WO2007136494A2 - Ethylene/ alpha-olefin/ diene solution polymerization process - Google Patents

Ethylene/ alpha-olefin/ diene solution polymerization process Download PDF

Info

Publication number
WO2007136494A2
WO2007136494A2 PCT/US2007/009842 US2007009842W WO2007136494A2 WO 2007136494 A2 WO2007136494 A2 WO 2007136494A2 US 2007009842 W US2007009842 W US 2007009842W WO 2007136494 A2 WO2007136494 A2 WO 2007136494A2
Authority
WO
WIPO (PCT)
Prior art keywords
phenyl
methyl
bis
oxoyl
phenoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2007/009842
Other languages
French (fr)
Other versions
WO2007136494A3 (en
Inventor
Harold W. Boone
Carl N. Iverson
Wayde V. Konze
Daniel D. Vanderlende
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=38572813&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2007136494(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to JP2009510950A priority Critical patent/JP5603595B2/en
Priority to MX2008014668A priority patent/MX2008014668A/en
Priority to CN2007800233160A priority patent/CN101472952B/en
Priority to ES07755918.5T priority patent/ES2475159T3/en
Priority to AU2007254428A priority patent/AU2007254428A1/en
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to US12/300,863 priority patent/US8299189B2/en
Priority to EP07755918.5A priority patent/EP2024399B1/en
Priority to KR1020087030629A priority patent/KR101401785B1/en
Priority to CA002652456A priority patent/CA2652456A1/en
Publication of WO2007136494A2 publication Critical patent/WO2007136494A2/en
Publication of WO2007136494A3 publication Critical patent/WO2007136494A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C08F10/02—Ethene
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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
    • Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen

Definitions

  • Catalyst compositions based on well defined donor ligand containing metal complexes referred to as post-metallocene complexes have been shown to give products having better comonomer incorporation and narrow molecular weight distribution.
  • these catalysts often have poor high temperature stability and suffer from poor catalytic efficiencies, especially at elevated polymerization temperatures.
  • ethylene, ⁇ -olefin and diene containing polymers especially ethylene, propylene, and ethyl idenenorbornene (ENB) containing polymers
  • the resulting polymer molecular weight and comonomer incorporation ratio is often deficient.
  • Examples .of one type of the foregoing post metallocene catalysts are disclosed in USP 6,827,976, where Group 3-6 or Lanthanide metal complexes, preferably Group 4 metal complexes, of bridged divalent aromatic ligands containing a divalent Lewis base chelating group are disclosed.
  • Group 3-6 or Lanthanide metal complexes, preferably Group 4 metal complexes, of bridged divalent aromatic ligands containing a divalent Lewis base chelating group are disclosed.
  • Higher solution reaction temperatures are particularly desired for ethylene/ ⁇ - olefin/diene polymerizations in order to improve operating efficiency.
  • the use of higher reaction temperatures often results in poor ⁇ -olefin and diene conversions. Accordingly, selection of catalyst compositions capable of incorporating increased amounts of ⁇ -olefin and diene comonomers at elevated reaction temperatures is highly desired.
  • metal complexes may be employed in a solution polymerization process to prepare high molecular weight ethylene containing interpolymers containing relatively large ⁇ -olefin and diene contents.
  • the resulting polymer products possess desirable properties such as increased tensile properties, reduced density (greater comonomer incorporation) and improved high temperature performance.
  • these catalyst compositions retain their high catalyst activity using relatively low molar ratios of conventional alumoxane cocatalysts.
  • interpolymers possessing relatively high molecular weights (with correspondingly low melt indices) and high levels of comonomer incorporation (low densities), having relatively good high temperature resistance.
  • This unique combination of polymer properties is also attainable by use of low molar ratios (200 or less, preferably 100 or less, more preferably 80 or less, based on zirconium) of an alkylalumoxa ⁇ e cocatalyst or a trialkylaluminum- modified alumoxane cocatalyst.
  • the polymers are capable of preparation under high temperature, high conversion conditions at high catalyst efficiencies.
  • the present invention is particularly advantageous for use under continuous solution polymerization conditions wherein a reaction mixture comprising a metal complex, an activating cocatalyst or cocatalyst mixture, optionally a chain transfer agent, ethylene, a C 3 . 30 ⁇ -olefin, especially propylene, and at least one C ⁇ . 2 0 conjugated or nonconjugated diene are continuously added to a reactor operating under solution polymerization conditions, and polymer product is continuously or semi-continuously removed therefrom.
  • the invention is used to prepare copolymers of ethylene, propylene and 5-ethylidene-2-norbornene having increased polymerized propylene and diene monomer contents.
  • the invention is particularly suitable for production of resins that are used in the preparation of adhesives, films (including membranes for roofing and architectural applications), and molded or extruded articles having improved high temperature use properties, with or without subsequent curing or cross-linking.
  • compositions claimed herein through use of the term “comprising” may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary.
  • hexane includes all isomers of hexane individually or collectively.
  • compound and “complex” are used interchangeably herein to refer to organic-, inorganic- and organometal compounds.
  • atom refers to the smallest constituent of an element regardless of ionic state, that is, whether or not the same bears a charge or partial charge or is bonded to another atom.
  • heteroatom refers to an atom other than carbon or hydrogen.
  • Preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge.
  • amorphous refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.
  • hydrocarbyl refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or noncyclic species. Examples include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, and alkynyl- groups. “Substituted hydrocarbyl” refers to a hydrocarbyl group that is substituted with one or more nonhydrocarbyl substituent groups.
  • heteroatom containing hydrocarbyl or “heterohydrocarbyl” refer to univalent groups in which at least one atom other than hydrogen or carbon is present along with one or more carbon atom and one or more hydrogen atoms.
  • heterocarbyl refers to groups containing one or more carbon atoms and one or more heteroatoms, but no hydrogen atoms.
  • the bond between the carbon atom and any heteroatom as well as the bonds between any two heteroatoms may be a single or multiple covalent bond or a coordinating or other donative bond.
  • an alkyl group substituted with a heterocycloalkyl-, aryl- substituted heterocycloalkyl-, heteroaryK alkyl- substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-, dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-, hydrocarbylthio-, or hydrocarbylseleno- group is within the scope of the term heteroalkyl.
  • specific heteroalkyl groups include cyanornethyl-, benzoylmethyl-, (2- pyridyl)methyl-, and trifluoromethyl- groups.
  • aromatic refers to a polyatomic, cyclic, conjugated ring system containing (45+2) ⁇ -electrons, wherein ⁇ is an integer greater than or equal to 1.
  • fused as used herein with respect to a ring system containing two or more polyatomic, cyclic rings means that with respect to at least two rings thereof, at least one pair of adjacent atoms is included in both rings.
  • aryl refers to a monovalent aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. Examples of aromatic ring(s) include phenyl, naphthyl, anthracenyl, and biphenyl, among others.
  • Substituted aryl refers to an aryl group in which one or more hydrogen atoms bound to any carbon is replaced by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (for example, CF 3 ), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety.
