2 Ph, 2,6-Et 2 Ph, 2,6-Pr 2 -Ph, 2,6-Bu 2 Ph, 2- MeNapthyl, 2,4,6-Me 3 Ph, 2,4,6-Et 3 Ph, 2,4,6-Pr 3 Ph, carbazole and substituted carbazoles; R 3 and R 5 through R 9 are H; each R 4 may be
  • M may be either Zr or Hf; and X may be any of F, Cl, Br, I, Me, Bnz, or CH 2 SiMe 3 .
  • M may be either Zr or Hf;
  • R 1 may be either (CH 2 ) 3 or (CH 2 ) 4 ;
  • each R 2 may be any of 2,6-Me2Ph, 2,6-Et2Ph, 2,6-Pr2-Ph, 2,6-Bu2Ph, 2-MeNapthyl, 2,4,6-Me3Ph, 2,4,6- Et3Ph, 2,4,6-Pr3Ph, and carbazole;
  • each R 4 may be any of H, Methyl or Butyl; and
  • X may be any of F, Cl, or Me.
  • the R 1 is (CH 2 ) 3 ;
  • each R 3 is either 2,4,6-Me3Ph or 2-MeNapthyl;
  • each R 4 is CH 3 ;
  • X is Cl
  • the amount of each catalyst component present in the catalyst systems of the disclosure may be varied within a range.
  • the amount of each catalyst component present in the catalyst systems may be dependent on one or more reaction parameters including but not limited to reactor temperature, hydrogen concentration, and comonomer concentration.
  • the low molecular weight catalyst is generally present in an amount greater than that of the high molecular weight catalyst.
  • the high molecular weight catalyst component is present in a catalyst system in an amount in a range of from about 0.001 to about 5.0 mol% of said low molecular weight catalyst component, preferably in a range of from about 0.05 to about 2.5 mol% of said low molecular weight catalyst component, more preferably in a range of from about 0.1 to about 2.0 mol% of said low molecular weight catalyst component.
  • the mol % of the high molecular weight catalyst may be calculated from the equation: 100(moles of high molecular weight catalyst)/(moles of low molecular weight catalyst + moles of high molecular weight catalyst).
  • the above described low and high molecular weight precatalyst compounds can be combined with an activator and optionally a support or carrier in a manner that will allow production of a polymer with low and high molecular weight components.
  • the term "cocatalyst” or “cocatalysts” may be used interchangeably with one or more "activators”. This activation yields catalyst compounds capable of polymerizing olefins.
  • coordinating ionic activator or ionizing activator or any other compound including Lewis bases, aluminum alkyls, conventional-type cocatalysts or an activator- support and combinations thereof that can convert a neutral precatalyst metal compound to a catalytically active cationic metal compound.
  • alumoxane or modified alumoxane as an activator, and/or to also use ionizing activators, neutral or ionic, such as tri (n-butyl)ammonium tetrakis(pentafluorophenyl)boron or a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor that would ionize the neutral precatalyst metal compound.
  • the low and high molecular weight catalyst precursors according to this invention may be activated for polymerization catalysis in any manner sufficient to allow coordination or cationic polymerization. This can be achieved for coordination polymerization when one ligand can be abstracted and another will either allow insertion of the unsaturated monomers or will be similarly abstractable for replacement with a ligand that allows insertion of the unsaturated monomer (labile ligands), eg. alkyl, silyl or hydride.
  • labile ligands eg. alkyl, silyl or hydride.
  • the traditional activators of coordination polymerization art are suitable, those typically include Lewis acids such as alumoxane compounds, and ionizing, anion precursor compounds that abstract one so as to ionize the bridged metallocene metal center in to a cation and provide a counterbalancing noncoordianting ion.
  • Lewis acids such as alumoxane compounds
  • anion precursor compounds that abstract one so as to ionize the bridged metallocene metal center in to a cation and provide a counterbalancing noncoordianting ion.
  • an activation method using ionizing ionic compounds not containing an active proton but capable of producing both a cationic metal compound catalyst and a non- coordinating anion are also contemplated, and are described in EP-A-O 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.
  • alumoxanes examples include methylalumoxane (MAO), modified methyl alumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U.S.
  • Alumoxanes may be produced by the hydrolysis of the respective trialkylaluminum compound.
  • MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum.
  • MMAO' s are generally more soluble in aliphatic solvents and more stable during storage.
  • a visually clear methylalumoxane 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.
  • Another preferred alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number US 5,041,584).
  • MMAO modified methyl alumoxane
  • Aluminum alkyl or organoaluminum compounds which may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.
  • an ionizing or stoichiometric activator such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459) or combination thereof.
  • neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • Ionizing compounds may contain an active proton, or some other cation associated with but not coordinated to or only loosely coordinated to the remaining ion of the ionizing compound.
  • Such compounds and the like are described in European Publication Nos. EP-A-O 570 982, EP-A-O 520 732, EP-A- 0 495 375, EP-A-500 944, EP-A-O 277 003 and EP-A-O 277 004, U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124, and U.S. Patent Application Serial No. 08/285,380, filed Aug. 3, 1994, all of which are herein fully incorporated by reference.
  • T is an element selected from Group 13 or 15 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted- hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide.
  • 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.
  • NCA also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • a suitable anion is a borate with three ortho- substituted fluoroaryl ligands and one alkyne ligand.
  • a suitable anion is a borate containing fluoroaryl groups with polar substitutents such as amines, ethers, silyl groups and derivatives thereof.
  • non-coordinating anion may be used interchangeably with the term weakly coordinating anion.
  • the ionic stoichiometric activator is N,N- dimethylanilinium tetrakis(perfluorophenyl)borate and/or triphenylcarbenium tetrakis(perfluorophenyl)borate.
  • NCA non-coordinating anion
  • Non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes.
  • Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the metal cation in the sense of balancing its ionic charge, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • These types of cocatalysts sometimes use tri-isobutyl aluminum or tri-octyl aluminum as a scavenger.
  • invention process also can employ cocatalyst compounds or activator compounds that are initially neutral Lewis acids but form a cationic metal complex and a noncoordinating anion, or a zwitterionic complex upon reaction with the invention compounds.
  • tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl or hydride ligand to yield an invention cationic metal complex and stabilizing noncoordinating anion, see EP-A-O 427 697 and EP-A-O 520 732 for illustrations of analogous Group-4 metallocene compounds.
  • EP-A-O 495 375 See U.S. Patents 5,624,878; 5,486,632; and 5,527,929.
  • X is a ligand, such as chloride, amido or alkoxy ligands, not capable of discrete ionizing abstraction with the ionizing, anion pre-cursor compounds
  • these functional group ligands can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-O 500 944, EP-Al-O 570 982 and EP-Al-O 612 768 for analogous processes describing the reaction of alkyl aluminum compounds with analogous dihalide substituted metallocene compounds prior to or with the addition of activating noncoordinating anion precursor compounds.
  • the catalyst-precursor-to-activator molar ratio may be any ratio.
  • Combinations of the described activator compounds may also be used for activation.
  • tris(perfluorophenyl) boron can be used with methylalumoxane.
  • activators include those described in PCT Publication No. WO 98/07515 such as tris (2, 2', 2"-nonafluorobiphenyl)fluoroaluminate, which publication is fully incorporated herein by reference.
  • Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, PCT Publication Nos. WO 94/07928 and WO 95/14044, and U.S. Patent Nos. 5,153,157 and 5,453,410, all of which are herein fully incorporated by reference.
  • WO 98/09996 incorporated herein by reference describes activating precatalyst metal compounds with perchlorates, periodates and iodates including their hydrates.
  • one or more alumoxanes may be used to activate the low and high molecular weight catalyst components.
  • one or more alumoxanes may be used to activate the low molecular weight precatalyst component while one or more ionizing activators are used to activate the high molecular weight precatalyst component.
  • one or more alumoxanes may be used to activate the high molecular weight precatalyst component while one or more ionizing activators are used to activate the low molecular weight precatalyst component.
  • one or more ionizing activator are used to activate the low and high molecular weight catalyst components.
  • one or more alumoxanes and one or more ionizing activators may be used to activate the low and high molecular weight precatalyst components.
  • any quantity of activators that activates precatalyst metal compounds may be used.
  • the catalysts of the invention comprise high and low molecular weight catalyst precursors, an activator and a support material.
  • Methods for preparing supported catalysts are well known in the art and are easily extendible to the preparation of catalysts with high and low molecular weight catalyst metal compounds.
  • the above described precatalyst metal compounds and activators may be combined with one or more support materials or carriers using one of the support methods well known in the art or as described below.
  • the method of the invention uses a polymerization catalyst in a supported form.
  • a catalyst system is in a supported form, for example deposited on, bonded to, contacted with, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.
  • support or carrier are used interchangeably and are any support material, preferably a porous support material, for example, talc, inorganic oxides and inorganic chlorides.
  • Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • the preferred carriers are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides.
  • the preferred supports include silica, alumina, silica- alumina, magnesium chloride, and mixtures thereof.
  • Other useful supports include magnesia, titania, zirconia, montmorillonite (EP-Bl 0 511 665) and the like.
  • combinations of these support materials may be used, for example, silica- chromium, silica-alumina, silica-titania and the like.
  • active catalysts may be prepared by supporting the ligands of the catalysts of the invention on support then treatment with a labile organometallic agent, such as Zr(CH 2 Ph) 4 , and an activator.
  • a labile organometallic agent such as Zr(CH 2 Ph) 4
  • an activator such as Zr(CH 2 Ph) 4
  • the catalyst compounds of the invention may contain a polymer bound ligand as described in U.S. Patent Nos. 5,473,202 and 5,770,755, which are herein fully incorporated by reference; the system of the invention may be spray dried as described in U.S. Patent No.
  • the liquid is an aliphatic or aromatic hydrocarbon, most preferably toluene.
  • the catalyst compound and activator solutions are mixed together and added to a porous support or the porous support is added to the solutions such that the total volume of the catalyst metal compound solution and the activator solution or the catalyst compound and activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.
  • the catalyst system comprises a precatalyst as described herein activated by methylaluminoxane (MAO) and supported by silica.
  • the MAO is first contacted with the silica and dried then treated with a solution of the high and low molecular weight precatalyst compounds then dried.
  • a supported catalyst is prepared by combining high and low molecular weight precatalysts, solvent and activator then addition of a support material; afterwards, solvent may optionally be removed.
  • a supported catalyst is prepared by combination of an activator with the support material, optionally in the presence of solvent, then a mixture or mixtures of high and low molecular weight precatalysts and solvent; afterwards, solvent may optionally be removed.
  • a supported catalyst is prepared by combination of a low molecular weight precatalyst, an activator and support and optionally solvent followed by the addition of a high molecular weight precatalyst; afterwards, solvent may optionally be removed.
  • a supported catalyst is prepared by combination of a high molecular weight precatalyst, an activator and support and optionally solvent followed by the addition of a low molecular weight precatalyst; afterwards, solvent may optionally be removed.
  • the catalyst systems of the disclosure may be produced by any one or more techniques known in the art useful for making catalyst compounds and any such methods suitable for use herein for example, but not limited to, the method disclosed in U.S Patent No. 6,608,153, incorporated herein by reference.
  • a support is combined with a diluent to form a support slurry, which may be stirred and optionally heated during mixing.
  • the first precatalyst compound, second precatalyst compound, and any one or more cocatalyst components may be added to the slurry in one or more steps and may be added individually or in any combination.
  • the resulting slurry is mixed to achieve the desired contact between the components.
  • Any one or more recovery technique may then be employed to recover the catalyst system.
  • suitable recovery techniques include filtration, evaporation, vacuum distillation, simple decanting, and combinations thereof.
  • the retrieved catalyst component may be washed any number of times with a suitable diluent, especially one or more aliphatic or cycloaliphatic hydrocarbons, or a mixture thereof.
  • the resulting recovered catalyst composition may be dried using conventional techniques, such as passing an inert gas, especially nitrogen, over the solid to form a solid, granular powdery catalyst composition or it may be combined with an inert liquid, especially a hydrocarbon such as a mineral oil, for storage and use.
  • the catalyst composition is preferably stored under an inert atmosphere.
  • the slurry comprising diluent and any one or more of the catalyst components and support particles may be heated during and/or after addition and/or mixing of each component.
  • the temperature of the slurry is generally sufficiently low so that the catalyst components are not inadvertently deactivated.
  • the temperature of the slurry is maintained at a temperature below 120°C to avoid deactivation of the catalyst components.
  • olefin(s), preferably C 2 to C 3 o olefin(s) or alpha-olefin(s), preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of the catalyst metal compound system of the invention prior to the main polymerization.
  • the prepolymerization can be carried out batchwise or continuously in gas, solution or slurry phase including at elevated pressures.
  • the prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen.
  • any molecular weight controlling agent such as hydrogen.
  • the present disclosure encompasses homopolymerization processes comprising a single olefin species such as ethylene or propylene, as well as 4 /
  • a copolymer may comprise ethylene copolymerized with a comonomer selected from 1-butene, 1- pentene, 1-hexene, 1-octene, 1-decene, or styrene.
  • the diene may be a polyunsaturated compound; containing at least two
  • polystyrene resin polystyrene resin
  • polyolefins are copolymers of ethylene and at least one comonomer selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and combinations thereof.
  • the polyolefins are bimodal copolymers of ethylene and at least one comonomer selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, and combinations thereof.
  • Polymerization reactors suitable for the present disclosure may be any type of reactor known in the art and may comprise at least one raw material feed system, at least one feed system for catalyst or catalyst components, at least one reactor system, at least one polymer recovery system or any suitable combination thereof. Suitable reactors for the present disclosure may further comprise any one or more of any of a catalyst storage system, an extrusion system, a cooling system, a diluent recycling system, or a control system. Such reactors may comprise continuous take-off and direct recycling of catalyst, diluent, and polymer.
  • continuous processes may comprise the continuous introduction of a monomer, a catalyst, and optionally a diluent into a polymerization reactor and the continuous removal from this reactor of polymer and recycling of diluent and unreacted monomers and comonomers.
  • the comonomer if present in the polymerization reactor, is present at any level that will achieve the desired weight percent incorporation of the comonomer into the finished polyethylene. This is expressed as a mole ratio of comonomer to ethylene as described herein, which is the ratio of the gas concentration of comonomer moles in the cycle gas to the gas concentration of ethylene moles in the cycle gas.
  • the comonomer is present with ethylene in the cycle gas in a mole ratio range of from 0 or 0.0001 (comonomer: ethylene) to 0.20 or 0.10, and from 0.001 to 0.080 in another embodiment, and from 0.001 to 0.050 in even another embodiment, and from 0.002 to 0.20 in still another embodiment.
  • the comonomer is present with ethylene in the cycle gas in a mole ratio range comprising any combination of any upper limit with any lower limit as described herein.
  • the ratio of hydrogen to total ethylene monomer (mol ppm H2: mol % ethylene) in the circulating gas stream is in a range of from 0 to 100, in a range of from 0.05 to 50 in another embodiment, in a range of from 0.10 to 40 in even another embodiment, and in a range of from 0.15 to 35 in still another embodiment.
  • the ratio of hydrogen to total ethylene monomer (mol ppm H2: mol % ethylene) in the circulating gas stream may be in a range comprising any combination of any upper mole ratio limit with any lower mole ratio limit described above.
  • the processes of the disclosure may be characterized in that the desired composition of high molecular weight to low molecular weight moiety can be achieved at any of the above hydrogen to ethylene ratios.
  • the process may also include "condensing agents" as is known in the art and disclosed in, for example, U.S. Patent Nos. 4,543,399, 5,405,922 and 462,999.
  • the condensing agent if present in the reactor can be at any level that will achieve the desired increase in the dew point in order to improve cooling and ultimately space time yields.
  • Suitable condensing agents include but are not limited to saturated hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, n-octane or mixtures thereof.
  • the catalysts and catalyst systems of the invention described above are suitable for use in any polymerization process over a wide range of temperatures and pressures.
  • the temperatures may be in the range of from -60°C to about 280 0 C, preferably from 50°C to about 200 0 C, and the pressures employed may be in the range from 1 atmosphere to about 500 atmospheres or higher.
  • the polymerization processes of the disclosure may be carried out in solution, in bulk, in suspension, in gas-phase, in slurry-phase, as a high-pressure process, or any combinations thereof. Generally solution, gas-phase and slurry- phase processes are preferred. The processes may be carried out in any one or more stages and/or in any one or more reactor having any one or more reaction zone and are conducted substantially in the absence of catalyst poisons. As known by one of skill in the art, organometallic compounds may be employed as scavenging agents for poisons to increase the catalyst activity. The polymerization processes may be carried out batchwise, continuously run, or any combinations thereof. In one non-limiting embodiment, the polymerization processes of the M
  • present disclosure are carried out in a continuous gas-phase reactor.
  • polymerization processes of the disclosure are carried out in a single gas-phase reactor.
  • Preferred processes for the invention are high-pressure, solution, slurry and gas-phase processes.
  • a gas-phase process of the present disclosure may comprise contacting the catalyst system with monomers in a reactor vessel of desirable configuration to form a polyolefin.
  • the contacting may take place in a first reactor vessel, followed by transfer of the formed polymer into another reactor vessel to allow further polymerization, optionally by adding the same or different monomers and optionally by adding the same or different catalyst components, activators, etc.
  • the catalyst system is contacted with monomers in a single reactor vessel, followed by isolation of a finished polyolefin resin.
  • a gas phase polymerization process of the disclosure may comprise use of a continuous cycle in which a cycling gas stream (i.e., a recycle stream or fluidizing medium) is heated in the reactor by the heat of polymerization. This heat may be removed from the recycle stream in another part of the cycle by a cooling system that is external to the reactor.
  • a cycling gas stream i.e., a recycle stream or fluidizing medium
  • This heat may be removed from the recycle stream in another part of the cycle by a cooling system that is external to the reactor.
  • a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers may be continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is preferably withdrawn from the fluidized bed and then recycled back into the reactor. Polymer product may be withdrawn from the reactor and fresh monomer added to replace the polymerized monomer.
  • the gas-phase reactor utilized in the present invention is capable and the process of the invention is producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
  • the reactor temperature in a gas phase process may vary from about 30°C to about 12O 0 C, preferably from about 60 0 C to about 115 0 C, more preferably in the range of from about 70 0 C to 110 0 C, and most preferably in the range of from about 70 0 C to about 95°C.
  • any one or more additives such as an antistatic or an alcohol may be used in the polymerization processes of the present disclosure, for example to improve the particle morphology of the olefin polymer.
  • any one or more of the numerous additives suitable in olefin polymerization processes to improve any one or more parameter such as but not limited to reactor operability, particle morphology, catalyst activity, catalyst performance, and polymerization efficiency.
  • the one or more additives may be fed directly into the polymerization system, either together with or separately from the catalyst system.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed.
  • Preferred processes for the invention are high-pressure, solution, slurry and gas-phase processes. More preferred processes are slurry and gas-phase processes.
  • the high molecular weight polymer generally has a weight average molecular weight (Mw) of greater than about 1 million g/mol, preferably greater than about 1.5 million g/mol, even more preferably greater than about 2 million g/mol, and still more preferably greater than about 3 million g/mol.