  • the common linking group may also be a carbonyl as in benzophenone, or oxygen as in diphenylether, or nitrogen as in diphenylamine.
  • Embodiments of the invention provide a new solution process for making ethylene/ ⁇ - olefin/diene interpolymers using a catalyst composition comprising a transition metal complex at high temperature, high catalyst efficiency and high monomer conversion.
  • the produced polymers are of high molecular weight (I 2 ⁇ 5.0).
  • Such polymers are suitably employed where improved high temperature performance is desired, such as in molding and extrusion grades of polymer especially for extruded films and profiles or molded parts applications.
  • polymer refers to a macromolecular compound prepared by polymerizing one or more monomers.
  • a polymer refers to homopolymers, copolymers, terpolymers, interpolymers, and so on.
  • interpolymer is used herein interchangeably with the term copolymer to refer to polymers incorporating in polymerized form at least two copolymerizable monomers, or incorporating long chain branching as a result of chain termination/olefin formation reactions in situ, and reincorporation of the in situ formed olefin. Accordingly, copolymers may result from the polymerization of a single monomer, under the correct operating conditions.
  • the least prevalent monomer or monomers in the resulting interpolymer are generally referred to by the term "comonomer".
  • the chain length of the resulting long chain branches referred to above is consequently longer than the carbon length resulting from polymerization of any deliberately added comonomer, and in particular, is longer than 6 carbons for ethylene/ 1-octene copolymers.
  • the presence of long chain branching may also be detected by the increased shear sensitivity of the polymer, as disclosed in EP-A-608,369, and elsewhere, or determined by Melt Index Ratio (MIR), a ratio of polymer melt viscosities measured under differing loads, especially
  • MIR Melt Index Ratio
  • the process described herein may be employed to prepare any olefin interpolymer, especially copolymers of ethylene, one or more C 3-2 o olefins, and one or more C 4 . 20 diolefins, and especially, ethylene/propylene/5-ethylidene-2-norbornene (EPDM) interpolymers.
  • EPDM ethylene/propylene/5-ethylidene-2-norbornene
  • Polymerization conditions generally refer to temperature, pressure, monomer content (including comonomer concentration), catalyst concentration, cocatalyst concentration, monomer conversion, or other conditions that influence the properties of the resulting polymer.
  • high molecular weight polymers may be prepared having relatively high comonomer incorporation with high catalyst activities, low cocatalyst usage and high molecular weights.
  • activities based on weight of polymer to weight of transition metal
  • activities greater than 0.5 g/ ⁇ g, preferably greater than 0.55 g/ ⁇ g, and even greater than 0.6 g/ ⁇ g are possible.
  • Polymer weight-average molecular weight is measured by gel permeation chromatography, one technique of which as described in USP 5,272,236.
  • melt index I 2 , 1 10 or I 2
  • melt index is inversely related to the molecular weight of the polymer. The higher the molecular weight, the lower the melt index, although the relationship is not necessarily linear.
  • Mooney viscosity ML 1+4 @ 100 0 C.
  • Suitable polymers are those having a Mooney viscosity in the range from 10 to 135, more preferably from 25 to 100, and most preferably from 30 to 80.
  • One embodiment of this invention entails a process which comprises contacting ethylene, one or more C 3 . 30 ⁇ -olefins, especially propylene, and a conjugated or non-conjugated diene, especially 5-ethylidene-2-norbornene in a solution polymerization process.
  • the present invented process is particularly advantageous for use under polymerization conditions wherein a reaction mixture comprising metal complex, activating cocatalyst, ethylene, and at least one C 3-30 ⁇ -olef ⁇ n comonomer (or the individual components thereof) is continuously or intermittently added to a reactor operating under solution polymerization conditions, optionally in the additional presence of a chain transfer agent, and polymerized product is continuously or semi-continuously removed therefrom.
  • the present process comprises polymerizing ethylene, one or more C 3 . 30 ⁇ -olefins, and a diolefin using a zirconium complex and from 10 to 200 moles per mole zirconium of an alumoxane, under continuous, solution polymerization conditions at a temperature from 120 to 250 0 C, preferably from 130 to 250 0 C, under high ethylene conversion conditions (>85 percent, preferably >90 percent) to prepare a polymer comprising from 0 to 99, preferably 50 to 90 percent ethylene, 9.5 to 99.5, preferably 10 to 50 percent ⁇ -olefin, and 0.1 to 50, preferably 0.1 to 20, more preferably 0.1 to 15 percent diene.
  • the present metal complexes are capable of producing polymers from diene monomers having extremely high molecular weight under a variety of polymerization conditions, and catalyst efficiencies of greater than 0.5 gpoiy m cr/ ⁇ g met ai,, thereby allowing the use of a chain transfer agent to control molecular weight without sacrificing molecular weight distribution, ⁇ - olefin content or diene content.
  • a sufficient quantity of chain transfer agent is preferably used so that a substantial decrease in molecular weight (>30 percent) occurs compared to a comparative polymerization without the use of chain transfer agent.
  • the chain transfer agent is hydrogen
  • at least 0.01 mol percent (based on ethylene) is used, and a maximum of about 2 mol percent is used.
  • high comonomer content polymers can be prepared with high levels of chain transfer agents, while still affording narrow molecular weight distribution polymers using low levels of alumoxane activators.
  • use of high levels of chain transfer agent and high levels of comonomer with conventional catalysts results in production of polymers having broadened molecular weight distributions.
  • the metal complexes are activated in various ways to yield catalyst compounds having a vacant coordination site that will coordinate, insert, and polymerize addition polymerizable monomers, especially olefin(s).
  • activator or "cocatalyst” is defined to be any compound or component or method which can activate the metal complex in the foregoing manner.
  • suitable activators include Lewis acids, non-coordinating ionic activators, ionizing activators, organometal compounds, and combinations of the foregoing substances capable of converting the neutral metal complex to a catalytically active species.
  • catalyst activation may involve formation of a cationic, partially cationic, or zwitterionic species, by means of proton transfer, oxidation, or other suitable activation process. It is to be understood that the present invention is operable and fully enabled regardless of whether or not such an identifiable cationic, partially cationic, or zwitterionic species actually results during the activation process, also interchangeably referred to herein as an "ionization” process or "ionic activation process".
  • Ionizing cocatalysts may contain an active proton, or some other cation associated with, but not coordinated to or only loosely coordinated to, an anion of the ionizing compound.
  • Such compounds are described in European publications EP-A-570982, EP-A-520732, EP-A-495375, EP- A-500944, EP-A-277 003 and EP-A-277004, and U.S. Patents: 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124.
  • ammonium cation containing salts especially those containing trihydrocarbyl- substituted ammonium cations containing one or two Ci 0-40 alkyl groups, especially methylbis(octadecyl)- ammonium- and methylbis(tetradecyl)-amrnonium- cations and a non-coordinating anion, especially a tetrakis(perfluoro)arylborate anion, especially tetrakis( ⁇ entafluorophenyl)borate.
  • the cation may comprise a mixture of hydrocarbyl groups of differing lengths.
  • the protonated ammonium cation derived from the commercially available long-chain amine comprising a mixture of two Ci 4 , Ci ⁇ or Ci 8 alkyl groups and one methyl group.
  • Such amines are available from Chemtura Corp., under the trade name KemamineTM T9701 , and from Akzo- Nobel under the trade name ArmeenTM M2HT.
  • a most preferred ammonium salt activator is methyldi(C
  • ionizing ionic compounds not containing an active proton but capable of forming active catalyst compositions are also contemplated for use herein, and are described in EP-A-426637, EP-A- 573403 and U.S. Patent 5,387,568.
  • strong Lewis acids especially tris(perfluoro)aryl borane compounds, such as tris(pentafluorophenyl)borane, which are capable of abstraction of a ligand groups, especially a hydrocarbyl ligand, thereby forming a non-coordinating counter anion for the cationic derivative of the metal complex.
  • a class of cocatalysts comprising non-coordinating anions generically referred to as expanded anions, further disclosed in U. S. Patent 6,395,671, may be suitably employed to activate the metal complexes of the present invention for olefin polymerization.
  • these cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted as follows:
  • A* + is a cation, especially a proton containing cation, and preferably is a trihydrocarbyl ammonium cation containing one or two Ci 0-40 alkyl groups, especially a methyldi(Ci ⁇ 2 oalkyl)ammonium- cation,
  • R 4 independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C] -2O alkyl, and
  • J*' is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).
  • these catalyst activators include trihydrocarbylammonium- salts, especially, methyldi(C I4-2 oalkyl)ammonium- salts of: bis(tris(pentafluorophenyl)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyI)borane)-2-heptadecylimidazoIide, bis(tris(pentafluorophenyl)borane)- 4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, bis(tris
  • 2-heptadecyIimidazolinide bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.
  • activators include those described in PCT publication WO 98/07515 such as tris (2,
  • activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-A-O 573120, PCT publications WO 94/07928 and WO 95/14044 and US Patents 5, 153, 157 and
  • WO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including their hydrates.
  • WO 99/18135 describes the use of organoboroaluminum activators.
  • EP-A-781299 describes using a silylium salt in combination with a non-coordinating compatible anion.
  • Other activators or methods for activating a catalyst compound are described in for example, U. S. Patents 5,849,852, 5,859, 653, 5,869,723, EP-A-615981, and PCT publication WO 98/32775.
  • alumoxanes also referred to as alkylaluminoxanes.
  • Alumoxanes are well known activators for use with metallocene type catalyst compounds to prepare addition polymerization catalysts.
  • metallocene type catalyst compounds to prepare addition polymerization catalysts.
  • methods for preparing alumoxanes and modified alumoxanes are described in U.S.
  • Preferred alumoxanes are Lewis acid modified alumoxanes, especially tri(C 3 .
  • alkylaluminum modified methylalumoxane including tri(isobutyl)aluminum modified methalumoxane, available commercially as JVIMAO-3A or tri(n-octyl)aluminum modified methalumoxane, available commercially as MMAO- 12, from Akzo Nobel, Inc. It is within the scope of this invention to use alumoxane(s) or modified alumoxane(s) as an activator or as a tertiary component in the invented process.
  • the compound may be used alone or in combination with other activators, either neutral or ionic, such as tri(alkyl)ammonium tetrakis(pentafluorophenyl)borate compounds, trisperfluoroaryl compounds, polyhalogenated heteroborane anions as disclosed in WO 98/43983, and combinations thereof.
  • activators either neutral or ionic, such as tri(alkyl)ammonium tetrakis(pentafluorophenyl)borate compounds, trisperfluoroaryl compounds, polyhalogenated heteroborane anions as disclosed in WO 98/43983, and combinations thereof.
  • the amount of alumoxane employed is generally less than that necessary to effectively activate the metal complex when employed alone. In this embodiment, it is believed, without wishing to be bound by such belief, that the alumoxane does not contribute significantly to actual catalyst activation.
  • Suitable alumoxanes include polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO) as well as Lewis acid- modified alumoxanes, especially trihydrocarbylaluminum-, halogenated tri(hydrocarbyl)aluminum- or halogenated tri(hydrocarbyl)boron- modified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group.
  • MAO methylalumoxane
  • Lewis acid- modified alumoxanes especially trihydrocarbylaluminum-, halogenated tri(hydrocarbyl)aluminum- or halogenated tri(hydrocarbyl)boron- modified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group.
  • Preferred Lewis acid- modified alumoxane compounds are tri(i-butyl)aluminum- modified methalumoxane and tri(n- octyl)aluminum- modified methalumoxane containing from 10 to 30, preferably 15 to 25 mole percent i-butyl content and 10 to 20, preferably 12 to 18 mole percent n-octyl contents, respectively, said molar percents based on total alkyl Iigand content.
  • the alumoxane or Lewis acid- modified alumoxane activator is preferably utilized in molar ratios cocatalystxatalyst from 20-200, more preferably from 20-150, and most preferably from 20-80.
  • the present zirconium complexes can achieve reduced levels of cocatalyst byproducts in the resulting polymer along with long chain branch formation in the resulting polymer. This in turn allows the polymers to be employed in demanding applications that have been previously unsuited for ethylene/ ⁇ -olefin interpolymers, such as wire and cable electrical insulation and extrusion forming process for profiles, pipes, and other applications, while retaining good flexibility and processing properties.
  • Multiple reactor polymerization processes may be suitably employed in the present invention. Examples include such systems as are disclosed in USP 3,914,342, among others.
  • the multiple reactors can be operated in series or in parallel, with at least one catalyst composition according to the present invention employed in at least one of the reactors.
  • One or both reactors may also contain at least two catalysts which have different comonomer incorporation capability and/or different molecular weight capability.
  • a relatively high molecular weight product (M w from 100,000 to over 1 ,000,000, more preferably 200,000 to 500,000) is formed while in the second reactor a product of a relatively low molecular weight (M w 2,000 to 300,000) is formed. Both of these reactor products can have similar or different densities and/or elastomer content.
  • the final product is a mixture of the two reactor effluents which are combined prior to devolatilization to result in a uniform mixing of the two or more polymer products.
  • one reactor may be used to prepare a high ethylene content copolymer optionally containing diene while the second reactor is employed to prepare a homopolymer of either ethylene or the ⁇ -olefin or a copolymer of ethylene and one or more ⁇ -olefins.
  • the reactors are connected in series, that is, the effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen is optionally added to the second reactor.
  • Reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is ideally in the range from 5:95 to 95:5.
  • the foregoing dual reactor process is capable of producing polymers having broadened molecular weight distribution or polydispersity index (PDI).
  • Preferred polymers made in the foregoing manner have PDI from 2.8 to 10.0, more preferably from 3.0 to 7.0.
  • the high molecular weight component contains higher quantities of ⁇ -olefin comonomer (lower density) than the low molecular weight component.