  • Mw weight average molecular weight
  • the low molecular weight polymer has an Mw in the range of from about 40,000 to about 200,000 g/mol, preferably from about 50,000 to about 180,000 g/mol, more preferably from about 60,000 to about 175,000 g/mol, and even more preferably from about 70,000 to about 150,000 g/mol.
  • the polymers of the disclosure comprise a high molecular weight component and a low molecular weight component.
  • high molecular weight is defined herein as being greater than about 1,000,000 g/mol, preferably greater than about 1,500,000 g/mol, more preferably greater than about 2,000,000 g/mol, and even more preferably greater than about 3,000,000 g/mol. In one non-limiting embodiment, high molecular weight is greater than 5,000,000 g/mol.
  • low molecular weight is defined herein as being in the range of from about 40,000 to about 200,000 g/mol, preferably from about 50,000 to about 180,000 g/mol, more preferably from about 60,000 to about 175,000 g/mol, and even more preferably from about 70,000 to about 150,000 g/mol. In one non-limiting embodiment, low molecular weight is about 100,000 g/mol.
  • the high molecular weight component comprises a molecular weight at least 10 times greater than the low molecular weight component, preferably at least 20 times greater than that of the low molecular weight component, more preferably at least 30 times greater than that of the low molecular weight component, and even more preferably at least 40 times greater than that of the low molecular weight component.
  • the polymers of the disclosure may have a density in the range of from about 0.86g/cc to 0.97 g/cm 3 as measured according to ASTM 1505-03.
  • the polymers of the present disclosure may have a melt index ("MI” or "I 2 ”) as measured by ASTM-D- 1238-E (190°C, 2.16 kg weight) in the range of from .001 dg/min to 25 dg/min.
  • MI melt index
  • ASTM-D- 1238-E 190°C, 2.16 kg weight
  • the polymers of the present disclosure may have a MI in a range of from about 0.001 dg/min to about 5 dg/min; in even other non-limiting embodiments a MI in a range of from about 0.01 dg/min to about 5 dg/min in other embodiments; and in still other non-limiting embodiments a MI in a range of from about 0.01 dg/min to about 1 dg/min.
  • the polymers of the present disclosure may have a melt flow ratio (MFR) in the range of from about 10 to 300.
  • MFR is defined as WI 2 , wherein I 2) is measured by ASTM-D- 1238-F, at 190°C, 21.6 kg weight.
  • the polymers of the present disclosure may have a MFR in a range of from about 15 to 250; in even other non- limiting embodiments, a MFR in a range of from about 15 to 200; and in still other non-limiting embodiments a MFR in a range of from about 20 to 150.
  • the extensional viscosity of a polymer increases with time.
  • the transient uniaxial extensional viscosity of a linear polymer can be predicted. Strain hardening occurs when a polymer is subjected to uniaxial extension and the transient extensional viscosity increases more than what is predicted from linear viscoelastic theory.
  • the strain hardening index is the ratio of the observed transient uniaxial extensional viscosity to the theoretically predicted transient uniaxial extensional viscosity. Strain hardening index is expressed herein as the following ratio: ⁇ E + observed / ⁇ E + predicted.
  • the strain hardening index of the polymers of the present disclosure is a ratio/value greater than 3 in some embodiments, a value greater than 5 in other embodiments, a value greater than 8 in even other embodiments, and a value greater than 10 in still other embodiments.
  • the polymers of the present disclosure may be characterized in that they exhibit an activation energy (Ea) of less than 7 kcal/mol/K. In other non-limiting embodiments, the Ea of the polymers of the present disclosure may be less than 6 kcal/mol/K.
  • FIG. 1 there are shown van Gurp-Palmen (vGP or VGP) plots of various linear polyethylene resins: a conventional monodispersed PE (hydrogenated polyputadiene) (closed circles), a conventional metallocene LLDPE resin with a narrow molecular weight distribution (closed squares), a conventional bimodal resin having a broad molecular weight distribution (asterisk), and an inventive resin of the disclosure (closed diamonds).
  • the molecular weights and molecular weight distributions of the conventional resins are shown in Table 1 below. Increasing polydispersity in comparative conventional resins stretches the curve along the abscissa, but does not change the monotonic nature of the vGP plot (note how their curves in FIG. 1 become less 3y
  • the resin (ExceedTM1018) and the bimodal resin (BorougeTM FB 2230) are commercially available resins.
  • the introduction of a high molecular weight fraction according to the disclosure may change the shape of the vGP plot in that it causes a maximum in the vGP plot as shown in FIG. 1.
  • the ratio of the z-average molecular weight (Mz) to the weight average molecular weight (Mw) of the polymers of the present disclosure may be a ratio having a value in a range of from about 6 to 12. In other non-limiting embodiments, the Mz/Mw ratio may be a value in a range of from about 7 to 15. In even other non-limiting embodiments, the Mz/Mw ratio may be a value greater than 10.
  • the ratio of the Mw to the number average molecular weight (Mn) (ratio of Mw/Mn is also referred to as polydispersity) can be in the range of from 2.5 to 8 in some non-limiting embodiments, from 3.0 to 10 in other non-limiting embodiments, and from 3.5 to 12 in even other non-limiting embodiments.
  • the Mz/Mw ratio is a value greater than the Mw/Mn ratio.
  • Mn is the number average molecular weight and may be expressed as ⁇ (M,N,)/ ⁇ N
  • Mw is the weight average molecular weight and may be expressed as Z(M 1 2 N 1 )ZX(M 1 N 1 );
  • Mz is the z-average molecular weight of a polymer and may be expressed as ⁇ (M, N,)/ ⁇ (M, N 1 ) wherein Ni is the number of molecules of molecular weight Mi. Techniques for determining these values are known in the art and any may be used herein.
  • the polymers of the disclosure generally show very high viscosities at low shear rates and exhibit strong shear thinning.
  • a shear thinning index may be expressed as the ratio of the complex viscosities ( ⁇ * ) at two given- oscillatory shear frequencies, arbitrarily selected herein to be 0.01 rad/sec ( ⁇ * o.oi) and 100 rad/sec ( ⁇ * ioo)-
  • the shear thinning index is expressed herein as C ⁇ * o.oi)/( ⁇ * ioo)- Both ( ⁇ * o.oi) and ( ⁇ * ioo) are obtained from oscillatory shear rheometry as described herein.
  • the shear thinning index ( ⁇ * o.oi/ ⁇ * ioo) of the polymers of the present disclosure may be a value in the range of 5 to 500.
  • the shear thinning index may be in the range of 25 to 500. In even other embodiments, the shear thinning index may be in the range of 50 to 500. In still other embodiments, the shear thinning index may be in the range of 100 to 500.
  • the molecular weights and molecular weight distributions of the resins described in the present disclosure were characterized using a High Temperature Size Exclusion Chromatograph (PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel 10mm Mixed-B columns were used. The nominal flow rate was 1.0 cm 3 /min, and the nominal injection volume was 300 ⁇ L. The various transfer lines, columns and differential refractometer (the DRI detector) were contained in an oven maintained at 160 C.
  • STEP 2 15g (0.067mol, leq) of l-Bromo-2-methyl naphthalene, 0.4g ( 5mol% ) of palladium tetrakis, 16g ( O.O ⁇ lmol, 1.2eq) of -0-MOM boronic acid, 29g of 2M solution of sodium carbonate and 150ml of toluene were taken in a RB to
  • PC precatalysts
  • toluene was added at a rate of ca. 0.5 mL/min to a slurry SMAO and pentane (amounts provided in Table 2 below), stirred with an overhead stirrer. After stirring for > 30 min, the mixture was filtered and dried in-vacuo.
  • Ethylene/ 1-hexene copolymers were produced according to the following procedure.
  • the catalyst composition was injected dry into a fluidized bed gas phase polymerization reactor. More particularly, polymerization was conducted in a 152.4 mm diameter gas-phase fluidized bed reactor operating at approximately 2068 kPa total pressure.
  • the reactor bed weight was approximately 2 kg.
  • Fluidizing gas was passed through the bed at a velocity of approximately 0.6 m per second.
  • the fluidizing gas exiting the bed entered a resin disengaging zone located at the upper portion of the reactor.
  • the fluidizing gas then entered a recycle loop and passed through a cycle gas compressor and water-cooled heat exchanger.
  • the shell side water temperature was adjusted to maintain the reactor temperature as specified in Tables 4-8.
  • C 6 ZC 2 flow ratio is the ratio of the lbs of 1- hexene comonomer feed to the pounds of ethylene feed to the reactor, whereas the C 6 ZC 2 ratio is the ratio of the gas concentration of 1-hexene moles in the cycle gas to the gas concentration of ethylene moles in the cycle gas.
  • the C 6 ZC 2 ratio is obtained from a cycle gas vapor fraction analyzer, whereas the C 6 ZC 2 Flow Ratio comes from some measure of the mass flow.
  • the cycle gas is the gas in the reactor, and is measured from a tap off the recirculating loop around the reactor. The ratios reported in the following tables are from the gas concentrations in the reactor. Samples are taken every 9 min, and thus reported C 6 ZC 2 ratios are running averages. Tables 4-8 provide summaries of run conditions and product properties / i
  • Table 7A Summary of Process Data - resin density 0.94 /y
  • melt strength is defined as the force required to draw a molten polymer extrudate at a rate of 12mm/s 2 and at an extrusion temperature (190 0 C and 250 0 C were used herein) until breakage of the extrudate whereby the force is applied by take up rollers.
  • the polymer is extruded at a velocity of 0.33 mm/s through an annular die of 2 mm diameter and 30 mm length.
  • Melt strength values reported herein are determined using a Gottfert Rheotens tester and are reported in centi-Newtons (cN). Additional experimental parameters for determining the melt strength are listed in Table 9. For the measurements of melt strength, the resins were stabilized with 500 ppm of Irganox 1076 and 1500 ppm of Irgafosl68.
  • strain hardening occurs when a polymer is subjected to uniaxial extension and the transient extensional viscosity increases more than what is predicted from linear viscoelastic theory.
  • strain hardening index is the ratio of the observed transient uniaxial extensional viscosity (j
  • the resins were stabilized with 500 ppm of Irganox 1076 and 1500 ppm of Irgafosl68.
  • the transient uniaxial extensional viscosity was measured at temperatures of 150 0 C and 190 0 C and different strain rates, 0.1 sec "1 , 1.0 sec "1 , and 10 sec “1 .
  • the transient uniaxial extensional viscosity can be measured using a SER-HV -401 Testing Platform, which is commercially available from Xpansion Instruments LLC, Tallmadge, OH, USA.
  • the SER Testing Platform was used on a Rheometrics ARES-LS rotational rheometer, which is available from TA Instruments.

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Abstract

An ethylene polymer including units derived from ethylene, at least one other alpha-olefin comonomer, and at least one diene, and having at least one of certain properties disclosed herein.

Description

ETHYLENE POLYMERS
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of Serial No. 61/003,181, filed November 15, 2007, the disclosure of which is incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] An ethylene polymer including units derived from ethylene, at least one other alpha-olefin comonomer, and at least one diene, and having at least one of certain properties discuseed in more detail below.
BACKGROUND
[0003] The use of metallocene compounds in polymerization catalysts, and the use of metallocene catalysts for polymerization are known. However, there remains an ongoing effort to develop metallocene catalysts, polymerization processes using such catalysts, and polyolefin resins and products made therewith, each having advantageous properties and performance.
[0004] There are numerous references discussing metallocene catalyst systems comprising at least two catalyst components, wherein at least one component is a metallocene catalyst. See, for example, U.S. Patent Nos. 4,530,914,. 4,937,299, 5,470,811, 5,516,848, 5,696,045, 6, 492,472, 7,141,632, 7,163,906, 7,172,987, and EP-A2-0 743 327, EP-B 1-0 310 734, EP-B 1-516 018.
[0005] Additionally, there are also references directed to polymerization processes in which two or more polymerization reactors are joined in series, where one catalyst is used in a first reactor to produce a first polymer that is then fed into a second reactor with the same or different catalyst, typically under different reactor conditions. See, for example, U.S. Patent No. 5,665,818 and EP- B l-O 527 221. However, series or multistage reactor processes are expensive and more difficult to operate. [0006] Thus, there remains a need for new processes, including new combinations of comonomer constituents, to produce novel polymers.
SUMMARY
[0007] According to one embodiment there is provided an ethylene polymer comprising units derived from ethylene, at least one other alpha-olefin comonomer, and at least one diene, and having at least one of the following properties: (i) melt strength value greater than 6*Mr0'6675, wherein MI is the melt index value of said polymer measured in accordance with ASTM-D-1238-E, (ii) a ratio of extensional viscosity measured at a strain rate of 1 sec"1, 19O0C, and time=4 seconds to that predicted by linear viscoelasticity at the same temperature and time of greater than 3, (iii) an activation energy (E3) of less than 7 kcal/mol/K, (iv) a Mz/Mw ratio greater than the Mw/Mn ratio, wherein Mz is the z-average molecular weight of said polymer, Mw is the weight average molecular weight of said polymer, Mn is the number average molecular weight of said polymer, and v) a van Gurp-Palmen plot comprising a positive slope and possessing a maximum, wherein the van Gurp-Palmen plot is a plot of the phase angle versus the absolute value of the complex shear modulus determined from dynamic rheology, more particularly, from frequency sweeps in the range from 0.01 to 100 rad/s at 190°C.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 provides a comparison of Van Gurp-Palmen plots of non-limiting example resins of the disclosure and conventional resins.
[0009] FIG. 2 provides a comparison of the melt strengths of non-limiting example resins of the disclosure and conventional resins having low MI.
[0010] FIG. 3 depicts the transient uniaxial extensional viscosity of non-limiting example resin 3 of the disclosure as a function of time.
[0011] FIG. 4 provides a comparison of the shear thinning characteristics of a non-limiting example resin of the disclosure and a control resin.
[0012] FIG. 5 provides a comparison of non-limiting example resins of the disclosure and conventional resins. [0013] FIG. 6 provides a comparison of Van Gurp-Palmen plots of non-limiting example resins of the disclosure and a control resin.
[0014] FIG. 7 provides a comparison of Van Gurp-Palmen plots of non-limiting example resins of the disclosure and conventional resins.
DETAILED DESCRIPTION
[0015] It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless otherwise specified. Thus, for example, reference to "a leaving group" as in a moiety "substituted with a leaving group" includes more than one leaving group, such that the moiety may be substituted with two or more such groups. Similarly, reference to "a halogen atom" as in a moiety "substituted with a halogen atom" includes more than one halogen atom, such that the moiety may be substituted with two or more halogen atoms, reference to "a substituent" includes one or more substituents, reference to "a ligand" includes one or more ligands, and the like.
[0016] As used herein, the phrase "characterized by the formula" is not intended to be limiting and is used in the same way that "comprising" is commonly used. The term "independently selected" is used herein to indicate that the R groups, e.g., R1, R2, R3, R4, and R5 can be identical or different (e.g. R1, R2, R3, R4, and R5 may all be substituted alkyls or R1 and R2 may be a substituted alkyl and R3 may be an aryl, etc.). Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name.
[0017] The terms "compound" and "complex" are generally used interchangeably in this specification, but those of skill in the art may recognize certain compounds as complexes and vice versa.
[0018] The terms "precatalyst", "catalyst", "precatalyst metal compound", "catalyst metal compound", "catalyst component" are generally used interchangeably in this specification, but those of skill in the art may recognize certain precatalysts as catalysts and vice versa. [0019] The terms "monomer" and "comonomer" are generally used interchangeably in this specification, but those of skill in the art may recognize certain monomers as comonomers and vice versa.
[0020] For the purposes of illustration, representative certain groups are defined herein. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the phrase "optionally substituted hydrocarbyl" means that a hydrocarbyl moiety may or may not be substituted and that the description includes both unsubstituted hydrocarbyl and hydrocarbyl where there is substitution.
[0021] The term "alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group typically although not necessarily containing 1 to about 50 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein may contain 1 to about 12 carbon atoms. The term "lower alkyl" intends an alkyl group of one to six carbon atoms, specifically one to four carbon atoms. The term alkyl also refers to divalent alkyls such as -CR2- which may be referred to as alkylenes or hydrocarbylenes and may be substituted with one or more substituent groups or heteroatom containing groups. "Substituted alkyl" refers to alkyl substituted with one or more substituent groups (e.g., benzyl or chloromethyl), and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to alkyl in which at least one carbon atom is replaced with a heteroatom (e.g., --CH2OCH3 is an example of a heteroalkyl).
[0022] The term "alkenyl" as used herein refers to a branched or unbranched hydrocarbon group typically although not necessarily containing 2 to about 50 carbon atoms and at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, and the like. Generally, although again not necessarily, alkenyl groups herein contain 2 to about 12 carbon atoms. The term "lower alkenyl" intends an alkenyl group of two to six carbon atoms, specifically two to four carbon atoms. "Substituted alkenyl" refers to alkenyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" refer to alkenyl in which at least one carbon atom is replaced with a heteroatom.
[0023] The term "alkynyl" as used herein refers to a branched or unbranched hydrocarbon group typically although not necessarily containing 2 to about 50 carbon atoms and at least one triple bond, such as ethynyl, n-propynyl, isopropynyl, n-butynyl, isobutynyl, octynyl, decynyl, and the like. Generally, although again not necessarily, alkynyl groups herein may have 2 to about 12 carbon atoms. The term "lower alkynyl" intends an alkynyl group of two to six carbon atoms, specifically three or four carbon atoms. "Substituted alkynyl" refers to alkynyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkynyl" and "heteroalkynyl" refer to alkynyl in which at least one carbon atom is replaced with a heteroatom.
[0024] The term "alkoxy" as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy" group may be represented as — O-alkyl where alkyl is as defined above. A "lower alkoxy" group intends an alkoxy group having one to six, more specifically one to four, carbon atoms. The term "aryloxy" is used in a similar fashion, with aryl as defined below. The term "hydroxy" refers to -OH.
[0025] Similarly, the term "alkylthio" as used herein intends an alkyl group bound through a single, terminal thioether linkage; that is, an "alkylthio" group may be represented as — S-alkyl where alkyl is as defined above. A "lower alkyl thio" group intends an alkyl thio group having one to six, more specifically one to four, carbon atoms. The term "arylthio" is used similarly, with aryl as defined below. The term "thioxy" refers to -SH.
[0026] The term "aryl" as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. More specific aryl groups contain one aromatic ring or two or three fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, and the like. In particular embodiments, aryl substituents have 1 to about 200 carbon atoms, typically 1 to about 50 carbon atoms, and specifically 1 to about 20 carbon atoms. "Substituted aryl" refers to an aryl moiety substituted with one or more substituent groups, (e.g., tolyl, mesityl and perfluorophenyl) and the terms "heteroatom-containing aryl" and "heteroaryl" refer to aryl in which at least one carbon atom is replaced with a heteroatom (e.g., rings such as thiophene, pyridine, isoxazole, pyrazole, pyrrole, furan, etc. or benzo-fused analogues of these rings are included in the term "heteroaryl"). In some embodiments herein, multi-ring moieties are substituents and in such an embodiment the multi-ring moiety can be attached at an appropriate atom. For example, "naphthyl" can be 1-naphthyl or 2-naphthyl; "anthracenyl" can be 1- anthracenyl, 2-anthracenyl or 9-anthracenyl; and "phenanthrenyl" can be 1- phenanthrenyl, 2-phenanthrenyl, 3 -phenanthrenyl, 4-phenanthrenyl or 9- phenanthrenyl.