  • one of the reactors in the polymerization process contains a heterogeneous Ziegler-Natta catalyst or a chromium containing catalyst, such as one of the numerous such catalysts known in the art.
  • Ziegler-Natta catalysts include, but are not limited to, titanium-based catalysts supported on MgCl 2 , and additionally comprise compounds of aluminum containing at least one aluminum-alkyl bond.
  • Suitable Ziegler-Natta catalysts and their preparation include, but are not limited to, those disclosed in USP's 4,612,300, 4,330,646, and 5,869,575.
  • Suitable chromium based catalysts are those disclosed in USP's 4,981,927, 4,835,219, 4,564,660, 4,173,548, 3,953,413, and elsewhere.
  • Single reactor, multiple catalyst processes are also useful in the present invention.
  • two or more catalysts are introduced into a single reactor at the high monomer conversion conditions that are herein disclosed, wherein each catalyst inherently produces different interpolymer products.
  • a relatively high molecular weight product (M w from 100,000 to over 1,000,000, more preferably 200,000 to 500,000) is formed from one catalyst while a product of a relatively low molecular weight (M w 2,000 to 300,000) is formed from the other catalyst.
  • M w molecular weight product
  • M w 2,000 to 300,000 a relatively low molecular weight
  • Both of these catalyst compositions can have similar or different comonomer incorporation ability, at least one of which comprises a metal complex as set forth herein.
  • the resulting polymer will have properties dependant on the ratio of the two catalysts that are employed in the single reactor.
  • the second catalyst composition may comprise a metal complex as herein disclosed, a metallocene or other ⁇ -bonded ligand group containing metal complex (including constrained geometry metal complexes), or a polyvalent heteroatom ligand group containing metal complex, especially polyvalent pyridylamine or imidizolylamine based complexes and tetradendate oxygen-ligated biphenylphenol based Group 4 metal complexes.
  • Suitable metal complexes for use according to the present invention include compounds corresponding to the formula:
  • R 20 independently each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen
  • T 3 is a divalent hydrocarbon or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof
  • R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 20 atoms, not counting hydrogen.
  • Ar 2 independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino- substituted arylene group of from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;
  • T 3 is a divalent hydrocarbon bridging group of from 2 to 20 atoms not counting hydrogen, preferably a divalent substituted or unsubstituted C 3-6 aliphatic, cycloaliphatic, or bis(alkylene)- substituted cycloaliphatic group; and
  • R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen.
  • metal complexes suitable for use herein include compounds of the formula:
  • Ar 4 independently each occurrence is Cg -2O aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, 3,5-di(tertbutyl)phenyl, dibenzo-lH- pyrrole-1-yl, ⁇ aphthyl, anthracen-5-yl, l,2,3,4,6,7,8,9-octahydroanthrace ⁇ -5-yl; T 4 independently each occurrence is a propylene-l,3-diyl group, a cyclohexan-l,2-diyl group, a bis(alkylene)cyclohexan-l,2-diyl group, a cyclohexen-4,5-diyl group, or an inertly substituted derivative thereof;
  • R 21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
  • R D independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.
  • Especially preferred metal complexes are compounds of the formula:
  • Ar 4 independently each occurrence, is 3,5-di(isopropyl)phenyl, 3,5- di(isobutyl)phenyl, 3,5-di(tertbutyl)phenyl, dibenzo-lH-pyrroIe-l-yl, or anthracen-5-yl,
  • R 2 ' independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
  • T 4 is propan-l,3-diyl, cyclohexanediyl, cyclohexen ⁇ 4,5-diyl, or bis(methylene)cyclohexan- 1,2-diyl;
  • R D independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a hydrocarbylene, hydrocarbadiyl or hydrocarbyls ⁇ anediyl group of up to 40 atoms not counting hydrogen.
  • metal complexes comprising a 1 ,4-butandiyl T 4 group
  • the foregoing complexes demonstrate improved catalyst efficiencies, especially at elevated polymerization temperatures.
  • Most highly preferred metal complexes according to the invention correspond to the formulas: wherein, R D independently each occurrence is chloro, methyl or benzyl.
  • suitable metal complexes are the following compounds: A) bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3 A6 J ⁇ octahydroanthracen-S-yO-SKmethyOphenyl ⁇ -phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2- ⁇ henoxy)-l,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyr
  • 1,3-propanediylzirconium (IV) dichloride bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-
  • the foregoing metal complexes may be conveniently prepared by standard metallation and liga ⁇ d exchange procedures involving a source of the transition metal and a neutral polyfunctional ligand source.
  • the complexes may also be prepared by means of an amide elimination and hydrocarbylation process starting from the corresponding transition metal tetraamide and a hydrocarbylating agent, such as trimethylaluminum.
  • the techniques employed are the same as or analogous to those disclosed in USP's 6,320,005, 6,103,657, WO 02/38628, WO 03/40195, US-A- 2004/0220050, and elsewhere.
  • the metal complex is activated to form the active catalyst composition by combination with the cocatalyst.
  • the activation may occur prior to addition of the catalyst composition to the reactor with or without the presence of other components of the reaction mixture, or in situ through separate addition of the metal complex and activating cocatalyst to the reactor.
  • Suitable olefin mixtures for use herein include mixtures of ethylene, one or more 0 3 . 30 ⁇ - olefins and one or more conjugated or nonconjugated dienes.
  • Suitable ⁇ -olefin comonomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, and 1-dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1- eicosene, 3-methyl- 1-butene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 4,6-dimethyl- 1-heptene, and vinylcyclohexane.
  • Suitable dienes for use herein include straight chain-, branched chain-, cyclic-, and polycyclic hydrocarbon dienes having from 6 to 15 carbon atoms.
  • suitable non- conjugated dienes include, but are not limited to, straight chain acyclic dienes, such as 1,4- hexadiene, 1 ,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5- methyl- 1 ,4-hexadiene; 3,7-dimethyl-l,6-octadiene; 3,7-dimethyl- 1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1 ,3-cyclopentadiene; 1 ,4-cyclohexadiene; 1 ,5-cyclooctadiene and 1,5-cyclododecad
  • the particularly preferred dienes are 1 ,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2- norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD).
  • the most especially preferred diene is 5-ethylidene-2-norbornene (ENB).
  • the polymerization may be accomplished at conditions well known in the prior art for olefin solution polymerization reactions.
  • Preferred polymerization temperatures are from 80 to 250 0 C, more preferably from 100-200 0 C.
  • Preferred polymerization pressures are from atmospheric to 3000 atmospheres (100 kPa to 300 MPa), more preferably from 1 MPa to 10 MPa.
  • the molar ratio of catalyst: polymerizable compound employed is from 10 "12 :l to 10 1 :1 , more preferably from 10 " ": 1 to I0 "5 : L
  • the reaction is conducted under continuous, solution polymerization conditions, that is, conditions wherein the monomer or monomers are continuously added to a reactor operating under solution polymerization conditions, and polymerized product is continuously or semi-continuously removed and recovered or forwarded to a second reactor.
  • the polymerization mixture comprises an aliphatic or alicyclic liquid diluent.
  • aliphatic or alicyclic liquid diluents include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcyclo- heptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C 4 . 10 alkanes, and the like.
  • a preferred liquid diluent is a hydrogenated oligomeric aliphatic hydrocarbon mixture having a distillation, ASTM D 86, IBP of 118 0 C, distillation, ASTM D 86, Dry Point of 137 0 C, and Specific Gravity, 15.6 0 C, ASTM D 1250 of 0.72 sold commercially under the trade designation IsoparTM E, available from ExxonMobil Corporation.
  • molecular weight control agents or chain transfer agents in the present process is desired.
  • molecular weight control agents include hydrogen, trialkyl aluminum compounds, or other known chain transfer agents. Hydrogen is a most preferred molecular weight control agent or chain transfer agent.
  • a particular benefit of the use of the present invention is the ability (depending on reaction conditions) to produce narrow molecular weight distribution ethylene/ ⁇ -olefin interpolymers.
  • Preferred polymers have Mw/Mn of less than 3.0, more preferably less than 2.6.
  • Such narrow molecular weight distribution polymer products are highly desirable due to improved tensile strength properties as well as reduced levels of extractables and metal values.
  • one means for carrying out the present polymerization process is as follows.
  • the monomers to be polymerized are introduced continuously together with any solvent or diluent.
  • the reactor contains a liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer.
  • Catalyst along with cocatalyst and optionally chain transfer agent are continuously or intermittently introduced in the reactor liquid phase or any recycled portion thereof.
  • the reactor temperature may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by use of cooling or heating coils, jackets or both.
  • the polymerization rate is controlled by the rate of catalyst addition.
  • Pressure is controlled by the monomer flow rate and partial pressures of volatile components.
  • the ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor.
  • the polymer product molecular weight is controlled, optionally, by controlling other polymerization variables such as the temperature, monomer concentration, or by the flow rate of he previously mentioned chain transfer agent.
  • a catalyst kill agent such as water, steam or an alcohol.
  • the polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous monomers as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a de volatilizing extruder.
  • the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, and preferably is from 10 minutes to 6 hours.
  • the foregoing polymerization may be carried out in a continuous loop reactor with or without a monomer, comonomer, catalyst or cocatalyst gradient established between differing regions thereof, optionally accompanied by separate addition of catalysts and/or chain transfer agent, and operating under adiabatic or non-adiabatic solution polymerization conditions or combinations of the foregoing reactor conditions.
  • suitable loop reactors and a variety of suitable operating conditions for use therewith are found in USFs 5,977,251 , 6, 319,989 and 6,683, 149.
  • a process for polymerization of ethylene, one or more C 3 - 30 ⁇ -olefins and one or more conjugated or nonconjugated dienes under continuous, solution polymerization conditions to prepare a high molecular weight interpolymer comprising conducting the polymerization in the presence of a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether corresponding to the formula:
  • R 20 independently each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen;
  • T 3 is a divalent hydrocarbon or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof;
  • R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen; and an activating cocatalyst at a temperature from 80 to 250 0 C and a pressure from 100 kPa to 300 MPa.
  • 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene, 5-methylene ⁇ 2-norbornene, and dicyclopentadiene is polymerized.
  • Ar 2 independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino- substituted arylene group of from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;
  • T 3 is a divalent hydrocarbon bridging group of from 2 to 20 atoms not counting hydrogen, preferably a divalent substituted or unsubstituted C 3-6 aliphatic, cycloaliphatic, or bis(alkylene)- substituted cycloaliphatic group; and
  • R D independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two R D groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen. 15.
  • the process of embodiment 14 wherein the metal complex corresponds to the formula: , where
  • Ar 4 independently each occurrence is C ⁇ . 2 o aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyI)phenyl, dibenzo-lH-pyrrole-1-y], naphthyl, anthracen-5-yl, 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yI ;
  • T 4 independently each occurrence is a propylene- 1 ,3-diyl group, a cyclohexan-l,2-diyl group, a bis(alkylene)cyclohexan-],2-diyl group, a cyclohexen-4,5-diy] group, or an inertly substituted derivative thereof;
  • R 21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
  • R D independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 R D groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.
  • R D independently each occurrence is chloro, methyl or benzyl.
  • ⁇ - propanediylzirconium (IV) dimethyl bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy)-1,3- propanediylzirconium (FV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrroIe- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-(I ,i-dimethyIethyl)phenyl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy)-l ,3- propanediylzirconium (IV) dimethyl, , bis((2-oxoyl-3-(
  • 4,5-cyclohexenediylzirconium (IV) dimethyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethyIethyl)phenyl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconiutn (IV) dibenzyl,
  • A3 bis((2-oxoyl-3-(3,5-bis-(l , 1 -dimethylethyl)
  • A4 bis((2-oxoyl-3-(dibenzo-1 H-pyrrole- 1 -yl)-5- phenyl)-5-(methyl)phenyl)-2- phenoxy)- (methyl)phenyl)-2-phenoxy)-
  • A5 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-
  • A6 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -y ⁇ )-5- (methyI)phenyD-2-phenoxy)-cis- (methyI) ⁇ henyr)-2-phenoxymethyl)- cis- 1 ,3-cycfohexanediyl zirconium (IV) dimethyl 4,5-cyck)hexenediyl zirconium (IV) dimethyl
  • A7 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yI)-5-
  • A8 bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- l-yl)-5- (niethyl)phenyl)-( ⁇ rrEthyl-2-phenoxyrnethyl))- (methyl)phenyI)-2- ⁇ henoxy)- trans 1 ⁇ -cyclohexanezirconium (TV) dimethyl 1 ,4-butanediylzirconium QV) dimethyl
  • A9 bis((2-oxoyl-3-(dibenzo-lH-py ⁇ O le- l-yT)-5-
  • A10 bis((2-oxoyl-3-(dibenzo-lH-py ⁇ Ole-l-yI)-5- (rrethyl)phenyI)-(5-(2-i ⁇ E thyI)pr O pane-2-yl)-2- (methyI)phenyI)-(5-(2-methyl)propane-2-yl)-2- phenoxy)- 1 ,3-propanediyI zirconium (IV) dirrethyl ptenoxy> 1 ,3-propanediyl zirconium (TV) dichloride
  • Al 1 bis((2-oxoyl-3-(3,5-bis-(l,l-di ⁇ thylethyI) Conrp: bis((2-oxoyl-3-(dibenzD- 1 H-pyrrole- 1 -yI)-5- phenyI)-5-(methyI)phenyl)-(5-2- ⁇ iethyI)propane (methyl)phenyr>-2-phenoxy ⁇ Ethyl)-trdns- -2-yj)2- pbsnoxy)- 1 ,3-propanediyl zirconium (IV) 1 ,2-cyctobsxanediylha ⁇ hium (TV) dimethyl dimethyl dimethyl
  • Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer.
  • Purified mixed alkanes solvent IsoparTM E available from ExxonMobil, Inc.