[0027] The term "aralkyl" refers to an alkyl group with an aryl substituent, and the term "aralkylene" refers to an alkylene group with an aryl substituent; the term "alkaryl" refers to an aryl group that has an alkyl substituent, and the term "alkarylene" refers to an arylene group with an alkyl substituent.
[0028] The terms "halo" and "halogen" and "halide" are used in the conventional sense to refer to a chloro, bromo, fluoro or iodo substituent. The terms "haloalkyl," "haloalkenyl" or "haloalkynyl" (or "halogenated alkyl," "halogenated alkenyl," or "halogenated alkynyl") refers to an alkyl, alkenyl or alkynyl group, respectively, in which at least one of the hydrogen atoms in the group has been replaced with a halogen atom.
[0029] The term "heteroatom-containing" as in a "heteroatom-containing hydrocarbyl group" refers to a molecule or molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus, boron or silicon. Similarly, the term "heteroalkyl" refers to an alkyl substituent that is heteroatom-containing, the term "heterocyclic" refers to a cyclic substituent that is heteroatom-containing, the term "heteroaryl" refers to an aryl substituent that is heteroatom-containing, and the like. When the term "heteroatom-containing" appears prior to a list of possible heteroatom- containing groups, it is intended that the term apply to every member of that group. That is, the phrase "heteroatom-containing alkyl, alkenyl and alkynyl" is to be interpreted as "heteroatom-containing alkyl, heteroatom-containing alkenyl and heteroatom-containing alkynyl."
[0030] "Hydrocarbyl" refers to hydrocarbyl radicals containing 1 to about 50 carbon atoms, specifically 1 to about 24 carbon atoms, most specifically 1 to about 16 carbon atoms, including branched or unbranched, saturated or unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term "lower hydrocarbyl" intends a hydrocarbyl group of one to six carbon atoms, specifically one to four carbon atoms. "Substituted hydrocarbyl" refers to hydrocarbyl substituted with one or more substituent groups, and the terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom.
[0031] By "substituted" as in "substituted hydrocarbyl," "substituted aryl," "substituted alkyl," "substituted alkenyl" and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, hydrocarbylene, alkyl, alkenyl, aryl or other moiety, at least one hydrogen atom bound to a carbon atom is replaced with one or more substituents that are functional groups such as hydroxyl, alkoxy, alkylthio, phosphino, amino, halo, silyl, and the like. When the term "substituted" appears prior to a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase "substituted alkyl, alkenyl and alkynyl" is to be interpreted as "substituted alkyl, substituted alkenyl and substituted alkynyl." Similarly, "optionally substituted alkyl, alkenyl and alkynyl" is to be interpreted as "optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl."
[0032] By "divalent" as in "divalent hydrocarbyl", "divalent alkyl", "divalent aryl" and the like, is meant that the hydrocarbyl, alkyl, aryl or other moiety is bonded at two points to atoms, molecules or moieties with the two bonding points being covalent bonds. The term "aromatic" is used in its usual sense, including unsaturation that is essentially delocalized across multiple bonds, such as around a ring.
[0033] As used herein the term "silyl" refers to the -SiZ1Z2Z3 radical, where each
1 0 "X of SiZ Z Z is independently selected from the group consisting of hydride and optionally substituted alkyl, alkenyl, alkynyl, heteroatom-containing alkyl, heteroatom-containing alkenyl, heteroatom-containing alkynyl, aryl, heteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.
[0034] As used herein the term "boryl" refers to the -BZ1Z2 group, where each of Z1 and Z2 is as defined above. As used herein, the term "phosphino" refers to the group -PZ1Z2, where each of Z1 and Z2 is as defined above. As used herein, the term "phosphine" refers to the group: PZ1Z2Z3, where each of Z1, Z2, Z3 as defined above. The term "amino" is used herein to refer to the group -NZ1Z2, where each of Z1 and Z2 is as defined above. The term "amine" is used herein to refer to the group: NZ1Z2Z3, where each of Z1, Z2, Z3 is as defined above.
[0035] The term "saturated" refers to lack of double and triple bonds between atoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, and the like. The term "unsaturated" refers to the presence of one or more double and triple bonds between atoms of a radical group such as vinyl, acetylide, oxazolinyl, cyclohexenyl, acetyl and the like.
Catalysts
[0036] It is contemplated that any suitable polymerization catalyst may be practiced with embodiments of the invention, or any combination of polymerization catalysts may be practiced with embodiments of the invention. Illustrative embodiments are listed below.
Conventional Catalyst
[0037] Conventional catalysts are those traditional Ziegler-Natta catalysts and Phillips-type chromium catalyst well known in the art. Examples of conventional- type transition metal catalysts are disclosed in U.S. Pat. Nos. 4,115,639, 4,077,904 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741. The conventional- type transition metal catalyst compounds that may be used in the present invention include, but are not limited to transition metal compounds from Groups III to VIII of the Periodic Table of the Elements. All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by the International Union of Pure and Applied Chemistry, Inc., 2004. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
[0038] These conventional-type transition metal catalysts may be represented by the formula: MRx, where M is a metal from Groups HIB to VIII, preferably Group IVB, more preferably titanium; R is a halogen or a hydrocarbyloxy group; and x is the valence of the metal M. Non-limiting examples of R may include alkoxy, phenoxy, bromide, chloride and fluoride. Conventional-type transition metal catalysts where M is titanium may include, but are not limited to, TiC14, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)C13, Ti(OC4H9)3 Cl, Ti(OC3H7)2C12, Ti(OC2H5)2Br2, TiC13.1/3AlC13 and Ti(OC 12H25)C13.
[0039] Conventional-type transition metal catalyst compounds based on magnesium/titanium electron-donor complexes that are useful in the invention are described in, for example, U.S. Pat. Nos. 4,302,565 and 4,302,566. The MgTiCIo (ethyl acetate)4 derivative is one such example. British Patent Application 2,105,355 describes various conventional-type vanadium catalyst compounds. Non-limiting examples of conventional-type vanadium catalyst compounds include vanadyl trihalide, alkoxy halides and alkoxides such as VOC13, VOC12(OBu) where Bu=butyl and VO(OC2 H5)3 ; vanadium tetra-halide and vanadium alkoxy halides such as VC14 and VCB(OBu); vanadium and vanadyl acetyl acetonates and chloroacetyl acetonates such as V(AcAc)3 and VOC12(AcAc) where (AcAc) is an acetyl acetonate. Examples of conventional- type vanadium catalyst compounds are VOC13, VC14 and VOC12— OR where R is a hydrocarbon radical, preferably a Cl to ClO aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-biityl, tertiary- butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates. [0040] Conventional-type chromium catalyst compounds, often referred to as Phillips-type catalysts, suitable for use in the present invention may include CrCβ, chromocene, silyl chromate, chromyl chloride (CrO2C12), chromium-2-ethyl- hexanoate, chromium acetylacetonate (Cr(AcAc)3), and the like. Non-limiting examples are disclosed in, for example, U.S. Pat. Nos. 3,242,099 and 3,231,550.
[0041] Still other conventional-type transition metal catalyst compounds and catalyst systems suitable for use in the present invention are disclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566 and 5,763,723 and published EP-A2 0 416 815 A2 and EP-Al 0 420 436. The conventional-type transition metal catalysts of the invention may also have the general formula M'lM"X2t Yu E, where M' is Mg, Mn and/or Ca; t is a number from 0.5 to 2; M" is a transition metal Ti, V and/or Zr; X is a halogen, preferably Cl, Br or I; Y may be the same or different and is halogen, alone or in combination with oxygen, — NR.sub.2, —OR, -SR, — COOR, or — OSOOR, where R is a hydrocarbyl radical, in particular an alkyl, aryl, cycloalkyl or arylalkyl radical, acetylacetonate anion in an amount that satisfies the valence state of M'; u is a number from 0.5 to 20; E is an electron donor compound selected from the following classes of compounds: (a) esters of organic carboxylic acids; (b) alcohols; (c) ethers; (d) amines; (e) esters of carbonic acid; (f) nitriles; (g) phosphoramides, (h) esters of phosphoric and phosphorus acid, and (j) phosphorus oxy-chloride. Non-limiting examples of complexes satisfying the above formula include: MgTiC15.2CH3COOC2H5,
Mg3Ti2C1127CH3COOC2H5, MgTiC15.6C2H5OH, MgTiC15.100CH3OH, MgTiC15 tetrahydrofuran, MgTi2C1127C6H5CN, MgTi2 C1126C6H5COOC2H5, MgTiC162CH3COOC2H5, MgTiC166C5H5N, MgTiC15(OCH3)2CH3COOC2H5, MgTiC15N(C6H5)23CH3COOC2H5, MgTiBr2C142(C2H5)O,
MnTiC154C2H5OH, Mg3V2 Cl 12. 7CH3COOC2H5, MgZrC164tetrahydrofuran. Other catalysts may include cationic catalysts such as A1C13, and other cobalt and iron catalysts well known in the art.
[0042] The conventional-type transition metal catalyst compounds disclosed herein may be activated with one or more of the conventional-type cocatalysts described below. Cocatalysts And Other Components
[0043] Conventional-type cocatalyst compounds for the above conventional-type transition metal catalyst compounds may be represented by the formula M3M4v X2c R3b-c, wherein M3 is a metal from Group IA, IIA, HB and IIIA of the Periodic Table of Elements; M4 is a metal of Group IA of the Periodic Table of Elements; v is a number from 0 to 1; each X2 is any halogen; c is a number from 0 to 3; each R3 is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4; and wherein b minus c is at least 1. Other conventional-type organometallic cocatalyst compounds for the above conventional-type transition metal catalysts have the formula M3R3k, where M3 is a Group IA, IIA, HB or IIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3 depending upon the valency of M3 which valency in turn normally depends upon the particular Group to which M3 belongs; and each R3 may be any monovalent hydrocarbon radical.
[0044] Examples of conventional-type organometallic cocatalyst compounds of Group IA, IIA and IIIA useful with the conventional-type catalyst compounds described above include, but are not limited to, methyllithium, butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium, di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminum alkyls, such as tri-hexyl- aluminum, triethylaluminum, trimethylaluminum, and tri-isobutylaluminum. Other conventional-type cocatalyst compounds may include mono-organohalides and hydrides of Group IIA metals, and mono- or di-organohalides and hydrides of Group IHA metals. Non-limiting examples of such conventional-type cocatalyst compounds may include di-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, ethylberyllium chloride, ethylcalcium bromide, di- isobutylaluminum hydride, methylcadmium hydride, diethylboron hydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminum hydride and bromocadmium hydride. Conventional-type organometallic cocatalyst compounds are known to those in the art and a more complete discussion of these compounds may be found in U.S. Pat. Nos. 3,221,002 and 5,093,415.
Metallocene Catalysts
[0045] The catalyst system may include at least one metallocene catalyst component. The metallocene catalyst component may include "half sandwich" and "full sandwich" compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one metal atom. Hereinafter, these compounds will be referred to as "metallocenes" or "metallocene catalyst components".
[0046] In one aspect, the one or more metallocene catalyst components are represented by the formula (I):
CpACpBMXn (I)
[0047] The metal atom "M" of the metallocene catalyst compound, as described throughout the specification and claims, may be selected from the group consisting of Groups 3 through 12 atoms and lanthanide Group atoms in one embodiment; and selected from the group consisting of Groups 3 through 10 atoms in a more particular embodiment, and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selected from the group consisting of Groups 4, 5 and 6 atoms in yet a more particular embodiment, and a Ti, Zr, Hf atoms in yet a more particular embodiment, and Zr in yet a more particular embodiment. The oxidation state of the metal atom "M" may range from 0 to +7 in one embodiment; and in a more particular embodiment, is +1, +2, +3, +4 or +5; and in yet a more particular embodiment is +2, +3 or +4. The groups bound the metal atom "M" is such that the compounds described below in the formulas and structures are neutral, unless otherwise indicated. The Cp ligand(s) form at least one chemical bond with the metal atom M to form the "metallocene catalyst compound". The Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.
[0048] M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; and n is 0 or an integer from 1 to 4, and either 1 or 2 in a particular embodiment.
[0049] The ligands represented by CpA and CpB in formula (I) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms and either or both of which may be substituted by a group R. In one embodiment, CpA and CpB are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
[0050] Independently, each CpA and CpB of formula (I) may be unsubstituted or substituted with any one or combination of substituent groups R. Non-limiting examples of substituent groups R as used in structure (I) include hydrogen radicals, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys, aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryls, heteroatom- containing groups, silyls, boryls, phosphinos, phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof.
[0051] More particular non-limiting examples of alkyl substituents R associated with formula (i) includes methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like. Other possible radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethyl sulfide. Other substituents R include olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like. In one embodiment, at least two R groups, two adjacent R groups in one embodiment, are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof. Also, a substituent group R group such as 1-butanyl may form a bonding association to the element M.
[0052] Each X in formula (I) is independently selected from the group consisting of: any leaving group in one embodiment; halogen ions, hydrides, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys, aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryls, heteroatom-containing groups, silyls, boryls, phosphinos, phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof. In another embodiment, X is Ci to Ci2 alkyls, C2 to Ci2 alkenyls, C6 to Ci2 aryls, C7 to C2o alkylaryls, Ci to Ci2 alkoxys, C6 to Ci6 aryloxys, C7 to Ci8 alkylaryloxys, Ci to Ci2 fluoroalkyls, C6 to Ci2 fluoroaryls, and Ci to Ci2 heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular embodiment; hydride, halogen ions, Ci to C6 alkyls, C2 to C6 alkenyls, C7 to Q8 alkylaryls, Ci to C6 alkoxys, C6 to C)4 aryloxys, C7 to Ci6 alkylaryloxys, Ci to C6 alkylcarboxylates, Ci to C6 fluorinated alkylcarboxylates, C6 to Ci2 arylcarboxylates, C7 to C)8 alkylarylcarboxylates, Ci to C6 fluoroalkyls, C2 to C6 fluoroalkenyls, and C7 to Ci8 fluoroalkylaryls in yet a more particular embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyl in yet a more particular embodiment; Ci to Ci2 alkyls, C2 to Ci2 alkenyls, C6 to Ci2 aryls, C7 to C2o alkylaryls, substituted Ci to Ci2 alkyls, substituted C6 to C]2 aryls, substituted C7 to C2o alkylaryls and Ci to Ci2 heteroatom-containing alkyls, Cj to Ci2 heteroatom-containing aryls and Ci to Ci2 heteroatom-containing alkylaryls in yet a more particular embodiment; chloride, fluoride, Ci to C6 alkyls, C2 to C6 alkenyls, C7 to Cis alkylaryls, halogenated C) to C6 alkyls, halogenated C2 to C6 alkenyls, and halogenated C7 to Ci8 alkylaryls in yet a more particular embodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyl (mono-, di-, tri-, tetra- and pentafluorophenyls) in yet a more particular embodiment.
[0053] Other non-limiting examples of X groups in formula (I) include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., -C6F5 (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF3C(O)O"), hydrides and halogen ions and combinations thereof. Other examples of X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N- methylanilide), dimethylamide, dimethylphosphide radicals and the like. In one embodiment, two or more X's form a part of a fused ring or ring system.
[0054] In another aspect, the metallocene catalyst component includes those of formula (I) where CpA and CpB are bridged to each other by at least one bridging group, (A), such that the structure is represented by formula (II):
CpA(A)CpBMXn (II) [0055] These bridged compounds represented by formula (II) are known as "bridged metallocenes". CpA, CpB, M, X and n are as defined above for formula (I); and wherein each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp. Non-limiting examples of bridging group (A) include divalent alkyls, divalent lower alkyls, divalent substituted alkyls, divalent heteroalkyls, divalent alkenyls, divalent lower alkenyls, divalent substituted alkenyls, divalent heteroalkenyls, divalent alkynyls, divalent lower alkynyls, divalent substituted alkynyls, divalent heteroalkynyls, divalent alkoxys, divalent lower alkoxys, divalent aryloxys, divalent alkylthios, divalent lower alkyl thios, divalent arylthios, divalent aryls, divalent substituted aryls, divalent heteroaryls, divalent aralkyls, divalent aralkylenes, divalent alkaryls, divalent alkarylenes, divalent haloalkyls, divalent haloalkenyls, divalent haloalkynyls, divalent heteroalkyls, divalent heterocycles, divalent heteroaryls, divalent heteroatom-containing groups, divalent hydrocarbyls, divalent lower hydrocarbyls, divalent substituted hydrocarbyls, divalent heterohydrocarbyls, divalent silyls, divalent boryls, divalent phosphinos, divalent phosphines, divalent aminos, divalent amines, divalent ethers, divalent thioethers. Additional non-limiting examples of bridging group A include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom and combinations thereof; wherein the heteroatom may also be C1 to Ci2 alkyl or aryl substituted to satisfy neutral valency. The bridging group (A) may also contain substituent groups R as defined above for formula (I) including halogen radicals and iron. More particular non-limiting examples of bridging group (A) are represented by Ci to C6 alkylenes, substituted Ci to C6 alkylenes, oxygen, sulfur, R'2C=, R'2Si=, — Si(R')2Si(R'2)— , R'2Ge=, R'P= (wherein "=" represents two chemical bonds), where R' is independently selected from the group consisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted Group 15 atoms, substituted Group 16 atoms, and halogen radical; and wherein two or more R' may be joined to form a ring or ring system. In one embodiment, the bridged metallocene catalyst component of formula (II) has two or more bridging groups (A).
[0056] Other non-limiting examples of bridging group (A) include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2- dimethylethylene, 1 ,2-diphenylethylene, 1 , 1 ,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n- hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t- butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and the corresponding moieties wherein the Si atom is replaced by a Ge or a C atom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.
[0057] In another embodiment, bridging group (A) may also be cyclic, comprising, for example 4 to 10, 5 to 7 ring members in a more particular embodiment. The ring members may be selected from the elements mentioned above, from one or more of B, C, Si, Ge, N and O in a particular embodiment. Non-limiting examples of ring structures which may be present as or part of the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O, in particular, Si and Ge. The bonding arrangement between the ring and the Cp groups may be either cis-, trans-, or a combination.
[0058] The cyclic bridging groups (A) may be saturated or unsaturated and/or carry one or more substituents and/or be fused to one or more other ring structures. If present, the one or more substituents are selected from the group consisting of hydrocarbyl (e.g., alkyl such as methyl) and halogen (e.g., F, Cl) in one embodiment. The one or more Cp groups which the above cyclic bridging moieties may optionally be fused to may be saturated or unsaturated and are selected from the group consisting of those having 4 to 10, more particularly 5, 6 or 7 ring members (selected from the group consisting of C, N, O and S in a particular embodiment) such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover, these ring structures may themselves be fused such as, for example, in the case of a naphthyl group. Moreover, these (optionally fused) ring structures may carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbyl (particularly alkyl) groups and halogen atoms.