  • ethylene, propylene, 5-ethylidene-2-norbornene, and hydrogen are continuously supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple.
  • the solvent feed to the reactor is measured by a mass-flow controller.
  • a variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At the discharge of the pump, a side stream is taken to provide flush flows for the catalyst and cocatalyst injection lines and the reactor agitator.
  • the remaining solvent is combined with monomers and hydrogen and fed to the reactor.
  • a mass flow controller is used to deliver hydrogen to the reactor as needed.
  • the temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor.
  • the catalyst and cocatalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor.
  • the cocatalyst used in runs 1-12 is a long-chain alkyl ammonium borate of approximate stoichiometry equal to methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate (MDB) combined with a tertiary component, tri(isobutyl)aluminum modified methalumoxane (MMAO) containing a molar ratio of i-butyl/methyl groups of about 1/3 in a molar ratio based on transition metal of 5/1.
  • MDB methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate
  • MMAO tri(isobutyl)aluminum modified methalumoxane
  • the cocatalyst is MAO alone in a molar ratio based on Zr of 50: 1.
  • the reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.
  • Product is removed through exit lines at the top of the reactor. All exit lines from the reactor are steam traced and insulated. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer.
  • the product stream is then heated by passing through a heat exchanger before devolatilization.
  • the polymer product is recovered by extrusion using a devolatilizing extruder and water cooled pelletizer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

A catalyst composition comprising a zirconium complex of a polyvalent aryloxyether and the use thereof in a continuous solution polymerization of ethylene, one or more C3-30 olefins, and a conjugated or nonconjugated diene to prepare interpolymers having improved processing properties are disclosed.

Description

ETHYLENTE/ α-OLEFIN/ DIENE SOLUTION POLYMERIZATION PROCESS AND POLYMER
Cross Reference Statement
This application claims the benefit of U.S. Provisional Application 60/801,182, filed May 17, 2006.
Background of the Invention
Catalyst compositions based on well defined donor ligand containing metal complexes, referred to as post-metallocene complexes have been shown to give products having better comonomer incorporation and narrow molecular weight distribution. However, these catalysts often have poor high temperature stability and suffer from poor catalytic efficiencies, especially at elevated polymerization temperatures. When employed to prepare ethylene, α-olefin and diene containing polymers, especially ethylene, propylene, and ethyl idenenorbornene (ENB) containing polymers, the resulting polymer molecular weight and comonomer incorporation ratio is often deficient.
Examples .of one type of the foregoing post metallocene catalysts are disclosed in USP 6,827,976, where Group 3-6 or Lanthanide metal complexes, preferably Group 4 metal complexes, of bridged divalent aromatic ligands containing a divalent Lewis base chelating group are disclosed. Higher solution reaction temperatures are particularly desired for ethylene/α- olefin/diene polymerizations in order to improve operating efficiency. However, the use of higher reaction temperatures often results in poor α-olefin and diene conversions. Accordingly, selection of catalyst compositions capable of incorporating increased amounts of α-olefin and diene comonomers at elevated reaction temperatures is highly desired.
We have now discovered that certain metal complexes may be employed in a solution polymerization process to prepare high molecular weight ethylene containing interpolymers containing relatively large α-olefin and diene contents. The resulting polymer products possess desirable properties such as increased tensile properties, reduced density (greater comonomer incorporation) and improved high temperature performance. In addition, we have discovered that these catalyst compositions retain their high catalyst activity using relatively low molar ratios of conventional alumoxane cocatalysts. The use of reduced quantities of alumoxaπe cocatalysts (reduced by up to 90 percent or more, compared to the quantities employed in conventional processes) allows for the preparation of polymer products having reduced metal content and consequently increased clarity, improved dielectric properties and other enhanced physical properties. In addition, the use of reduced quantities of alumoxane cocatalysts results in reduction in polymer production costs. Summary of the Invention
According to the present invention there is now provided a process for polymerization of ethylene, one or more C3.20 α-olefins and a conjugated or non-conjugated diene under solution polymerization conditions with a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether which affords interpolymers having high α-olefin and diene contents compared to the use of conventional catalysts.
Additionally, according to the invention it is possible to produce interpolymers possessing relatively high molecular weights (with correspondingly low melt indices) and high levels of comonomer incorporation (low densities), having relatively good high temperature resistance. This unique combination of polymer properties is also attainable by use of low molar ratios (200 or less, preferably 100 or less, more preferably 80 or less, based on zirconium) of an alkylalumoxaπe cocatalyst or a trialkylaluminum- modified alumoxane cocatalyst. The polymers are capable of preparation under high temperature, high conversion conditions at high catalyst efficiencies. The present invention is particularly advantageous for use under continuous solution polymerization conditions wherein a reaction mixture comprising a metal complex, an activating cocatalyst or cocatalyst mixture, optionally a chain transfer agent, ethylene, a C3.30 α-olefin, especially propylene, and at least one Cφ.20 conjugated or nonconjugated diene are continuously added to a reactor operating under solution polymerization conditions, and polymer product is continuously or semi-continuously removed therefrom. In one embodiment, the invention is used to prepare copolymers of ethylene, propylene and 5-ethylidene-2-norbornene having increased polymerized propylene and diene monomer contents.
The invention is particularly suitable for production of resins that are used in the preparation of adhesives, films (including membranes for roofing and architectural applications), and molded or extruded articles having improved high temperature use properties, with or without subsequent curing or cross-linking.
Detailed Description of the Invention
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 2003. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight and all test methods are current as of the filing date hereof. For purposes of United States patent practice, the contents of any patent, patent application, or publication referenced herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is so incorporated by reference) especially with respect to the disclosure of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.
The term "comprising" and derivatives thereof is not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as in any combination.
As used herein with respect to a chemical compound, unless specifically indicated otherwise, the singular includes all isomeric forms and vice versa (for example, "hexane", includes all isomers of hexane individually or collectively). The terms "compound" and "complex" are used interchangeably herein to refer to organic-, inorganic- and organometal compounds. The term, "atom" refers to the smallest constituent of an element regardless of ionic state, that is, whether or not the same bears a charge or partial charge or is bonded to another atom. The term "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge. The term "amorphous" refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.
The term, "hydrocarbyl" refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or noncyclic species. Examples include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, and alkynyl- groups. "Substituted hydrocarbyl" refers to a hydrocarbyl group that is substituted with one or more nonhydrocarbyl substituent groups. The terms, "heteroatom containing hydrocarbyl" or "heterohydrocarbyl" refer to univalent groups in which at least one atom other than hydrogen or carbon is present along with one or more carbon atom and one or more hydrogen atoms. The term "heterocarbyl" refers to groups containing one or more carbon atoms and one or more heteroatoms, but no hydrogen atoms. The bond between the carbon atom and any heteroatom as well as the bonds between any two heteroatoms, may be a single or multiple covalent bond or a coordinating or other donative bond. Thus, an alkyl group substituted with a heterocycloalkyl-, aryl- substituted heterocycloalkyl-, heteroaryK alkyl- substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-, dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-, hydrocarbylthio-, or hydrocarbylseleno- group is within the scope of the term heteroalkyl. Examples of specific heteroalkyl groups include cyanornethyl-, benzoylmethyl-, (2- pyridyl)methyl-, and trifluoromethyl- groups.
As used herein the term "aromatic" refers to a polyatomic, cyclic, conjugated ring system containing (45+2) π-electrons, wherein δ is an integer greater than or equal to 1. The term "fused" as used herein with respect to a ring system containing two or more polyatomic, cyclic rings means that with respect to at least two rings thereof, at least one pair of adjacent atoms is included in both rings. The term "aryl" refers to a monovalent aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. Examples of aromatic ring(s) include phenyl, naphthyl, anthracenyl, and biphenyl, among others.
"Substituted aryl" refers to an aryl group in which one or more hydrogen atoms bound to any carbon is replaced by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (for example, CF3), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety. The common linking group may also be a carbonyl as in benzophenone, or oxygen as in diphenylether, or nitrogen as in diphenylamine.
Embodiments of the invention provide a new solution process for making ethylene/ α- olefin/diene interpolymers using a catalyst composition comprising a transition metal complex at high temperature, high catalyst efficiency and high monomer conversion. Highly desirably, the produced polymers are of high molecular weight (I2 < 5.0). Such polymers are suitably employed where improved high temperature performance is desired, such as in molding and extrusion grades of polymer especially for extruded films and profiles or molded parts applications.
The term "polymer" as used herein refers to a macromolecular compound prepared by polymerizing one or more monomers. A polymer refers to homopolymers, copolymers, terpolymers, interpolymers, and so on. The term "interpolymer" is used herein interchangeably with the term copolymer to refer to polymers incorporating in polymerized form at least two copolymerizable monomers, or incorporating long chain branching as a result of chain termination/olefin formation reactions in situ, and reincorporation of the in situ formed olefin. Accordingly, copolymers may result from the polymerization of a single monomer, under the correct operating conditions. \The least prevalent monomer or monomers in the resulting interpolymer are generally referred to by the term "comonomer". The chain length of the resulting long chain branches referred to above, is consequently longer than the carbon length resulting from polymerization of any deliberately added comonomer, and in particular, is longer than 6 carbons for ethylene/ 1-octene copolymers. The presence of long chain branching may also be detected by the increased shear sensitivity of the polymer, as disclosed in EP-A-608,369, and elsewhere, or determined by Melt Index Ratio (MIR), a ratio of polymer melt viscosities measured under differing loads, especially
Figure imgf000006_0001
The process described herein may be employed to prepare any olefin interpolymer, especially copolymers of ethylene, one or more C3-2o olefins, and one or more C4.20 diolefins, and especially, ethylene/propylene/5-ethylidene-2-norbornene (EPDM) interpolymers.
Polymerization conditions generally refer to temperature, pressure, monomer content (including comonomer concentration), catalyst concentration, cocatalyst concentration, monomer conversion, or other conditions that influence the properties of the resulting polymer. By operation according to the prescribed polymerization conditions of the invention, high molecular weight polymers may be prepared having relatively high comonomer incorporation with high catalyst activities, low cocatalyst usage and high molecular weights. In particular, activities (based on weight of polymer to weight of transition metal) greater than 0.5 g/μg, preferably greater than 0.55 g/μg, and even greater than 0.6 g/μg are possible. Polymer weight-average molecular weight (Mw) is measured by gel permeation chromatography, one technique of which as described in USP 5,272,236. Alternatively, melt index, I2, 110 or I2), measured, for example, according to ASTM D-1238 may be employed as an indication of molecular weight. Generally, melt index is inversely related to the molecular weight of the polymer. The higher the molecular weight, the lower the melt index, although the relationship is not necessarily linear. Alternatively, Mooney viscosity (ML 1+4 @ 1000C.) may be used as a measure of molecular weight. Suitable polymers are those having a Mooney viscosity in the range from 10 to 135, more preferably from 25 to 100, and most preferably from 30 to 80.
One embodiment of this invention entails a process which comprises contacting ethylene, one or more C3.30 α-olefins, especially propylene, and a conjugated or non-conjugated diene, especially 5-ethylidene-2-norbornene in a solution polymerization process. The present invented process is particularly advantageous for use under polymerization conditions wherein a reaction mixture comprising metal complex, activating cocatalyst, ethylene, and at least one C3-30 α-olefϊn comonomer (or the individual components thereof) is continuously or intermittently added to a reactor operating under solution polymerization conditions, optionally in the additional presence of a chain transfer agent, and polymerized product is continuously or semi-continuously removed therefrom.
In a general sense, the present process comprises polymerizing ethylene, one or more C3.30 α-olefins, and a diolefin using a zirconium complex and from 10 to 200 moles per mole zirconium of an alumoxane, under continuous, solution polymerization conditions at a temperature from 120 to 2500C, preferably from 130 to 2500C, under high ethylene conversion conditions (>85 percent, preferably >90 percent) to prepare a polymer comprising from 0 to 99, preferably 50 to 90 percent ethylene, 9.5 to 99.5, preferably 10 to 50 percent α-olefin, and 0.1 to 50, preferably 0.1 to 20, more preferably 0.1 to 15 percent diene.
Surprisingly, the present metal complexes are capable of producing polymers from diene monomers having extremely high molecular weight under a variety of polymerization conditions, and catalyst efficiencies of greater than 0.5 gpoiymcr/μgmetai,, thereby allowing the use of a chain transfer agent to control molecular weight without sacrificing molecular weight distribution, α- olefin content or diene content. A sufficient quantity of chain transfer agent is preferably used so that a substantial decrease in molecular weight (>30 percent) occurs compared to a comparative polymerization without the use of chain transfer agent. When the chain transfer agent is hydrogen, at least 0.01 mol percent (based on ethylene) is used, and a maximum of about 2 mol percent is used. Especially surprising is the fact that high comonomer content polymers can be prepared with high levels of chain transfer agents, while still affording narrow molecular weight distribution polymers using low levels of alumoxane activators. Generally, use of high levels of chain transfer agent and high levels of comonomer with conventional catalysts results in production of polymers having broadened molecular weight distributions.
The metal complexes are activated in various ways to yield catalyst compounds having a vacant coordination site that will coordinate, insert, and polymerize addition polymerizable monomers, especially olefin(s). For the purposes of this patent specification and appended claims, the term "activator" or "cocatalyst" is defined to be any compound or component or method which can activate the metal complex in the foregoing manner. Non-limiting examples of suitable activators include Lewis acids, non-coordinating ionic activators, ionizing activators, organometal compounds, and combinations of the foregoing substances capable of converting the neutral metal complex to a catalytically active species. It is believed, without desiring to be bound by such belief, that in one embodiment of the invention, catalyst activation may involve formation of a cationic, partially cationic, or zwitterionic species, by means of proton transfer, oxidation, or other suitable activation process. It is to be understood that the present invention is operable and fully enabled regardless of whether or not such an identifiable cationic, partially cationic, or zwitterionic species actually results during the activation process, also interchangeably referred to herein as an "ionization" process or "ionic activation process".