[0059] The ligands CpA and CpB of formula (I) and (II) are different from each other in one embodiment, and the same in another embodiment.
[0060] In yet another aspect, the metallocene catalyst components include mono- ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components) such as described in WO 93/08221 for example. In this embodiment, the at least one metallocene catalyst component is a bridged "half-sandwich" metallocene represented by the formula (III):
CpA(A)QMXn (III) wherein CpΛ is defined above and is bound to M; (A) is defined above and is a bridging group bonded to Q and CpA; and wherein an atom from the Q group is bonded to M; and n is 0 or an integer from 1 to 3; 1 or 2 in a particular embodiment. In formula (III), CpA, (A) and Q may form a fused ring system. The X groups and n of formula (III) are as defined above in formula (I) and (II). In one embodiment, CpA is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted versions thereof, and combinations thereof.
[0061] In formula (III), Q is a heteroatom-containing ligand in which the bonding atom (the atom that is bonded with the metal M) is selected from the group consisting of Group 15 atoms and Group 16 atoms in one embodiment, and selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur atom in a more particular embodiment, and nitrogen and oxygen in yet a more particular embodiment. Non-limiting examples of Q groups include ethers, amines, phosphines, thioethers, alkylamines, arylamines, mercapto compounds, ethoxy compounds, carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene, phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzene other compounds comprising Group 15 and Group 16 atoms capable of bonding with M. [0062] In yet another aspect, the at least one metallocene catalyst component is an unbridged "half sandwich" metallocene represented by the formula (iV):
CpAMQqXn (IV) wherein CpA is defined as for the Cp groups in (I) and is a ligand that is bonded to M; each Q is independently bonded to M; Q is also bound to CpA in one embodiment; X is a leaving group as described above in (I); n ranges from 0 to 3, and is 1 or 2 in one embodiment; q ranges from 0 to 3, and is 1 or 2 in one embodiment. In one embodiment, CpA is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted version thereof, and combinations thereof.
[0063] In formula (iV), Q is selected from the group consisting of ROO", RO-, R(O)-, -NR-, -CR2-, -S-, -NR2, -CR3, -SR, -SiR3, -PR2, -H, and substituted and unsubstituted aryl groups, wherein R is selected from the group consisting of hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys, aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryls, heteroatom-containing groups, silyls, boryls, phosphinos, phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof. In another embodiment, R is selected from Cj to C6 alkyls, C6 to Ci2 aryls, Ci to C6 alkylamines, C6 to C]2 alkylarylamines, Ct to C6 alkoxys, C6 to Ci2 aryloxys, and the like. Non-limiting examples of Q include Ci to Ci2 carbamates, Ci to Ci2 carboxylates (e.g., pivalate), C2 to C20 allyls, and C2 to C2o heteroallyl moieties.
[0064] Described another way, the "half sandwich" metallocenes above can be described as in formula (II), such as described in, for example, US 6,069,213: CpAM(Q2GZ)Xn or T(CpAM(Q2GZ)Xn)m (V) wherein M, CpΛ, X and n are as defined above;
Q2GZ forms a polydentate ligand unit (e.g., pivalate), wherein at least one of the Q groups form a bond with M, and is defined such that each Q is independently selected from the group consisting of -O-, -NR-, -CR2 — and -S-; G is either carbon or silicon; and Z is selected from the group consisting of R, - OR, -NR2, -CR3, -SR, -SiR3, -PR2, and hydride, providing that when Q is -NR-, then Z is selected from the group consisting of -OR, -NR2, -SR, -SiR3, -PR2; and provided that neutral valency for Q is satisfied by Z; and wherein each R is independently selected from the group consisting of hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxys, hydroxyls, alkylthios, lower alkyls thios, arylthios, thioxys, aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alkaryls, alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryls, heteroatom-containing groups, silyls, boryls, phosphinos, phosphines, aminos, amines, cycloalkyls, acyls, aroyls, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof. In another embodiment, R is selected from the group consisting of Ci to Cio heteroatom containing groups, Ci to Cio alkyls, C6 to Ci2 aryls, C6 to Ci2 alkylaryls, Ci to Cio alkoxys, and C6 to Ci2 aryloxys; n is 1 or 2 in a particular embodiment; and
T is a bridging group selected from the group consisting of Ci to Cio alkylenes, C6 to Ci2 arylenes and Ci to Cio heteroatom containing groups, and C6 to Ci2 heterocyclic groups; wherein each T group bridges adjacent "CpAM(Q2GZ)Xn" groups, and is chemically bonded to the CpA groups. m is an integer from 1 to 7; m is an integer from 2 to 6 in a more particular embodiment. [0065] In one non-limiting embodiment, the metallocene compound is selected from the group consisting of (Pentamethylcyclopentadienyl)(Propyl cyclopentadienyl)ZrX' 2, (Tetramethylcyclopentadienyl)(Propyl cyclopentadienyl)ZrX'2, (Pentamethylcyclopentadienyl)(Butyl cyclopentadienyl)ZrX'2, (Tetramethylcyclopentadienyl)(Butyl cyclopentadienyl)ZrX'2, Me2Si(Indenyl)2ZrX2,
Me2Si(Tetrahydroindenyl)2ZrX'2, (n-propyl cyclopentadienyl)2ZrX'2, (n-propyl cyclopentadienyl)2HfX'2, (n-butyl cyclopentadienyl)2ZrX'2, (n- butyl cyclopentadienyl)2HfX'2, (1-Methyl, 3-Butyl cyclopentadienyl)2ZrX'2, HN(CH2CH2N(2,4,6-Me3Phenyl))2ZrX'2, HN(CH2CH2N(2,3,4,5,6-
Me5Phenyl))2ZrX'2, (1-Me, 3-Bu-Cp)2ZrC12, (CpPr)(Me4Cp)HfC12, (CpBu)2ZrC12, (CpPr)2ZrC12, (CpBu)2HfC12, (CpPr)2HfC12, and any combinations thereof.
[0066] By "derivatives thereof, it is meant any substitution or ring formation as described above; and in particular, replacement of the metal "M" (Cr, Zr, Ti or Hf) with an atom selected from the group consisting of Cr, Zr, Hf and Ti; and replacement of the "X" group with any of C1 to C5 alkyls, C6 aryls, C6 to Cio alkylaryls, fluorine or chlorine; n is 1, 2 or 3.
[0067] It is contemplated that the metallocene catalysts components described above include their structural or optical or enantiomeric isomers (racemic mixture), and may be a pure enantiomer in one embodiment.
[0068] As used herein, a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.
[0069] The "metallocene catalyst component" may comprise any combination of any "embodiment" described herein.
[0070] Metallocene compounds and catalysts are known in the art and any one or more may be utilized herein. Suitable metallocenes include but are not limited to all of the metallocenes disclosed and referenced in the U.S. Patents cited above, as well as those disclosed and referenced in U.S. Patent Nos. 7,179,876, 7,169,864, 7,157,531,7,129,302, 6,995,109, 6,958,306, 6,884748, 6,689,847, U.S. Patent Application publication number 2007/0055028, and published PCT Application Nos. WO 97/22635, WO 00/699/22, WO 01/30860, WO 01/30861, WO 02/46246, WO 02/50088, WO 04/026921, and WO 06/019494, all fully incorporated herein by reference. Additional catalysts suitable for use herein include those referenced in U.S. Patent Nos. 6,309,997, 6,265,338, U.S. Patent Application publication number 2006/019925, and the following articles: Chem Rev 2000, 100, 1253, Resconi; Chem Rev 2003, 103, 283; Chem Eur. J. 2006, 12, 7546 Mitsui; J MoI Catal A 2004, 213, 141; Macromol Chem Phys, 2005, 206, 1847; and J Am Chem Soc 2001, 123, 6847.
Group 15-Containing Catalysts
[0071] "Group 15-containing catalyst components", as referred to herein, include Group 3 to Group 12 metal complexes, wherein the metal is 2 to 4 coordinate, the coordinating moiety or moieties including at least two Group 15 atoms, and up to four Group 15 atoms. In one embodiment, the Group 15-containing catalyst component is a complex of a Group 4 metal and from one to four ligands such that the Group 4 metal is at least 2 coordinate, the coordinating moiety or moieties including at least two nitrogens. Representative Group 15-containing compounds are disclosed in, for example, WO 98/46651, WO 99/01460; EP Al 0 893,454; EP Al 0 894 005; US 5,318,935; US 5,889,128 US 6,333,389 B2 and US 6,271,325 Bl.
[0072] The Group 15-containing catalyst components are prepared by methods known in the art, such as those disclosed in, for example, EP 0 893 454 Al, US 5,889,128, US 6,333,389 B2 and WO 00/37511.
Phenoxide Transition Metal Catalysts
[0073] Phenoxide transition metal catalyst compositions are heteroatom substituted phenoxide ligated Group 3 to 10 transition metal or lanthanide metal compounds wherein the metal is bound to the oxygen of the phenoxide group. Phenoxide transition metal catalyst compounds may be represented by Formula XIV or XV:
Figure imgf000024_0001
(XIV)
or
Figure imgf000024_0002
(XV)
[0074] wherein R1 is hydrogen or a C4 to Cioo group, preferably a tertiary alkyl group, preferably a C4 toC2o alkyl group, preferably a C4 toC2o tertiary alkyl group, preferably a neutral C4 to Ci oo group and may or may not also be bound to M; at least one of R2 to R5 is a heteroatom containing group, the rest of R2 to R5 are independently hydrogen or a Ci to Ci00 group, preferably a C4 to C20 alkyl group, preferred examples of which include butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl, dodecyl, and any of R2 to R5 also may or may not be bound to M;
Each R1 to R5 group may be independently substituted or unsubstituted with other atoms, including heteroatoms or heteroatom containing group(s); O is oxygen;
M is a Group 3 to Group 10 transition metal or lanthanide metal, preferably a Group 4 metal, preferably M is Ti, Zr or Hf; n is the valence state of the metal M, preferably 2, 3, 4, or 5; and
Q is, and each Q may be independently be, an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydride or alkoxide group, or a bond to an R group containing a heteroatom which may be any of R to R . [0075] A heteroatom containing group may be any heteroatom or a heteroatom bound to carbon, silicon or another heteroatom. Preferred heteroatoms include boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, and tellurium. Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus, and sulfur. Even more particularly preferred heteroatoms include nitrogen and oxygen. The heteroatom itself may be directly bound to the phenoxide ring or it may be bound to another atom or atoms that are bound to the phenoxide ring. The heteroatom containing group may contain one or more of the same or different heteroatoms. Preferred heteroatom containing groups include imines, amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines, thioethers, and the like. Particularly preferred heteroatom containing groups include imines. Any two adjacent R groups may form a ring structure, preferably a 5 or 6 membered ring. Likewise the R groups may form multi-ring structures. In one embodiment any two or more R groups do not form a 5 membered ring.
[0076] In a preferred embodiment the heteroatom substituted phenoxide transition metal compound is an iminophenoxide Group 4 transition metal compound, and more preferably an iminophenoxidezirconium compound.
[0077] It is further contemplated by the invention that other catalysts can be combined with the compounds of the invention. For example, see Hlatky, G.G. Chem. Rev. (2000), 100, 1347; Alt, H.; Koppl, A. Chem. Rev. (2000), 100, 1205; Resconi, L. et al, Chem. Rev. (2000), 100, 1253; Bryntzinger, H.H. et.ai, Angew. Chem. Int. Ed. Engl. (1995), 34, 1143; Ittel, S.D. et al, Chem. Rev. (2000), 100, 1169; Gibson, V.C. et al, Chem. Rev. (2003), 103, 283; Skupinska, J., Chem. Rev. (1991), 91, 613; Carter, A. et al, Chem. Cornmun.. 2002, 858; Z3
McGuinness, D.S.; et al, J. Am. Chem. Soc. (2003), 125, 5272; McGuiness, D.S., Chem. Commun. (2003), 334; U.S. Patent Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241, all of which are herein fully incorporated herein reference.
[0078] In another embodiment of the invention one or more catalyst compounds or catalyst systems may be used in combination with one or more conventional- type catalyst compounds or catalyst systems. Non-limiting examples of mixed catalysts and catalyst systems are described in U.S. Patent Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031, and PCT Publication No. WO 96/23010 published Aug. 1, 1996, all of which are herein fully incorporated by reference.
High Molecular Weight Catalysts
[0079] With respect to the catalyst systems of the disclosure wherein the high molecular weight catalyst compound is a non-metallocene compound generally the compound is a biphenyl phenol catalyst (BPP) compound. BPP catalyst compounds are known in the art and any are suitable for use herein such as, but not limited to those disclosed in U.S. Patent Nos. 7,091,282, 7,030,256, 7,060,848, 7,126,031, 6,841,502, U. S. Patent Application publication numbers 2006/0025548, 2006/020588, 2006/00211892, and published PCT application numbers WO 2006/020624, WO 2005/108406, and WO 2003/091262, all incorporated herein by reference.
[0080] Preference may be given to BPP compounds having formula (XVI) shown below:
zo
formula TXVD
Figure imgf000027_0001
wherein M may be Ti, Zr, or Hf. In one embodiment R1 of formula 1 is hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, amine.
[0081] In some embodiments, the bridging group R1 is selected from the group consisting of optionally substituted divalent hydrocarbyl and divalent heteroatom containing hydrocarbyl. In other embodiments, R1 is selected from the group consisting of optionally substituted divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkyl thio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent halide, divalent haloalkyl, divalent haloalkenyl, divalent z /
haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbyl, divalent lower hydrocarbyl, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent thioether. In still other embodiments, R1 can be represented by the general formula -(Q11R 2-z")z— wherein each Q" is either carbon or silicon and each R40 may be the same or different from the others such that each R40 is selected from the group consisting of hydride and optionally substituted hydrocarbyl, and optionally two or more R40 groups may be joined into a ring structure having from 3 to 50 atoms in the ring structure (not counting hydrogen atoms); and z' is an integer from 1 to 10, more specifically from 1 5 and even more specifically from 2 5 and z" is 0, 1 or 2. For example, when z" is 2, there is no R40 groups associated with Q", which allows for those cases where one Q" is multiply bonded to a second Q". In more specific embodiments, R40 is selected from the group consisting of hydride, halide, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thioxy, alkyl thio, arylthio, and combinations thereof. Specific R1 groups within these embodiments include ~(CH2)2--, -(CH2)3~, -(CH2)4~ and -(CH2HC6H4)- (CH2)-. Other specific bridging moieties are set forth in the example ligands and complexes herein.
[0082] In one embodiment R2 - R9 of formula (XVI) are optionally hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, or amine.
[0083] Each X in formula (XVI) is independently selected from the group consisting of: any leaving group in one embodiment; halogen ions, hydrides, Ci to Ci2 alkyls, C2 to Ci2 alkenyls, C6 to Ci2 aryls, C7 to C20 alkylaryls, Ci to Ci2 alkoxys, C6 to C]6 aryloxys, C7 to Ci8 alkylaryloxys, Ci to Ci2 fluoroalkyls, C6 to Ci2 fluoroaryls, and Ci to Ci2 heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular embodiment; hydride, halogen ions, Ci to C6 alkyls, C2 to C6 alkenyls, C7 to Ct8 alkylaryls, Ci to C6 alkoxys, C6 to Ci4 aryloxys, C7 to Ci6 alkylaryloxys, Ci to C6 alkylcarboxylates, Ci to C6 fluorinated alkylcarboxylates, C6 to Ci2 arylcarboxylates, C7 to Ci8 alkylarylcarboxylates, Ci to C6 fluoroalkyls, C2 to C6 fluoroalkenyls, and C7 to C]8 fluoroalkylaryls in yet a more particular embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyls in yet a more particular embodiment; Ci to Ci2 alkyls, C2 to Ci2 alkenyls, C6 to Ci2 aryls, C7 to C20 alkylaryls, substituted Ci to Ci2 alkyls, substituted C6 to Ci2 aryls, substituted C7 to C2o alkylaryls and Ci to Ci2 heteroatom-containing alkyls, Ci to Ci2 heteroatom-containing aryls and Ci to Ci2 heteroatom-containing alkylaryls in yet a more particular embodiment; chloride, fluoride, Ci to C6 alkyls, C2 to C6 alkenyls, C7 to Ci8 alkylaryls, halogenated Ci to C6 alkyls, halogenated C2 to C6 alkenyls, and halogenated C7 to Ci8 alkylaryls in yet a more particular embodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls) in yet a more particular embodiment.
[0084] Other non-limiting examples of X groups in formula (XVI) include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., -C6F5 (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF3C(O)O"), hydrides and halogen ions and combinations thereof. Other examples of X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like. In one embodiment, two or more X's form a part of a fused ring or ring system. zy
[0085] In one embodiment of the compound represented by formula (XVI), M may be Ti, Zr, or Hf. R1, R3, R5 through R9 are H; each R2 may be any of alkyl, aryl, or heteroaryl; each R4 may be any of H, alkyl, aryl; and each X may be any of F, Cl, Br, I, Me, Bnz, CH2SiMe3, or Cl to C5 alkyls.
[0086] In another non-limiting embodiment of the compound represented by formula (XVI), M may be Ti, Zr, or Hf; R1 may be any of CH2CH2, (CH2)3, (CH2)4, CH2CHMeCH2, CH2CMe2CH2, Me2Si, CH2SiMe2CH2, each R2 may be any of an aryl group, defined here to bind through the 1 -position to the BPP ring, with substituents in the 2-position or substituents in the 2 and 6 positions such as 2,4-Me2Ph, 2,5-Me2Ph, 2,6-Me2Ph, 2,6-Et2Ph, 2,6-Pr2-Ph, 2,6-Bu2Ph, 2- MeNapthyl, 2,4,6-Me3Ph, 2,4,6-Et3Ph, 2,4,6-Pr3Ph, carbazole and substituted carbazoles; R3 and R5 through R9 are H; each R4 may be any of H, Methyl, Ethyl, Propyl, Butyl, Pentyl; and each X may be any of F, Cl, Br, I, Me, Bnz, CH2SiMe3, or Cl to C5 alkyls.
[0087] In one preferred embodiment, M may be either Zr or Hf; and X may be any of F, Cl, Br, I, Me, Bnz, or CH2SiMe3. In another preferred embodiment, M may be either Zr or Hf; R1 may be either (CH2)3 or (CH2)4; each R2 may be any of 2,6-Me2Ph, 2,6-Et2Ph, 2,6-Pr2-Ph, 2,6-Bu2Ph, 2-MeNapthyl, 2,4,6-Me3Ph, 2,4,6- Et3Ph, 2,4,6-Pr3Ph, and carbazole; each R4 may be any of H, Methyl or Butyl; and X may be any of F, Cl, or Me. In even another preferred embodiment, the R1 is (CH2)3; each R3 is either 2,4,6-Me3Ph or 2-MeNapthyl; each R4 is CH3; X is Cl; and M is Zr.
[0088] In another non-limiting embodiment, the high molecular weight catalyst component may be any catalyst that produces a polymer having a weight average molecular weight (Mw) of greater than about 1 million g/mol, preferably greater than about 1.5 million g/mol, even more preferably greater than about 2 million g/mol, and still more preferably greater than about 3 million g/mol. The low molecular weight catalyst may be any catalyst that produces a polymer having a weight average molecular weight (Mw) in the range of from about 40,000 to about 200,000 g/mol, preferably from about 50,000 to about 180,000 g/mol, more preferably from about 60,000 to about 175,000 g/mol, and even more preferably from about 70,000 to about 150,000 g/mol. In one preferred embodiment, the high molecular weight catalyst produces polymer having an Mw greater than about 5 million g/mol, and the low molecular weight catalyst produces polymer having an Mw of about 100,000 g/mol.
[0089] The amount of each catalyst component present in the catalyst systems of the disclosure may be varied within a range. The amount of each catalyst component present in the catalyst systems may be dependent on one or more reaction parameters including but not limited to reactor temperature, hydrogen concentration, and comonomer concentration. The low molecular weight catalyst is generally present in an amount greater than that of the high molecular weight catalyst. Generally, the high molecular weight catalyst component is present in a catalyst system in an amount in a range of from about 0.001 to about 5.0 mol% of said low molecular weight catalyst component, preferably in a range of from about 0.05 to about 2.5 mol% of said low molecular weight catalyst component, more preferably in a range of from about 0.1 to about 2.0 mol% of said low molecular weight catalyst component. For example, in the case of one high and one low molecular weight catalyst, the mol % of the high molecular weight catalyst may be calculated from the equation: 100(moles of high molecular weight catalyst)/(moles of low molecular weight catalyst + moles of high molecular weight catalyst).
Activators and Activation Methods
[0090] The above described low and high molecular weight precatalyst compounds can be combined with an activator and optionally a support or carrier in a manner that will allow production of a polymer with low and high molecular weight components. The term "cocatalyst" or "cocatalysts" may be used interchangeably with one or more "activators". This activation yields catalyst compounds capable of polymerizing olefins.
[0091] For the purposes of this patent specification and appended claims, the term
"activator" is defined to be any compound or component or method which can activate any of the precatalyst metal compounds of the invention as described above. Non-limiting activators, for example may include a Lewis acid or a non- J l
coordinating ionic activator or ionizing activator or any other compound including Lewis bases, aluminum alkyls, conventional-type cocatalysts or an activator- support and combinations thereof that can convert a neutral precatalyst metal compound to a catalytically active cationic metal compound. It is within the scope of this invention to use alumoxane or modified alumoxane as an activator, and/or to also use ionizing activators, neutral or ionic, such as tri (n-butyl)ammonium tetrakis(pentafluorophenyl)boron or a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor that would ionize the neutral precatalyst metal compound.
[0092] The low and high molecular weight catalyst precursors according to this invention may be activated for polymerization catalysis in any manner sufficient to allow coordination or cationic polymerization. This can be achieved for coordination polymerization when one ligand can be abstracted and another will either allow insertion of the unsaturated monomers or will be similarly abstractable for replacement with a ligand that allows insertion of the unsaturated monomer (labile ligands), eg. alkyl, silyl or hydride. The traditional activators of coordination polymerization art are suitable, those typically include Lewis acids such as alumoxane compounds, and ionizing, anion precursor compounds that abstract one so as to ionize the bridged metallocene metal center in to a cation and provide a counterbalancing noncoordianting ion. In one embodiment, an activation method using ionizing ionic compounds not containing an active proton but capable of producing both a cationic metal compound catalyst and a non- coordinating anion are also contemplated, and are described in EP-A-O 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.
[0093] Alkylalumoxanes and modified alkylalumoxane are suitable as catalyst activators, particularly for the invention metal compounds where R1 = halide or other functional group. Alkylalumoxanes and modified alkylalumoxane are also suitable as catalyst for the invention metal compounds where R1 = hydrocarbyl or substituted hydrocarbyl. In one embodiment, one or more alumoxanes are utilized as an activator in the catalyst composition of the invention. Alumoxanes, sometimes called aluminoxanes in the art, are generally oligomeric compounds containing -Al(R)-O- subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methyl alumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U.S. Patents 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 Al, EP 0 279 586 Bl, EP 0 516 476 A, EP 0 594 218 Al and WO 94/10180.
[0094] Alumoxanes may be produced by the hydrolysis of the respective trialkylaluminum compound. MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum. MMAO' s are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Patent No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publications EP-A- 0 561 476, EP-Bl-O 279 586, EP-A-O 594-218 and EP-Bl-O 586 665, and PCT publications WO 94/10180 and WO 99/15534, all of which are herein fully incorporated by reference. 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. Another preferred alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number US 5,041,584).
[0095] Aluminum alkyl or organoaluminum compounds which may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like. a
[0096] It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459) or combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
[0097] Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides. Preferably, the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronaphthyl boron.
[0098] Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound. Such compounds and the like are described in European publications EP-A-O 570 982, EP-A-O 520 732, EP-A-O 495 375, EP-Bl-O 500 944, EP-A-O 277 003 and EP-A-O 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No. 08/285,380, filed August 3, 1994, all of which are herein fully incorporated by reference. [0099] Preferred activators include a cation and an anion component, and may be represented by the following formula: J4
Figure imgf000035_0001
St+ is a cation component having the charge t+
NCAV" is a non-coordinating anion having the charge v- t is an integer from 1 to 3. v is an integer from 1 to 3. u and v are constrained by the relationship: (u) x (t) = (v) x (w).
[00100] The cation component, (St+) 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 akyl or aryl, from an analogous metallocene or Group 15 containing transition metal catalyst precursor, resulting in a cationic transition metal species.
[00101] In a preferred embodiment, the activators include a cation and an anion component, and may be represented by the following formula:
(LB-Ht+)U (NCA v')w wherein LB is a neutral Lewis base; H is hydrogen;
NCAV" is a non-coordinating anion having the charge v- t is an integer from 1 to 3, v is an integer from 1 to 3, u and v are constrained by the relationship: (u) x (t) = (v) x (w).
[00102] The activating cation (St+) may be a Bronsted acid, (LB -Ht+), 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 N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene and mixtures thereof.
[00103] Ionizing compounds may contain an active proton, or some other cation associated with but not coordinated to or only loosely coordinated to the remaining ion of the ionizing compound. Such compounds and the like are described in European Publication Nos. EP-A-O 570 982, EP-A-O 520 732, EP-A- 0 495 375, EP-A-500 944, EP-A-O 277 003 and EP-A-O 277 004, U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124, and U.S. Patent Application Serial No. 08/285,380, filed Aug. 3, 1994, all of which are herein fully incorporated by reference.
[00104] The activating cation (St+) may also be an abstracting moiety such as silver, carbeniums, carbyliums, tropylium, ferroceniums and mixtures, preferably carbeniums. (Carbeniums are defined as carbon based cations with one less substituent than the corresponding neutral atom, sometimes referred to a carbonium ions, while carbyliums are defined as carbon based cations with one more substituent, generally H, than the corresponding neutral atom.)
[00105] Most preferably (St+) is triphenyl carbenium or N, N-dimethylanilinium. [00106] The anion component (NCA ") includes those having the formula
Y-L. y,.
[T Qy] wherein x is an integer from 1 to 3; y is an integer from 2 to 6; y - x = v; T is an element selected from Group 13 or 15 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted- hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, 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.
[00107] Examples of suitable (NCA ") also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference. Another example of a suitable anion is a borate with three ortho- substituted fluoroaryl ligands and one alkyne ligand. Another example of a suitable anion is a borate containing fluoroaryl groups with polar substitutents such as amines, ethers, silyl groups and derivatives thereof.
[00108] The term non-coordinating anion may be used interchangeably with the term weakly coordinating anion.
[00109] Additional suitable anions are known in the art and will be suitable for use with the catalysts of the invention. See in particular, patents US 5,278,119, WO2002102857, WO2002051884, WO200218452, WO2000037513, WO2000029454, WO2000004058, WO9964476, WO2003049856, WO2003051892, WO2003040070, WO2003000740, WO2002036639, WO2002000738, WO2002000666, WO2001081435, WO2001042249, WO2000004059. Also see the review articles by S. H. Strauss, "The Search for Larger and More Weakly Coordinating Anions", Chem. Rev., 93, 927-942 (1993) and C. A. Reed, "Carboranes: A New Class of Weakly Coordinating Anions for Strong Electrophiles, Oxidants and Superacids", Ace. Chem. Res., 31, 133 -139 (1998).
[00110] Illustrative, but not limiting examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N- diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis(heptafluoronaphthyl)borate, triethylammonium M
tetrakis(heptafluoronaphthyl)borate, tripropylammonium tetrakis(heptafluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(heptafluoronaphthyl)borate, tri(sec-butyl)ammonium tetrakis(heptafluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)borate, N,N-diethylanilinium tetrakis(heptafluoronaphthyl)borate, trimethylammonium (2- perfluorobiphenyl)3(perfluorophenylalkynyl)borate, triethylammonium (2- perfluorobiphenyl)3(perfluorophenylalkynyl)borate, tripropylammonium (2- perfluorobiphenyl)3(perfluorophenylalkynyl)borate, tri(n-butyl)ammonium (2- perfluorobiphenyl)3(perfluorophenylalkynyl)borate, tri(sec-butyl)ammonium (2- perfluorobiphenyl)3(perfluorophenylalkynyl)borate, N,N-dimethylanilinium (2- perfluorobiphenyl)3(perfluorophenylalkynyl)borate, N,N-diethylanilinium (2- peifluorobiphenyl)3(perfluorophenylalkynyl)borate, trimethylammonium tetrakis- (2,3,4,6-tetrafluorophenylborate, triethylammonium tetrakis-(2,3,4,6- tetrafluorophenyl) borate, tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N- dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N- diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, and N,N-dimethyl- (2,4,6-trimethylanilinium)tetrakis-(2,3 ,4,6-tetrafluorophenyl) borate; dialkyl ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; and tri- substituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; non-Bronsted acids such as triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(heptafluoronaphthyl)borate, triphenylcarbenium (2- perfluorobiphenyl)3(perfluorophenylalkynyl)borate, trisperfluorophenyl borane, and triperfluoronaphthyl borane. [00111] Most preferably, the ionic stoichiometric activator is N,N- dimethylanilinium tetrakis(perfluorophenyl)borate and/or triphenylcarbenium tetrakis(perfluorophenyl)borate.
[00112] In one embodiment, activation methods using ionizing ionic compounds not containing an active proton but capable of producing an analogous metallocene catalyst cation and their non-coordinating anion are also contemplated and are described in EP-A- 0 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference. [00113] The term "non-coordinating anion" (NCA) means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. "Compatible" non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the metal cation in the sense of balancing its ionic charge, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization. These types of cocatalysts sometimes use tri-isobutyl aluminum or tri-octyl aluminum as a scavenger. [00114] Invention process also can employ cocatalyst compounds or activator compounds that are initially neutral Lewis acids but form a cationic metal complex and a noncoordinating anion, or a zwitterionic complex upon reaction with the invention compounds. For example, tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl or hydride ligand to yield an invention cationic metal complex and stabilizing noncoordinating anion, see EP-A-O 427 697 and EP-A-O 520 732 for illustrations of analogous Group-4 metallocene compounds. Also, see the methods and compounds of EP-A-O 495 375. For formation of zwitterionic complexes using analogous Group 4 compounds, see U.S. Patents 5,624,878; 5,486,632; and 5,527,929.
[00115] Additional neutral Lewis-acids are known in the art and are suitable for abstracting anionic ligands. See in particular the review article by E. Y. -X. Chen and T.J. Marks, "Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships", Chem. Rev., 100, 1391-1434 (2000).
[00116] When X is a ligand, such as chloride, amido or alkoxy ligands, not capable of discrete ionizing abstraction with the ionizing, anion pre-cursor compounds, these functional group ligands can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-O 500 944, EP-Al-O 570 982 and EP-Al-O 612 768 for analogous processes describing the reaction of alkyl aluminum compounds with analogous dihalide substituted metallocene compounds prior to or with the addition of activating noncoordinating anion precursor compounds.
[00117] When the cations of noncoordinating anion precursors are Bronsted acids such as protons or protonated Lewis bases (excluding water), or reducible Lewis acids such as ferrocenium or silver cations, or alkali or alkaline earth metal cations such as those of sodium, magnesium or lithium, the catalyst-precursor-to-activator molar ratio may be any ratio. Combinations of the described activator compounds may also be used for activation. For example, tris(perfluorophenyl) boron can be used with methylalumoxane.
[00118] Other useful ion forming Lewis acids include those having two or more Lewis acidic sites, such as those described in WO 99/06413 or Piers, et al. "New Bifunctional Perfluoroaryl Boranes: Synthesis and Reactivity of the ortho- Phenylene-Bridged Diboranes 1,2-(B(C6F5)2)2C6X4(X = H, F)", J. Am. Chem. Soc, 1999, 121, 3244 3245, both of which are incorporated herein by reference. Other useful Lewis acids will be evident to those of skill in the art. Combinations of ion forming activators may be used.
[00119] Other activators include those described in PCT Publication No. WO 98/07515 such as tris (2, 2', 2"-nonafluorobiphenyl)fluoroaluminate, which publication is fully incorporated herein by reference. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, PCT Publication Nos. WO 94/07928 and WO 95/14044, and U.S. Patent Nos. 5,153,157 and 5,453,410, all of which are herein fully incorporated by reference. WO 98/09996 incorporated herein by reference describes activating precatalyst metal compounds with perchlorates, periodates and iodates including their hydrates. PCT Publication Nos. WO 98/30602 and WO 98/30603, which are incorporated by reference herein, describe the use of lithium (2,2'-bisphenyl-ditrimethylsilicate). 4THF as an activator for a precatalyst metal compound. Also, methods of activation such as using radiation (see EP-Bl-O 615 981 herein incorporated by reference), electro-chemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral precatalyst metal compound or precursor to a cationic catalyst metal compound capable of polymerizing olefins. [00120] In one non-limiting embodiment, one or more alumoxanes may be used to activate the low and high molecular weight catalyst components. In another non- limiting embodiment, one or more alumoxanes may be used to activate the low molecular weight precatalyst component while one or more ionizing activators are used to activate the high molecular weight precatalyst component. In another non- limiting embodiment, one or more alumoxanes may be used to activate the high molecular weight precatalyst component while one or more ionizing activators are used to activate the low molecular weight precatalyst component. In another embodiment one or more ionizing activator are used to activate the low and high molecular weight catalyst components. In another non-limiting example, one or more alumoxanes and one or more ionizing activators may be used to activate the low and high molecular weight precatalyst components.
[00121] In general the combined activator and metal compounds are combined in ratios of about 1000:1 to about 0.5:1.
[00122] When the activator is an alumoxane (modified or unmodified), any quantity of alumoxane that activates a precatalyst metal compound may be used. Preferably, the ratio of Aluminum to the total molar amount of precatalyst or catalyst metal is between 1000: 1 and 1:1. More preferably, the ratio is from 500:1 to 25:1. Even more preferably, the ratio is from 250:1 to 50: 1. Even more preferably, the ratio is between 200:1 and 75: 1.
[00123] When the activator is an ionizing activator, any quantity of ionizing activator that activates a precatalyst metal compound may be used. Preferably, the ratio of ionizing activator to the total molar amount of precatalyst or catalyst metal is between 10:1 and 1: 10. More preferably, the ratio is from 5:1 to 1:5. Even more preferably, the ratio is from 4:1 to 1:4. Even more preferably, the ratio is between 2:1 and 1:2.
[00124] When a combination of activators is employed, any quantity of activators that activates precatalyst metal compounds may be used.
Supports and Methods of Supporting
[00125] In a preferred embodiment, the catalysts of the invention comprise high and low molecular weight catalyst precursors, an activator and a support material. Methods for preparing supported catalysts are well known in the art and are easily extendible to the preparation of catalysts with high and low molecular weight catalyst metal compounds.
[00126] The above described precatalyst metal compounds and activators may be combined with one or more support materials or carriers using one of the support methods well known in the art or as described below. In the preferred embodiment, the method of the invention uses a polymerization catalyst in a supported form. For example, in a most preferred embodiment, a catalyst system is in a supported form, for example deposited on, bonded to, contacted with, or incorporated within, adsorbed or absorbed in, or on, a support or carrier. [00127] The terms "support" or "carrier" are used interchangeably and are any support material, preferably a porous support material, for example, talc, inorganic oxides and inorganic chlorides. Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
[00128] The preferred carriers are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica, alumina, silica- alumina, magnesium chloride, and mixtures thereof. Other useful supports include magnesia, titania, zirconia, montmorillonite (EP-Bl 0 511 665) and the like. Also, combinations of these support materials may be used, for example, silica- chromium, silica-alumina, silica-titania and the like.
[00129] It is preferred that the carrier, most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m2/g, pore volume in the range of from about 0.1 to about 4.0 mL/g and average particle size in the range of from about 5 to about 500 μm . More preferably, the surface area of the carrier is in the range of from about 50 to about 500 m2/g, pore volume of from about 0.5 to about 3.5 mL/g and average particle size of from about 10 to about 200 μm. Most preferably the surface area of the carrier is in the range is from about 100 to about 400 m2/g, pore volume from about 0.8 to about 3.0 mL/g and average particle size is from about 5 to about 100 μm. The average pore size of the carrier of the invention typically has pore size in the range of from 10 to 1000 A, preferably 50 to about 500 A, and most preferably 75 to about 350 A.
[00130] Examples of supporting catalyst systems are described in Hlatky, Chem. Rev. (2000), 100, 1347 1376 and Fink et al, Chem. Rev. (2000), 100, 1377 1390, U.S. Patent Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032 and 5,770,664, U.S. Application Serial No. 271,598 filed July 7, 1994 and Serial No. 788,736 filed January 23, 1997, and PCT Publication Nos. WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297, all of which are herein fully incorporated by reference.
[00131] In one embodiment, the catalyst compounds of the invention may be deposited on the same or separate supports together with an activator, or the activator may be used in an unsupported form, or may be deposited on a support different from the supported catalyst metal compounds of the invention, or any combination thereof.
[00132] In another embodiment, active catalysts may be prepared by supporting the ligands of the catalysts of the invention on support then treatment with a labile organometallic agent, such as Zr(CH2Ph)4, and an activator. [00133] There are various other methods in the art for supporting a polymerization catalyst compound or catalyst system of the invention. For example, the catalyst compounds of the invention may contain a polymer bound ligand as described in U.S. Patent Nos. 5,473,202 and 5,770,755, which are herein fully incorporated by reference; the system of the invention may be spray dried as described in U.S. Patent No. 5,648,310, which is herein fully incorporated by reference; the support used with the catalyst system of the invention is functionalized as described in European Publication No. EP-A-O 802 203, which is herein fully incorporated by reference, or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880, which is herein fully incorporated by reference. [00134] In a preferred embodiment, the invention provides for a supported catalyst system that includes an antistatic agent or surface modifier that is used in the preparation of the supported catalyst system as described in PCT Publication No. WO 96/11960, which is herein fully incorporated by reference. The catalyst systems of the invention can be prepared in the presence of an olefin, for example hexene-1.
[00135] A preferred method for producing the supported catalyst system of the invention is described below and is described in U.S. Application Serial No. 265,533, filed June 24, 1994 and Serial No. 265,532, filed June 24, 1994, and PCT Publication Nos. WO 96/00245 and WO 96/00243 both published January 4, 1996, all of which are herein fully incorporated by reference. In this preferred method, precatalyst compounds are slurried in a liquid to form a solution and a separate solution is formed containing an activator and a liquid. The liquid may be any compatible solvent or other liquid capable of forming a solution or the like with the catalyst compounds and/or activator of the invention. In the most preferred embodiment the liquid is an aliphatic or aromatic hydrocarbon, most preferably toluene. The catalyst compound and activator solutions are mixed together and added to a porous support or the porous support is added to the solutions such that the total volume of the catalyst metal compound solution and the activator solution or the catalyst compound and activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range. [00136] In another preferred embodiment, the catalyst system comprises a precatalyst as described herein activated by methylaluminoxane (MAO) and supported by silica. In a preferred embodiment, the MAO is first contacted with the silica and dried then treated with a solution of the high and low molecular weight precatalyst compounds then dried.
[00137] The precatalysts, activator and support may be combined in any order and under any process conditions (temperatures, pressures, concentrations) that produces a viable catalyst system. The combination may take place in the presence of a solvent. Preferred solvents are those that do not contain functional groups that would adversely effect the subsequent olefin polymerization. Non- limiting examples of preferred solvents include aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, octane, benzene and toluene. [00138] In one non-limiting embodiment of the invention, a supported catalyst is prepared by combining high and low molecular weight precatalysts, solvent and activator then addition of a support material; afterwards, solvent may optionally be removed. In another non-limiting embodiment of the invention, a supported catalyst is prepared by combination of an activator with the support material, optionally in the presence of solvent, then a mixture or mixtures of high and low molecular weight precatalysts and solvent; afterwards, solvent may optionally be removed. In another non-limiting embodiment of the invention, a supported catalyst is prepared by combination of a low molecular weight precatalyst, an activator and support and optionally solvent followed by the addition of a high molecular weight precatalyst; afterwards, solvent may optionally be removed. In another non-limiting embodiment of the invention, a supported catalyst is prepared by combination of a high molecular weight precatalyst, an activator and support and optionally solvent followed by the addition of a low molecular weight precatalyst; afterwards, solvent may optionally be removed.
[00139] The catalyst systems of the disclosure may be produced by any one or more techniques known in the art useful for making catalyst compounds and any such methods suitable for use herein for example, but not limited to, the method disclosed in U.S Patent No. 6,608,153, incorporated herein by reference. Generally, for supported catalysts, a support is combined with a diluent to form a support slurry, which may be stirred and optionally heated during mixing. The first precatalyst compound, second precatalyst compound, and any one or more cocatalyst components may be added to the slurry in one or more steps and may be added individually or in any combination. The resulting slurry is mixed to achieve the desired contact between the components. Any one or more recovery technique may then be employed to recover the catalyst system. Examples of suitable recovery techniques include filtration, evaporation, vacuum distillation, simple decanting, and combinations thereof. The retrieved catalyst component may be washed any number of times with a suitable diluent, especially one or more aliphatic or cycloaliphatic hydrocarbons, or a mixture thereof. The resulting recovered catalyst composition may be dried using conventional techniques, such as passing an inert gas, especially nitrogen, over the solid to form a solid, granular powdery catalyst composition or it may be combined with an inert liquid, especially a hydrocarbon such as a mineral oil, for storage and use. The catalyst composition is preferably stored under an inert atmosphere.
[00140] The slurry comprising diluent and any one or more of the catalyst components and support particles may be heated during and/or after addition and/or mixing of each component. When the catalyst compounds are added to the slurry, either singly or in combination, the temperature of the slurry is generally sufficiently low so that the catalyst components are not inadvertently deactivated. Generally the temperature of the slurry is maintained at a temperature below 120°C to avoid deactivation of the catalyst components.
[00141] In one embodiment of the invention, olefin(s), preferably C2 to C3o olefin(s) or alpha-olefin(s), preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of the catalyst metal compound system of the invention prior to the main polymerization. The prepolymerization can be carried out batchwise or continuously in gas, solution or slurry phase including at elevated pressures. The prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen. For examples of prepolymerization procedures, see U.S. Patent Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578, European Publication No. EP-B-0279 863, and PCT Publication No. WO 97/44371, all of which are herein fully incorporated by reference.
[00142] In one embodiment the polymerization catalyst is used in an unsupported form, preferably in a liquid form such as described in U.S. Patent Nos. 5,317,036 and 5,693,727, and European Publication No. EP-A-O 593 083, all of which are herein incorporated by reference. The polymerization catalyst in liquid form can be fed to a reactor as described in PCT Publication No. WO 97/46599, which is fully incorporated herein by reference.
[00143] In one embodiment, the catalysts of the invention can be combined with a carboxylic acid salt of a metal ester, for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Patent No. 6,300,436.
Polymerization Processes
[00144] The catalyst systems and polymerization processes of the present disclosure are directed to polymerization of one or more olefin monomers having from 2 to 30 carbon atoms. The catalysts and polymerization processes are particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, 4-methyl- 1-pentene, 1-isobutene, 1-isobutene and 1-decene. Other monomers useful in the processes of the disclosure include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins. Non-limiting monomers useful in the disclosure may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
[00145] The present disclosure encompasses homopolymerization processes comprising a single olefin species such as ethylene or propylene, as well as 4 /
copolymerization reactions between one olefin species (referred to herein as the "monomer" and "monomer compound") and at least a second olefin species (referred to herein as "comonomer" and "comonomer compound") different from the first species. Generally a copolymer will comprise a major amount of the monomer compound (i.e., greater than about 50 mole percent) and a minor amount of the comonomer (i.e., less than about 50 mole percent). The comonomers generally have from three to about 20 carbon atoms in their molecular chain and examples include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl- 1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-l- pentene, 4-methyl- 1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-l-hexene, 1- heptene, 2-heptene, 3-heptene, the four normal octenes, the four normal nonenes, or the five normal decenes. In one non-limiting embodiment, a copolymer may comprise ethylene copolymerized with a comonomer selected from 1-butene, 1- pentene, 1-hexene, 1-octene, 1-decene, or styrene.
[00146] In another embodiment of the process of the invention, ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer. In one embodiment, terpolymer comprisses units derived from ethylene, at least one other alpha-olefin, such as butene or hexene, and a diene such as octadiene.
[00147] The diene may be a polyunsaturated compound; containing at least two
C=C bonds and may be aliphatic as well as alicyclic. Aliphatic polyunsaturated compounds in general contain 4 to 20 carbon atoms, while the double bonds may be conjugated or non-conjugated.
[00148] Examples of such compounds are: 1,3-butadiene, isoprene, 2,3-dimethyl butadiene- 1,3, 2-ethyl butadiene- 1,3, piperylene, myrcene, allenes, 1,2-butadiene,
1,4,9-decatrienes, 1,4-hexadiene, octadiene, 1,5-hexadiene and 4-methyl hexadiene-1,4.
[00149] Alicyclic polyunsaturated compounds, with or without a briding group, may be either monocyclic or polycyclic. Examples of such compounds are norbornadiene and its alkyl derivatives; the alkylidene norbornenes, in particular the 5-alkylidene norbornenes-2, in which the alkylidene group contains 1 to 20, by preference 1 to 8 carbon atoms; the alkenyl norbornenes, in particular the 5alkenyl norbornenes-2, in which the alkenyl group contains 2 to 20, by preference 2 to 10 carbon atoms, for instance vinyl norbornene, 5-(2'-methyl-2'butenyl)-norbornene- 2 and 5-(3'methyl-2'butenyl)-norbornene-2; dicyclopentadiene and the polyunsaturated compounds of bicyclo-(2,2,l)-heptane, bicyclo-(2,2,2,)-octane, bicylco(3,2,l)-octane and bicyclo(3,2,2)-nonane, with at least one of the rings being unsaturated. Further, compounds such as 4,7,8, 9tetrahydroindene and isoproylidene tetrahydroindene may be used. In particular, dicyclopentadiene, ethylidene norbornene, vinyl norbornene, or hexadiene may be used used. Mixtures of the above may also be used.
[00150] The diene is present in the polymer in quantities of up to 30 weight %, typically, however, up to 10-15 weight percent based upon the total weight percent of the polymer. Alternatively, the diene may be present in the copolymer from .1-10.0 weight %, particularly, between 1 and 8 weight %, based upon the total weight percent of the polymer.
[00151] The polymerization processes of the present disclosure may be utilized for production of any polyolefin though preference is given to homopolymers and copolymers of polyethylene. In one non-limiting embodiment, the polyolefins are copolymers of ethylene and at least one comonomer selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and combinations thereof. In another non-limiting embodiment, the polyolefins are bimodal copolymers of ethylene and at least one comonomer selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, and combinations thereof.
[00152] Polymerization reactors suitable for the present disclosure may be any type of reactor known in the art and may comprise at least one raw material feed system, at least one feed system for catalyst or catalyst components, at least one reactor system, at least one polymer recovery system or any suitable combination thereof. Suitable reactors for the present disclosure may further comprise any one or more of any of a catalyst storage system, an extrusion system, a cooling system, a diluent recycling system, or a control system. Such reactors may comprise continuous take-off and direct recycling of catalyst, diluent, and polymer. Generally, continuous processes may comprise the continuous introduction of a monomer, a catalyst, and optionally a diluent into a polymerization reactor and the continuous removal from this reactor of polymer and recycling of diluent and unreacted monomers and comonomers.
[00153] The comonomer, if present in the polymerization reactor, is present at any level that will achieve the desired weight percent incorporation of the comonomer into the finished polyethylene. This is expressed as a mole ratio of comonomer to ethylene as described herein, which is the ratio of the gas concentration of comonomer moles in the cycle gas to the gas concentration of ethylene moles in the cycle gas. In one embodiment, the comonomer is present with ethylene in the cycle gas in a mole ratio range of from 0 or 0.0001 (comonomer: ethylene) to 0.20 or 0.10, and from 0.001 to 0.080 in another embodiment, and from 0.001 to 0.050 in even another embodiment, and from 0.002 to 0.20 in still another embodiment. In yet another embodiment, the comonomer is present with ethylene in the cycle gas in a mole ratio range comprising any combination of any upper limit with any lower limit as described herein.
[00154] The processes of the present disclosure may be characterized in that the desired composition of high molecular weight to low molecular weight moiety can be achieved at any of the above comonomer to ethylene ratios.
[00155] Hydrogen, if present in the polymerization reactor, is present at any level that will achieve the desired melt index (MI, or 12) and molecular weights of the high and the low molecular weight component. Using the catalyst systems of the present disclosure increasing the concentration of hydrogen may increase the melt index of the polyolefin generated. MI can thus be influenced by the hydrogen concentration. The amount of hydrogen in the polymerization can be expressed as a mole ratio relative to the total polymerizable monomer, for example, ethylene, or a blend of ethylene and another alpha olefin. The amount of hydrogen used in the polymerization processes of the present disclosure is an amount necessary to achieve the desired MI of the final polyolefin resin.
[00156] In one embodiment, the ratio of hydrogen to total ethylene monomer (mol ppm H2: mol % ethylene) in the circulating gas stream is in a range of from 0 to 100, in a range of from 0.05 to 50 in another embodiment, in a range of from 0.10 to 40 in even another embodiment, and in a range of from 0.15 to 35 in still another embodiment. In yet another embodiment, the ratio of hydrogen to total ethylene monomer (mol ppm H2: mol % ethylene) in the circulating gas stream may be in a range comprising any combination of any upper mole ratio limit with any lower mole ratio limit described above.
[00157] The processes of the disclosure may be characterized in that the desired composition of high molecular weight to low molecular weight moiety can be achieved at any of the above hydrogen to ethylene ratios.
[00158] The process may also include "condensing agents" as is known in the art and disclosed in, for example, U.S. Patent Nos. 4,543,399, 5,405,922 and 462,999. The condensing agent, if present in the reactor can be at any level that will achieve the desired increase in the dew point in order to improve cooling and ultimately space time yields. Suitable condensing agents include but are not limited to saturated hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, n-octane or mixtures thereof.
[00159] The catalysts and catalyst systems of the invention described above are suitable for use in any polymerization process over a wide range of temperatures and pressures. The temperatures may be in the range of from -60°C to about 2800C, preferably from 50°C to about 2000C, and the pressures employed may be in the range from 1 atmosphere to about 500 atmospheres or higher.
[00160] The polymerization processes of the disclosure may be carried out in solution, in bulk, in suspension, in gas-phase, in slurry-phase, as a high-pressure process, or any combinations thereof. Generally solution, gas-phase and slurry- phase processes are preferred. The processes may be carried out in any one or more stages and/or in any one or more reactor having any one or more reaction zone and are conducted substantially in the absence of catalyst poisons. As known by one of skill in the art, organometallic compounds may be employed as scavenging agents for poisons to increase the catalyst activity. The polymerization processes may be carried out batchwise, continuously run, or any combinations thereof. In one non-limiting embodiment, the polymerization processes of the M
present disclosure are carried out in a continuous gas-phase reactor. In another non-limiting embodiment, polymerization processes of the disclosure are carried out in a single gas-phase reactor.
[00161] Preferred processes for the invention are high-pressure, solution, slurry and gas-phase processes.
[00162] A gas-phase process of the present disclosure may comprise contacting the catalyst system with monomers in a reactor vessel of desirable configuration to form a polyolefin. In one non-limiting embodiment, the contacting may take place in a first reactor vessel, followed by transfer of the formed polymer into another reactor vessel to allow further polymerization, optionally by adding the same or different monomers and optionally by adding the same or different catalyst components, activators, etc. In another non-limiting embodiment, the catalyst system is contacted with monomers in a single reactor vessel, followed by isolation of a finished polyolefin resin.
[00163] For example, a gas phase polymerization process of the disclosure may comprise use of a continuous cycle in which a cycling gas stream (i.e., a recycle stream or fluidizing medium) is heated in the reactor by the heat of polymerization. This heat may be removed from the recycle stream in another part of the cycle by a cooling system that is external to the reactor. In a gas fluidized bed process for producing polymers, a gaseous stream containing one or more monomers may be continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is preferably withdrawn from the fluidized bed and then recycled back into the reactor. Polymer product may be withdrawn from the reactor and fresh monomer added to replace the polymerized monomer. (See for example U.S. Patent Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661, 5,627,242, 5,665,818, 5,677,375, and 5,668,228, incorporated herein by reference).
[00164] Other gas phase processes contemplated by the process of the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and European Publication Nos. EP-A-O 794 200, EP-A-O 802 202 and EP-B-634 421, all of which are herein fully incorporated by reference. [00165] In a preferred embodiment, the gas-phase reactor utilized in the present invention is capable and the process of the invention is producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
[00166] The reactor temperature in a gas phase process may vary from about 30°C to about 12O0C, preferably from about 600C to about 1150C, more preferably in the range of from about 700C to 1100C, and most preferably in the range of from about 700C to about 95°C.
[00167] The reactor pressure in a gas phase process of the disclosure may be in the range of from about 100 psig to about 500 psig (about 690 kPa to about 3448 kPa), preferably from about 200 psig to about 400 psig (about 1379 kPa to about 2759 kPa), and more preferably from about 250 psig to about 350 psig (about 1724 kPa to about 2414 kPa).
[00168] The catalyst system may be supplied to the polymerization system as a solid, a paste or in the form of a suspension in a hydrocarbon, and/or may be treated with inert components, such as paraffins, oils, or waxes, to achieve better metering. If the catalyst system is to be metered into the reactor together with the monomer to be polymerized or the monomer mixture to be polymerized, the mixing unit and the metering line are preferably cooled.
[00169] Any one or more additives such as an antistatic or an alcohol may be used in the polymerization processes of the present disclosure, for example to improve the particle morphology of the olefin polymer. In general it is possible to use any one or more of the numerous additives suitable in olefin polymerization processes to improve any one or more parameter such as but not limited to reactor operability, particle morphology, catalyst activity, catalyst performance, and polymerization efficiency. The one or more additives may be fed directly into the polymerization system, either together with or separately from the catalyst system.
[00170] Another preferred polymerization process is a slurry polymerization process. A slurry polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres and even greater and temperatures in the range of 0°C to about 120°C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed.
[00171] A preferred polymerization technique of the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution. Such technique is well known in the art, and described in for instance U.S. Patent No. 3,248,179, which is fully incorporated herein by reference. Other slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Also, other examples of slurry processes are described in U.S. Patent No. 4,613,484, which is herein fully incorporated by reference.
[00172] In an embodiment the reactor used in the slurry process of the invention is capable of and the process of the invention is producing greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactor used in the process of the invention is producing greater than 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr). [00173] Examples of solution processes are described in U.S. Patent Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are fully incorporated herein by reference.
[00174] A preferred process of the invention is where the process, preferably a slurry or gas phase process is operated in the presence of a catalyst metal compound system of the invention and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like. This preferred process is described in PCT Publication No. WO 96/08520 and U.S. Patent No. 5,712,352 and 5,763,543, which are herein fully incorporated by reference.
[00175] Preferred processes for the invention are high-pressure, solution, slurry and gas-phase processes. More preferred processes are slurry and gas-phase processes.
[00176] The polymers of the present disclosure may also be produced by any one or more blending process whereby a high molecular weight polymer may be blended with a low molecular weight polymer. The resulting mixed copolymer may then be precipitated out of the blended solution. Blending processes are known in the art and any are suitable for use herein. Generally a high molecular weight polymer and a low molecular weight polymer are solution blended and the resulting copolymer is precipitated out of the blended solution. Preferably the blending process results in molecular mixing of the high molecular weight polymer and the low molecular weight polymer.
[00177] For blending embodiments of the present disclosure, the high molecular weight component may be present in an amount ranging from about 0.01% to 25% with the low molecular weight component making up the balance. Preferably, the high MW fraction is present from about 0.05 to about 20%, more preferably from about 0.075 to about 15% of a very high molecular weight component, even more preferably from about 0.1 to about 12.5%.
[00178] For blending embodiments of the disclosure, the high molecular weight polymer generally has a weight average molecular weight (Mw) of greater than about 1 million g/mol, preferably greater than about 1.5 million g/mol, even more preferably greater than about 2 million g/mol, and still more preferably greater than about 3 million g/mol. Generally the low molecular weight polymer has an Mw in the range of from about 40,000 to about 200,000 g/mol, preferably from about 50,000 to about 180,000 g/mol, more preferably from about 60,000 to about 175,000 g/mol, and even more preferably from about 70,000 to about 150,000 g/mol. Generally the high molecular weight polymer comprises an Mw at least 10 times greater than the Mw of the low molecular weight polymer, preferably at least 20 times greater than the Mw of the low molecular weight polymer, more preferably at least 30 times greater than the Mw of the low molecular weight polymer and even more preferably at least 40 times greater than the Mw of the low molecular weight polymer.
[00179] The polymers of the disclosure may comprise a unimodal, bimodal or multimodal molecular weight distribution (MWD). A bimodal polymer/resin is defined herein as a polymer/resin comprising two peaks in it's molecular weight distribution, one of the two peaks having a higher average molecular weight (defined herein as the high molecular weight component) than the other component (defined as the low molecular weight component). A multimodal polymer/resin is defined as a polymer/resin comprising more than two peaks in the molecular weight distribution.
[00180] Generally, the polymers of the disclosure comprise a high molecular weight component and a low molecular weight component. The polymers of the disclosure generally comprise from about 0.01 to about 25% of the high molecular weight component, preferably from about 0.05 to about 20%, more preferably from about 0.075 to about 15% of a very high molecular weight component, even more preferably from about 0.1 to about 12.5% of a very high molecular weight component, wherein the fraction of the high molecular weight component is determined by integrating the area under the molecular weight vs. dwt%/dLogM curve from molecular weight = 1,000,000 to molecular weight = 10,000,000.
[00181] As described previously, "high molecular weight" is defined herein as being greater than about 1,000,000 g/mol, preferably greater than about 1,500,000 g/mol, more preferably greater than about 2,000,000 g/mol, and even more preferably greater than about 3,000,000 g/mol. In one non-limiting embodiment, high molecular weight is greater than 5,000,000 g/mol. As described previously, "low molecular weight" is defined herein as being in the range of from about 40,000 to about 200,000 g/mol, preferably from about 50,000 to about 180,000 g/mol, more preferably from about 60,000 to about 175,000 g/mol, and even more preferably from about 70,000 to about 150,000 g/mol. In one non-limiting embodiment, low molecular weight is about 100,000 g/mol.
[00182] Generally the high molecular weight component comprises a molecular weight at least 10 times greater than the low molecular weight component, preferably at least 20 times greater than that of the low molecular weight component, more preferably at least 30 times greater than that of the low molecular weight component, and even more preferably at least 40 times greater than that of the low molecular weight component.
[00183] Generally the polymers of the disclosure may have a density in the range of from about 0.86g/cc to 0.97 g/cm3 as measured according to ASTM 1505-03.
[00184] The resins of the disclosure generally exhibit melt strength values greater than that of conventional linear or long chain branched polyethylene of similar melt index. As used herein "melt strength" refers to the force required to draw a molten polymer extrudate at a rate of 12mm/s2 at an extrusion temperature (190°C and 250°C were used herein) until breakage of the extrudate whereby the force is applied by take up rollers. The melt strength of the polymers of the disclosure, also referred to herein as "melt tension", may be expressed as a function of the melt index (MI) value, and generally may be greater than 6*MI" α6675. In other non-limiting embodiments, the MI value may be greater than 8*MI" °'6675. In still non-limiting embodiments, the MI value may be greater than 10*MI"
0.6675 [00185] In one non-limiting embodiment, the polymers of the present disclosure may have a melt index ("MI" or "I2") as measured by ASTM-D- 1238-E (190°C, 2.16 kg weight) in the range of from .001 dg/min to 25 dg/min. In other non- limiting embodiments, the polymers of the present disclosure may have a MI in a range of from about 0.001 dg/min to about 5 dg/min; in even other non-limiting embodiments a MI in a range of from about 0.01 dg/min to about 5 dg/min in other embodiments; and in still other non-limiting embodiments a MI in a range of from about 0.01 dg/min to about 1 dg/min.
[00186] In one non-limiting embodiment, the polymers of the present disclosure may have a melt flow ratio (MFR) in the range of from about 10 to 300. MFR is defined as WI2, wherein I2) is measured by ASTM-D- 1238-F, at 190°C, 21.6 kg weight. In other non-limiting embodiments, the polymers of the present disclosure may have a MFR in a range of from about 15 to 250; in even other non- limiting embodiments, a MFR in a range of from about 15 to 200; and in still other non-limiting embodiments a MFR in a range of from about 20 to 150. [00187] As known by one of skill in the art, when subjected to uniaxial extension at a given strain rate, the extensional viscosity of a polymer increases with time. As also known by one of skill in the art, the transient uniaxial extensional viscosity of a linear polymer can be predicted. Strain hardening occurs when a polymer is subjected to uniaxial extension and the transient extensional viscosity increases more than what is predicted from linear viscoelastic theory. As defined herein, the strain hardening index is the ratio of the observed transient uniaxial extensional viscosity to the theoretically predicted transient uniaxial extensional viscosity. Strain hardening index is expressed herein as the following ratio: ηE +observed / ηE +predicted.
At conditions characteristic of film blowing, for example strain rate of 1 sec 1, temperature of 19O0C, and time of 4 seconds (i.e., a strain (ε) of 4), generally the strain hardening index of the polymers of the present disclosure is a ratio/value greater than 3 in some embodiments, a value greater than 5 in other embodiments, a value greater than 8 in even other embodiments, and a value greater than 10 in still other embodiments. [00188] The polymers of the present disclosure may be characterized in that they exhibit an activation energy (Ea) of less than 7 kcal/mol/K. In other non-limiting embodiments, the Ea of the polymers of the present disclosure may be less than 6 kcal/mol/K.
[00189] In the present disclosure, the activation energy is determined from dynamic oscillatory shear rheology measurements at five different temperatures, 1500C, 1700C, 1900C, 2100C, 2300C and 250 0C. At each temperature, scans are performed as a function of angular shear frequency (from ω = 100 rad/s to ω = 0.01 rad/s) at a constant shear strain. Master curves of storage modulus, G', and loss modulus, G", are obtained by time-temperature (t-T) superposition and the flow activation energies (E3) are obtained from an Arrhenius plot, aτ=exp (Ea/kT), where 1/T is plotted as a function of ln( ax), which relates the shift factor (ax) to
Ea.
[00190] As known by one of skill in the art, rheological data may be presented by plotting the phase angle versus the absolute value of the complex shear modulus to produce a van Gurp-Palmen (vGP) plot. The vGP plot of conventional polyethylene polymers shows monotonic behavior and a negative slope toward higher G* values. Conventional LLDPE polymer both with and without long chain branches also exhibit a negative slope on a vGP plot. The vGP plots of the polymers described in the present disclosure exhibit two slopes - a positive slope at lower G* values and a negative slope at higher G* values.
[00191] Referring now to FIG. 1, there are shown van Gurp-Palmen (vGP or VGP) plots of various linear polyethylene resins: a conventional monodispersed PE (hydrogenated polyputadiene) (closed circles), a conventional metallocene LLDPE resin with a narrow molecular weight distribution (closed squares), a conventional bimodal resin having a broad molecular weight distribution (asterisk), and an inventive resin of the disclosure (closed diamonds). The molecular weights and molecular weight distributions of the conventional resins are shown in Table 1 below. Increasing polydispersity in comparative conventional resins stretches the curve along the abscissa, but does not change the monotonic nature of the vGP plot (note how their curves in FIG. 1 become less 3y
steep). The resin (Exceed™1018) and the bimodal resin (Borouge™ FB 2230) are commercially available resins. In non-limiting embodiments of the present disclosure, the introduction of a high molecular weight fraction according to the disclosure may change the shape of the vGP plot in that it causes a maximum in the vGP plot as shown in FIG. 1.
Table 1:
Figure imgf000060_0001
[00192] In non-limiting embodiments, the ratio of the z-average molecular weight (Mz) to the weight average molecular weight (Mw) of the polymers of the present disclosure may be a ratio having a value in a range of from about 6 to 12. In other non-limiting embodiments, the Mz/Mw ratio may be a value in a range of from about 7 to 15. In even other non-limiting embodiments, the Mz/Mw ratio may be a value greater than 10. The ratio of the Mw to the number average molecular weight (Mn) (ratio of Mw/Mn is also referred to as polydispersity) can be in the range of from 2.5 to 8 in some non-limiting embodiments, from 3.0 to 10 in other non-limiting embodiments, and from 3.5 to 12 in even other non-limiting embodiments. Generally for the polymers of the disclosure, the Mz/Mw ratio is a value greater than the Mw/Mn ratio. As known in the art, Mn is the number average molecular weight and may be expressed as Σ(M,N,)/ΣN,; Mw is the weight average molecular weight and may be expressed as Z(M1 2N1)ZX(M1N1); and Mz is the z-average molecular weight of a polymer and may be expressed as Σ(M, N,)/Σ(M, N1) wherein Ni is the number of molecules of molecular weight Mi. Techniques for determining these values are known in the art and any may be used herein. [00193] The polymers of the disclosure generally show very high viscosities at low shear rates and exhibit strong shear thinning. A shear thinning index may be expressed as the ratio of the complex viscosities (η*) at two given- oscillatory shear frequencies, arbitrarily selected herein to be 0.01 rad/sec (η*o.oi) and 100 rad/sec (η*ioo)- Thus, the shear thinning index is expressed herein as Cη*o.oi)/(η*ioo)- Both (η*o.oi) and (η*ioo) are obtained from oscillatory shear rheometry as described herein. The shear thinning index (η*o.oi/η*ioo) of the polymers of the present disclosure may be a value in the range of 5 to 500. In other non-limiting embodiments, the shear thinning index may be in the range of 25 to 500. In even other embodiments, the shear thinning index may be in the range of 50 to 500. In still other embodiments, the shear thinning index may be in the range of 100 to 500.
[00194] The resins of the disclosure are suitable for use in a variety of products and end-use applications including, but not limited to film, sheets, laminating, jacketing, insulating, and a variety of articles produced by injection molding, blow molding, extrusion coating, profile extrusion, and combinations thereof.
EXAMPLES
[00195] It is to be understood that while the invention has been described in conjunction with the specific embodiments thereof, the foregoing description is intended to illustrate and not limit the scope of the invention. Other aspects, advantages and modifications will be apparent to those skilled in the art to which the invention pertains.
[00196] Therefore, the following examples are put forth so as to provide those skilled in the art with a complete disclosure and description of how to make and use the compounds of the invention, and are not intended to limit the scope of that which the inventors regard as their invention. Because of the high molecular weights of the polyethylene resins described herein, it is necessary to measure size exclusion chromatography at elevated temperatures to ensure adequate solubility of the polymer molecules. Molecular weights and molecular weight distributions of the resins described herein were determined using high temperature size exclusion chromatography. O l
Measurements of Molecular Weights and Molecular Weight Distributions
100197] The molecular weights and molecular weight distributions of the resins described in the present disclosure were characterized using a High Temperature Size Exclusion Chromatograph (PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel 10mm Mixed-B columns were used. The nominal flow rate was 1.0 cm3 /min, and the nominal injection volume was 300 μL. The various transfer lines, columns and differential refractometer (the DRI detector) were contained in an oven maintained at 160 C.
[00198] Polymer solutions were prepared in filtered 1,2,4-Trichlorobenzene (TCB) containing 1000 ppm of butylated hydroxy toluene (BHT). The same solvent was used as the SEC eluent. Polymer solutions were prepared by dissolving the desired amount of dry polymer in the appropriate volume of SEC eluent to yield concentrations ranging from 0.5 to 1.5 mg/mL. The sample mixtures were heated at 160°C with continuous agitation for about 2 to 2.5 hours. Sample solution will be filtered off-line before injecting to GPC with 2μm filter using the Polymer Labs SP260 Sample Prep Station.
[00199] The separation efficiency of the column set was calibrated using a series of narrow MWD polystyrene standards, which reflects the expected MW range for samples and the exclusion limits of the column set. Eighteen individual polystyrene standards, ranging from Mp -580 to 10,000,000, were used to generate the calibration curve. The polystyrene standards are obtained from Polymer Laboratories (Amherst, MA). To assure internal consistency, the flow rate is corrected for each calibrant run to give a common peak position for the flow rate marker (taken to be the positive inject peak) before determining the retention volume for each polystyrene standard. The flow marker peak position thus assigned was also used to correct the flow rate when analyzing samples; therefore, it is an essential part of the calibration procedure. A calibration curve (logMp 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 ^nd bl
order polynomial. The equivalent polyethylene molecular weights are determined by using the following Mark-Houwink coefficients:
Figure imgf000063_0001
Dynamic Rheologv
[00200] For dynamic oscillatory shear measurements, the resins were stabilized with 500 ppm of Irganox 1076 and 1500 ppm of Irgafosl68. The measurements were carried out on an oscillatory rheometer (Rheometrics RDS-2, ARES) with 25mm diameter parallel plates in a dynamic mode under nitrogen atmosphere. For all experiments, the rheometer was thermally stable at 190°C for at least 30 minutes before inserting compression-molded sample of resin onto the parallel plates. To determine the samples viscoelastic behavior, frequency sweeps in the range from 0.01 to 100 rad/s were carried out at 1900C under constant strain. To determine the activation energy, the sweeps were carried out at 5 different temperatures as described herein.
Structures of Precatalysts and Ligands
bό
Figure imgf000064_0001
Precat A Ligand A Precat B
Figure imgf000064_0002
Ligand B Precat C Precat D
[00201] Anhydrous oxygen free solvents were used. Thirty-weight percent methylaluminoxane (MAO) and (1-Me, 3-BuCp)2ZrCl2 were obtained from Albemarle Corporation. (n-PrCp)2HfCl2 was obtained from Boulder Scientific, (n- PrCp)2HfMe2 may be prepared by methylation of (n-PrCp)2HfCl2 with methyl lithium in toluene. Ligand B was obtained from Symyx Technologies. Zr(CH2Ph)2Cl2(OEt2) was prepared by reaction of ZrBnZ4 and ZrCl4 in diethyl ether. The comparative supported catalyst (1-Me, 3-Bu Cp)2ZrCl2 is a commercial catalyst (HPlOO) obtained from Univation Technologies.
Example 1. Preparation of Ligand A
Figure imgf000065_0001
Figure imgf000065_0002
Figure imgf000065_0003
[00202] STEP 1. A solution of 3Og (0.13mol, leq) of O-MOM- bromo methyl compound in 300ml of dry tetrahydrofuran was cooled to -76°C. 53 ml of n-butyl lithium (1.2eq, 0.155 mol) was added in such a manner that the temperature did not rise beyond -700C. The resulting mixture was stirred for another 4 hours at - 78°C. 53ml (O.lδmol, 1.4eq) of n-butyl borate was then added to the reaction mass maintaining the temperature from -76°C to -700C. Stirring was then continued for another 5hours after which the reaction mass was quenched with 150ml of water. This was stirred for another lOhrs. The organic layer and the aqueous layer were separated. The aqueous layer was washed with petroleum ether and the organic layer was washed with 10% sodium hydroxide solution. The aqueous layer and the sodium hydroxide layer were then combined and acidified using 505 cone. HCl solution. A white solid was obtained which was filtered off and dried under vacuum. Yield = 2Og.
[00203] STEP 2. 15g (0.067mol, leq) of l-Bromo-2-methyl naphthalene, 0.4g ( 5mol% ) of palladium tetrakis, 16g ( O.Oδlmol, 1.2eq) of -0-MOM boronic acid, 29g of 2M solution of sodium carbonate and 150ml of toluene were taken in a RB to
flask and heated to 1200C. After 16 hrs, the reaction mass was diluted with ethyl acetate and the two layers were separated. The resulting organic layer was washed with water followed by brine. This was then dried over sodium sulfate, filtered and concentrated. The crude obtained (25g) was then taken for further step without any purification.
[00204] STEP 3. The 25g of crude material obtained from STEP 2 was stirred along with 240ml of methanolic HCl solution at RT for 16 hrs. The reaction mass was then diluted with excess of ethyl acetate. The organic layer was then washed with water followed by brine. This was then dried over sodium sulfate, filtered and concentrated. The crude obtained was then purified by column chromatography using 1% of ethyl acetate in petroleum ether. Yield= 11.8g.
[00205] STEP 4. 11.8g (0.047 mol, leq) of methynaphthyl phenol obtained from the above step and 7ml (0.047mol, leq) of triethyl amine were taken in 110ml of dry dichloromethane and stirred well. A solution of 13g (0.007mol, 1.5eq) of N- bromo succinimide in 300ml of dry dichloromethane was added over a period of 30mins. The reaction mass was then stirred for 24 hours after which it was quenched with 1.5N HCl. The organic layer was separated and washed with water and brine. It was then dried over sodium sulfate and concentrated. The crude obtained (17g) was then taken for further step without any purification as it was pure enough. (98%).
[00206] STEP 5. To a solution of 17g (0.052mol, leq) of the bromo phenol compound and 43ml (0.26mol, 5eq) of diisopropyl ethyl amine in 170ml of dry dichloromethane, 16ml (0.208mol, 4eq) of MOM chloride was added in drops. The resulting mass was stirred at RT for 16 hrs. The reaction mass was diluted with 1.5N HCl solution. The organic layer was separated and washed with water and brine. It was then dried over sodium sulfate and concentrated. The crude obtained was purified by column chromatography using petroleum ether and ethyl acetate as eluant which was 99% pure by HPLC. This was taken for the further step. Yield= 12g.
[00207] STEP 6. A solution of 12g (0.0323mol, leq) of O-MOM- bromo compound in 120ml of dry tetrahydrofuran was cooled to -76°C. To this 13.5ml of Oti
n-butyl lithium (1.2eq, 0.034mol) was added in such a manner that the temperature did not rise beyond -700C. The resulting mixture was stirred for another lhr at -78°C. 13ml (0.045mol, 1.4eq) of n-butyl borate was then added to the reaction mass maintaining the temperature from -76°C to -700C. The reaction mass was then quenched with 50ml of water and extraction was done in ethyl acetate. This was dried over sodium sulfate, filtered and concentrated. The crude (1 Ig) obtained was taken along with 3.7g (10mol% ) of palladium tetrakis, 3.8g ( 0.008mol) of C3 iodo ether (prepared from the 2-iodophenol and 1,2- dibromopropane), 27g (0.258mol,8eq) of 2M solution of sodium carbonate and 120ml of toluene, in a RB flask and heated to 1200C. After 16 hrs, the reaction mass was diluted with ethyl acetate and the two layers were separated. The resulting organic layer was washed with water followed by brine. This was then dried over sodium sulfate, filtered and concentrated. The crude obtained (17g) was then taken for further step without any purification.
[00208] STEP 7. The 17g of crude material obtained from STEP 6 was stirred along with 170ml of methanolic HCl solution and 3 ml of dichloromethane at RT for 16 hrs. The reaction mass was then diluted with excess of ethyl acetate. The organic layer was then washed with water followed by brine. This was then dried over sodium sulfate, filtered and concentrated. The crude obtained was then purified by column chromatography using 1% of ethyl acetate in petroleum ether. Two fractions were collected and analyzed by HPLC, NMR and LCMS. The first fraction was 4g and consisted of two isomers which were confirmed by NMR, LCMS AND HPLC. The second fraction (550mg) also consists of two isomers which were confirmed by NMR and LCMS.
Example 2. Preparation of Precatalyst A
[00209] To a solution consisting of Ligand A (2.750 grams, 3.814 mmol) in approximately 80 milliliters of toluene was added a solution of Zr(CH2Ph)2Cl2(Et2O) (1.603 grams) in 20 milliliters of toluene. An additional 20 milliliters of solvent were added to the mixture. After stirring the mixture at room temperature for 1 hour, the reaction was heated to 80 °C for 2 hours. o/
Approximately 70% of the solvent was removed, and pentane added to induce further precipitation of the product. The mixture was chilled. The solids collected by filtration and washed with minimum pentane.
Example 3. Preparation of Precatalyst B
[00210] A solution of Zr(CH2Ph)2Cl2(Et2O) i.2 (58.7 mg, 0.1355 mmol) in toluene (8 mL) was added to a hot solution (120 °C) of Ligand B (100 mg, 0.129 mmol) in toluene (32 mL) over a period of 5 minutes while stirring. After 15 min, the reaction was chilled and the solvent mostly removed. When there was 1-2 mL left, the solution was placed in about 15 mL of pentane. The solvents were reduced to ca 1/2 of the original volume. The slurry was decanted and the solids dried. Yield 39 mg.
Example 4. Preparation of Methyl Aluminoxane Supported on Silica (SMAO) [00211] In a typical procedure, Crosfield ES757 silica (741 g), dehydrated at 6000C, was added to a stirred (overhead mechanical conical stirrer) mixture of toluene (2 L) and 30 wt% solution of methyl aluminoxane in toluene (874 g, 4.52 mol). The silica was chased with toluene (200 mL) then the mixture was heated to 90°C for 3 h. Afterwards, volatiles were removed by application of vacuum and mild heat (40°C) overnight then the solid was allowed to cool to room temperature.
Examples 5-21. Supported Catalyst Preparations
[00212] A solution of precatalysts (PC) and toluene was added at a rate of ca. 0.5 mL/min to a slurry SMAO and pentane (amounts provided in Table 2 below), stirred with an overhead stirrer. After stirring for > 30 min, the mixture was filtered and dried in-vacuo.
Table 2 Supported Catalyst preparations
Figure imgf000068_0001
Oδ
Figure imgf000069_0001
Examples 22-42. Polymerization Testing in a Continuous Fluidized Bed Reactor [00213] These catalysts were tested in a continuous fluidized-bed gas-phase reactor with a nominal 14" reactor diameter, an average bed weight of about 1900 g, gas- velocity of about 1.6 ft/s, production rate of about 500 g/h. The reactor was operated at a temperature of 79.4 °C, and a pressure of 300 psig. The composition of ethylene, hydrogen, and 1-hexene is indicated in Table 3 below; the balance being nitrogen.
Figure imgf000070_0001
Example 43 - Catalyst Evaluation / Polymer production in LGPR
[00214] The test catalysts were evaluated in a continuous run gas phase reactor R125 (LGPR). The reactor was lined out with standard HPlOO catalyst at /υ
conditions used to make 1.2 MI, 0.917 density (LGPR condition 51-2006). Product was collected and the reactor was transitioned to each of the other catalysts.
[00215] Ethylene/ 1-hexene copolymers were produced according to the following procedure. The catalyst composition was injected dry into a fluidized bed gas phase polymerization reactor. More particularly, polymerization was conducted in a 152.4 mm diameter gas-phase fluidized bed reactor operating at approximately 2068 kPa total pressure. The reactor bed weight was approximately 2 kg. Fluidizing gas was passed through the bed at a velocity of approximately 0.6 m per second. The fluidizing gas exiting the bed entered a resin disengaging zone located at the upper portion of the reactor. The fluidizing gas then entered a recycle loop and passed through a cycle gas compressor and water-cooled heat exchanger. The shell side water temperature was adjusted to maintain the reactor temperature as specified in Tables 4-8. Ethylene, hydrogen, 1-hexene and nitrogen were fed to the cycle gas loop just upstream of the compressor at quantities sufficient to maintain the desired gas concentrations as specified in Tables 4-8. Gas concentrations were measured by an on-line vapor fraction analyzer. Product (polyethylene particles) was continuously withdrawn from the reactor in batch mode into a purging vessel before it was transferred into a product bin. Residual catalyst and activator in the resin was deactivated in the product drum with a wet nitrogen purge. The catalyst was fed to the reactor bed through a stainless steel injection tube at a rate sufficient to maintain the desired polymer production rate. "C6ZC2 flow ratio ("FR")" is the ratio of the lbs of 1- hexene comonomer feed to the pounds of ethylene feed to the reactor, whereas the C6ZC2 ratio is the ratio of the gas concentration of 1-hexene moles in the cycle gas to the gas concentration of ethylene moles in the cycle gas. The C6ZC2 ratio is obtained from a cycle gas vapor fraction analyzer, whereas the C6ZC2 Flow Ratio comes from some measure of the mass flow. The cycle gas is the gas in the reactor, and is measured from a tap off the recirculating loop around the reactor. The ratios reported in the following tables are from the gas concentrations in the reactor. Samples are taken every 9 min, and thus reported C6ZC2 ratios are running averages. Tables 4-8 provide summaries of run conditions and product properties / i
of non-limiting examples of the present disclosure for resins with densities of 0.91 - 0.95 as indicated in the tables.
[00216] The MI and HLMI values reported in Tables 4-8 as "QC, reactor granules" were obtained from the polymer granules that were isolated from the polymerization reactor. Each granular resin was dry-blended with 1500 ppm BHT (2,6-bis( 1,1 -dimethyl ethyl)-4-methylphenol). MI and HLMI were then measured according to ASTM -D-1238-E and ASTM D-1238-F, respectively.
[00217] The MI and HLMI values reported in Tables 4-8 as "ASTM, pellets" were obtained from compounded resins. To compound the resins, 500 ppm Irganox 1076 and 1500 ppm Igrafos 168 (both available from Ciba Chemicals) were added to the reactor granules and the admixture extruded using a %" Haake twin screw extruder. The melt temperature was 2100C. The output rate was about 3.5 lbs/hr. The MI and HLMI of the pellets were then measured according to ASTM -D- 1238-E and ASTM D-1238-F, respectively.
[00218] The density values reported in Tables 4-8 as "QC, reactor granules" were obtained from the polymer granules that were isolated from the polymerization reactor. Each granular resin was dry-blended with 1500 ppm BHT and compression molded plaques were produced by heating the polymers in a mold to 179°C and subsequently cooling them to 23°C at a rate of 15°C. The molding pressure was chosen such that air pockets are removed and a uniform samples result. The density was then determined by immersing solid specimens of the compression molded plaques in a column filled with liquid of uniformly gradient density. The gradient density was in accordance with ASTM 1505.
[00219] The density values reported in Tables 4-8 as "ASTM, pellets" were obtained from compounded resins. To compound the resins, 500 ppm Irganox 1076 and 1500 ppm Igrafos 168 were added to the reactor granules and the admixture extruded using a %" Haake twin screw extruder. The melt temperature was 2100C. The output rate was about 3.5 lbs/hr. The density of the pellets was then measured according to ASTM 1505-03. Il
Table 4A: Sum mary of Process Data - resin density 0.91
HP-100 + HP-100 + HP-100 base 0.05% Unιv8 0.1% Unιv8
Example 21 22 23 I
Catalyst from Example HP100 5 6
PROCESS DATA
H2 conc (molppm) 251 246 244
Hydrogen (low (seem) 6 72 6 22 688
Comonomer cone (mol%) 1 083 1 109 1 097
C2 conc (mol%) 35 0 35 0 35 0
Comonomer/C2 Flow Ratio 0 135 0 135 0 135
C2 flow (g/hr) 590 606 624
H2/C2 Ratio 7 2 70 7 0
Comonomer/C2 Ratio 0 031 0032 0031
Rx Pressure (psig) 300 300 300
Reactor Temp (F) 175 175 175
Avg Bedweιght (g) 1894 1930 1903
Production (g/hr) 494 462 533
Residence Time (hr) 3 8 4 2 36
C2 Utilization (gC2/gC2 poly) 1 19 1 31 1 17
Avg Velocity (ft/s) 1 58 1 57 1 46
Catalyst Timer (minutes) 15 0 500 38 0
Catalyst Feed (g/hr) 0694 0208 0274
Cat Prod (g/g) - MB(new= 249) 496 1546 1356
Product Data
Bulk Density 0 3565 0 3993
Powder Flow Time 7 63 7 25
Total Production (grams) 26978 12717 18669
Number of Bedturnovers 14.2 6.6 9.8
Basic Resin Data (QC)
Ml (QC reactor granules) 5 92 547 4 51
HLMI (QC reactor granules) 112 31 104 81
HLMI/MI (QC reactor granules) 18 97 2324
Density (QC reactor granules) 09115 0 9107 09105 Ii
Figure imgf000074_0001
/4
Figure imgf000075_0001
/5
Figure imgf000076_0001
/t>
Figure imgf000077_0001
/ /
Table 6B: Summar of Resin Data - resin densit 0.93
Figure imgf000078_0001
/8
Table 7A: Summary of Process Data - resin density 0.94
Figure imgf000079_0001
/y
Table 7B: Summary of Resin Data - resin density 0.94
Figure imgf000080_0001
8U
Figure imgf000081_0001
O l
Table 8B: Summary of Resin Data - resin density 0.94
HP-100 VP-100 + VP-1 OO + VP-100 + base VP-100 base n 0.i1V /o ι U,nnhivΛβ 025% °'5%
Figure imgf000082_0001
[00220] The present inventors have found that the polymers produced by a catalyst system of the disclosure comprising a metallocene catalyst component and a non- metallocene catalyst component possess advantageous properties in comparison to polymer produced using the metallocene catalyst alone, and in comparison to conventional polymers.
[00221] As used herein, "melt strength" is defined as the force required to draw a molten polymer extrudate at a rate of 12mm/s2 and at an extrusion temperature (1900C and 2500C were used herein) until breakage of the extrudate whereby the force is applied by take up rollers. The polymer is extruded at a velocity of 0.33 mm/s through an annular die of 2 mm diameter and 30 mm length. Melt strength values reported herein are determined using a Gottfert Rheotens tester and are reported in centi-Newtons (cN). Additional experimental parameters for determining the melt strength are listed in Table 9. For the measurements of melt strength, the resins were stabilized with 500 ppm of Irganox 1076 and 1500 ppm of Irgafosl68.
Table 9: Melt Strength test parameters
Figure imgf000082_0002
JSZ
[00222] FIG. 2 shows the melt strength of non-limiting inventive resins 1, 2, and 3 compared with several conventional resins having low MI (BMC-100 untailored, BMC-100 tailored, Borouge FB2230, and EZP 1804). As seen in FIG. 2, the melt strength of inventive resin 3 is an order of magnitude higher than that of linear or long chain branched polyethylenes of similar MI.
[00223] It is known in the art that when a polymer is subjected to uniaxial extension, the extensional viscosity of the polymer increases with strain rate. It is also known that the transient uniaxial extensional viscosity of a linear polymer can be predicted. "Strain hardening" occurs when a polymer is subjected to uniaxial extension and the transient extensional viscosity increases more than what is predicted from linear viscoelastic theory. As defined herein, the strain hardening index is the ratio of the observed transient uniaxial extensional viscosity (j|E +observed) to the theoretically predicted transient uniaxial extensional viscosity OlE +predicted). Strain hardening index is expressed herein as the following ratio: ηE +observed / ηE +predicted.
[00224] Referring now to FIG. 3 there is provided the extensional viscosity of inventive resin 3 at a function of time. At conditions characteristic of film blowing for example strain rate of 1 sec 1, temperature of 190°C, and time of 4 seconds (i.e., a strain (ε) of 4), the strain hardening index of the polymers of the present disclosure is a value greater than 3 in some embodiments, a value greater than 5 in other embodiments, a value greater than 8 in even other embodiments, and a value greater than 10 in still other embodiments.
[00225] or extensional viscosity measurements, the resins were stabilized with 500 ppm of Irganox 1076 and 1500 ppm of Irgafosl68. The transient uniaxial extensional viscosity was measured at temperatures of 150 0C and 190 0C and different strain rates, 0.1 sec"1, 1.0 sec"1, and 10 sec"1. For example, the transient uniaxial extensional viscosity can be measured using a SER-HV -401 Testing Platform, which is commercially available from Xpansion Instruments LLC, Tallmadge, OH, USA. The SER Testing Platform was used on a Rheometrics ARES-LS rotational rheometer, which is available from TA Instruments. Inc., Newcastle, DE, USA. The SER Testing Platform is described in US patent 6,578,413, which is incorporated herein by reference. A general description of transient uniaxial extensional viscosity measurements is provided, for example in, "Strain hardening of various polyolefins in uniaxial elongational flow", The Society of Rheology, Inc. J. Rheol. 47(3), 619-630 (2003); and "Measuring the transient extensional rheology of polyethylene melts using the SER universal testing platform", The Society of Rheology, Inc. J. Rheol. 49(3), 585-606 (2005), incorporated herein by reference.
[00226] Extensional rheology data from the Sentmanat Extensional Rhoemeter (SER) indicate the inventive resins show strain hardening behavior and extremely high transient uniaxial extensional viscosities (also referred to herein simply as "extensional viscosity"). FIG. 3 shows extensional viscosity of inventive resin 3 as a function of time. The reference line in FIG. 3 is the predicted linear viscoelastic envelop.
[00227] The inventive resins show strong shear thinning. They can be readily extruded but have very high viscosities at low shear rates, providing for the high melt strength. FIG. 4 shows the shear thinning characteristics of inventive resins 1, 2 and 3 compared to the XCAT-HP base resin. As can be seen in FIG. 4, the inventive resins have similar viscosities at high frequencies but much higher viscosities at low frequencies than the base resin (shear thinning). FIG. 5 compares inventive resins 1, 2, and 3 with conventional resins (Borouge FB2230 and EZP 1804), which show very high/strong shear thinning characteristics. As can be seen in FIG. 5, the inventive resins have similar viscosities at high frequencies but much higher viscosities at low frequencies than comparative resins (comparative resins already show very high shear thinning).
[00228] In FIG. 6, the Van Gurp-Palmen plots of non-limiting inventive resins 2 and 3 are shown in comparison with the HP-100 base resin. FIG. 7 shows a comparison of the van Gurp-Palmen plots of non-limiting inventive resins 2 and 3 and two conventional resins (Borouge FB2230 and EZP 1804). EZP1804 exhibits the signature of a highly branched long-chain LLDPE. Borouge 2230 is a commercial bimodal LLDPE that does not have long chain branches. Both conventional resins show the expected behavior.
Example 44 - Film Products
[00229] Despite the high viscosities, the material could readily be made into film with good bubble stability. Blown films were made using Haake Rheomex 252P single screw extruder in connection with a Brabender blown film die. The extruder was equipped with a 19 mm (0.75 inch) metering screw that has a compression ratio 3:1. Ratio of screw diameter over length was 20: 1. Output rate was about 3.5 lbs/hr. Additional film blowing parameters are provided in Table 10.
Table 10: Film Blowing parameters
Figure imgf000085_0001
[00230] Tables 11 and 12 provide some properties of non-limiting example films produced from resins of the disclosure. »3
Table 11: Film Properties - Resin Density 0.93
Figure imgf000086_0001
δθ
Figure imgf000087_0001
Figure imgf000087_0002
Figure imgf000088_0001
'exhausted sample and unable to obtain 10/10 ratio
[00231] The phrases, unless otherwise specified, "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, as along as such steps, elements, or materials, do not affect the basic and novel characteristics of the invention, additionally, they do not exclude impurities normally associated with the elements and materials used.
[00232] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may δδ
be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
[00233] All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present invention. Further, all documents and references cited herein, including testing procedures, publications, patents, journal articles, etc. are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present invention.
[00234] While the invention has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the invention as disclosed herein.

Claims

CLAIMSWhat is claimed is:
1. An ethylene polymer comprising units derived from ethylene, at least one other alpha-olefin comonomer, and at least one diene, and having at least one of the following properties: (i) melt strength value greater than 6*MF0'6675, wherein MI is the melt index value of said polymer measured in accordance with ASTM- D-1238-E, (ii) a ratio of extensional viscosity measured at a strain rate of 1 sec"1, 19O0C, and time=4 seconds to that predicted by linear viscoelasticity at the same temperature and time of greater than 3, (iii) an activation energy (Ea) of less than 7 kcal/mol/K, (iv) a Mz/Mw ratio greater than the Mw/Mn ratio, wherein Mz is the z-average molecular weight of said polymer, Mw is the weight average molecular' weight of said polymer, Mn is the number average molecular weight of said polymer, and v) a van Gurp-Palmen plot comprising a positive slope and possessing a maximum, wherein the van Gurp-Palmen plot is a plot of the phase angle versus the absolute value of the complex shear modulus determined from dynamic rheology, more particularly, from frequency sweeps in the range from 0.01 to 100 rad/s at 1900C.
2. The ethylene polymer of claim 1, wherein the at least one other alpha- olefin comonomer is selected from the group consisting of propylene, 1-butene, t- pentene, 1-hexene, 1-heptene, 1-octene, and combinations thereof.
3. The ethylene polymer of claim 1 or 2, wherein the at least one diene is selected from a C4 to C2o aliphatic or alicyclic polyunsaturated compound.
4. The ethylene polymer of any one of claims 1-3, wherein the at lest one diene is selected from 1,3-butadiene, isoprene, 2,3-dimethyl butadiene- 1,3, 2- ethyl butadiene- 1,3, piperylene, myrcene, allenes, 1,2-butadiene, 1,4,9- decatrienes, 1,4-hexadiene, octadiene, 1,5-hexadiene and 4-methyl hexadiene-1,4, and mixtures thereof. yυ
5. The ethylene polymer of any one of claims 1-4, wherein said polymer comprises at least two of said properties (i), (ii), (iii), (iv) and (v).
6. The ethylene polymer of any one of claims 1-4, wherein said polymer comprises at least three of said properties (i), (ii), (iii), (iv) and (v).
7. The ethylene polymer of any one of claims 1-4, wherein said polymer comprises at least four of said properties (i), (ii), (iii), (iv) and (v).
8. The ethylene polymer of any one of claims 1-4, wherein said polymer comprises said properties (i), (ii), (iii), (iv) and (v).
9. The ethylene polymer of any one of claims 1-8, wherein in property (i) said melt strength value is greater than 8*MΓ0 6675.
10. The ethylene polymer of any one of claims 1-8, wherein in property (i) said melt strength value is greater than 10*MI"α6675.
11. The ethylene polymer of any one of claims 1-10, wherein in property (ii) said ratio is greater than 5.
12. The ethylene polymer of any one of claims 1-10, wherein in property (ii) said ratio is greater than 8.
13. The ethylene polymer of any one of claims 1-12, wherein said polymer exhibits a bimodal molecular weight distribution comprising a first molecular weight component having a weight average molecular weight (Mw) of greater than 1 million g/mol, and a second molecular weight component comprising a Mw in the range of 40,000 to 200,000 g/mol, and wherein said first component is present in said polymer in an amount in the range of about 0.05% to about 20%. yi
14. The ethylene polymer of any one of claims 1-13, wherein said ethylene polymer has a density measured in accordance with ASTM 1505-03 in the range of 0.89 g/cm3 to 0.97 g/cm3.
15. An article produced from the ethylene polymer of any one of claims 1-14.
16. The article of claim 15, wherein said article is a film.
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