Ionizing cocatalysts may contain an active proton, or some other cation associated with, but not coordinated to or only loosely coordinated to, an anion of the ionizing compound. Such compounds are described in European publications EP-A-570982, EP-A-520732, EP-A-495375, EP- A-500944, EP-A-277 003 and EP-A-277004, and U.S. Patents: 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124. Preferred among the foregoing activators are ammonium cation containing salts, especially those containing trihydrocarbyl- substituted ammonium cations containing one or two Ci0-40 alkyl groups, especially methylbis(octadecyl)- ammonium- and methylbis(tetradecyl)-amrnonium- cations and a non-coordinating anion, especially a tetrakis(perfluoro)arylborate anion, especially tetrakis(ρentafluorophenyl)borate. It is further understood that the cation may comprise a mixture of hydrocarbyl groups of differing lengths. For example, the protonated ammonium cation derived from the commercially available long-chain amine comprising a mixture of two Ci4, Ciβ or Ci8 alkyl groups and one methyl group. Such amines are available from Chemtura Corp., under the trade name Kemamine™ T9701 , and from Akzo- Nobel under the trade name Armeen™ M2HT. A most preferred ammonium salt activator is methyldi(C|φ.20alkyl)ammonium tetrakis(pentafluorophenyl)borate.
Activation methods using ionizing ionic compounds not containing an active proton but capable of forming active catalyst compositions, such as ferrocenium salts of the foregoing non- coordinating anions are also contemplated for use herein, and are described in EP-A-426637, EP-A- 573403 and U.S. Patent 5,387,568. Also included is the use of strong Lewis acids, especially tris(perfluoro)aryl borane compounds, such as tris(pentafluorophenyl)borane, which are capable of abstraction of a ligand groups, especially a hydrocarbyl ligand, thereby forming a non-coordinating counter anion for the cationic derivative of the metal complex.
A class of cocatalysts comprising non-coordinating anions generically referred to as expanded anions, further disclosed in U. S. Patent 6,395,671, may be suitably employed to activate the metal complexes of the present invention for olefin polymerization. Generally, these cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted as follows:
Figure imgf000008_0001
wherein:
A*+ is a cation, especially a proton containing cation, and preferably is a trihydrocarbyl ammonium cation containing one or two Ci0-40 alkyl groups, especially a methyldi(Ciφ 2oalkyl)ammonium- cation, R4, independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C]-2O alkyl, and
J*' is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane). Examples of these catalyst activators include trihydrocarbylammonium- salts, especially, methyldi(CI4-2oalkyl)ammonium- salts of: bis(tris(pentafluorophenyl)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyI)borane)-2-heptadecylimidazoIide, bis(tris(pentafluorophenyl)borane)- 4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, bis(tris(pentafluorophenyl)borane)imidazolinide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)borane)-2- heptadecylimidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(uπdecyl)imidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide, bis(tris(pentafluorophenyl)borane)-5,6-dirnethylbenzirnidazolide, bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide, bis(tris(pentafluorophenyl)alumane)irnidazolide, bis(tris(pentafluorophenyI)alumane)-2-undecyIimidazolide, bis(tris(pentafluorophenyl)aIumane)-2- heptadecylimidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)irnidazolide, bis(tris(pentafluorophenyl)alumane)imidazolinide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)alumane)-
2-heptadecyIimidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.
Other activators include those described in PCT publication WO 98/07515 such as tris (2,
2', 2"-nonafIuorobiphenyl) fluoroaluminate. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-A-O 573120, PCT publications WO 94/07928 and WO 95/14044 and US Patents 5, 153, 157 and
5,453,410. WO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including their hydrates. WO 99/18135 describes the use of organoboroaluminum activators. EP-A-781299 describes using a silylium salt in combination with a non-coordinating compatible anion. Other activators or methods for activating a catalyst compound are described in for example, U. S. Patents 5,849,852, 5,859, 653, 5,869,723, EP-A-615981, and PCT publication WO 98/32775.
Another suitable class of organometal activators or cocatalysts are alumoxanes, also referred to as alkylaluminoxanes. Alumoxanes are well known activators for use with metallocene type catalyst compounds to prepare addition polymerization catalysts. There are a variety of methods for preparing alumoxanes and modified alumoxanes, non-limiting examples of which are described in U.S. Patents 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; European publications EP-A- 561476, EP-A-279586 and EP-A-594218; and PCT publication WO 94/10180. Preferred alumoxanes are Lewis acid modified alumoxanes, especially tri(C3.6)alkylaluminum modified methylalumoxane, including tri(isobutyl)aluminum modified methalumoxane, available commercially as JVIMAO-3A or tri(n-octyl)aluminum modified methalumoxane, available commercially as MMAO- 12, from Akzo Nobel, Inc. It is within the scope of this invention to use alumoxane(s) or modified alumoxane(s) as an activator or as a tertiary component in the invented process. That is, the compound may be used alone or in combination with other activators, either neutral or ionic, such as tri(alkyl)ammonium tetrakis(pentafluorophenyl)borate compounds, trisperfluoroaryl compounds, polyhalogenated heteroborane anions as disclosed in WO 98/43983, and combinations thereof. When used as a tertiary component, the amount of alumoxane employed is generally less than that necessary to effectively activate the metal complex when employed alone. In this embodiment, it is believed, without wishing to be bound by such belief, that the alumoxane does not contribute significantly to actual catalyst activation. Not withstanding the foregoing, it is to be understood that some participation of the alumoxane in the activation process is not necessarily excluded. Suitable alumoxanes include polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO) as well as Lewis acid- modified alumoxanes, especially trihydrocarbylaluminum-, halogenated tri(hydrocarbyl)aluminum- or halogenated tri(hydrocarbyl)boron- modified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group. Such activating cocatalysts are previously disclosed in USP' s 6,214,760, 6,160,146, 6,140,521, and 6,696,379, and elsewhere. Preferred Lewis acid- modified alumoxane compounds are tri(i-butyl)aluminum- modified methalumoxane and tri(n- octyl)aluminum- modified methalumoxane containing from 10 to 30, preferably 15 to 25 mole percent i-butyl content and 10 to 20, preferably 12 to 18 mole percent n-octyl contents, respectively, said molar percents based on total alkyl Iigand content. The alumoxane or Lewis acid- modified alumoxane activator is preferably utilized in molar ratios cocatalystxatalyst from 20-200, more preferably from 20-150, and most preferably from 20-80.
Because of the ability to be activated at relatively low levels of alumoxane or Lewis acid modified alumoxane cocatalysts while maintaining high catalyst efficiency, the present zirconium complexes can achieve reduced levels of cocatalyst byproducts in the resulting polymer along with long chain branch formation in the resulting polymer. This in turn allows the polymers to be employed in demanding applications that have been previously unsuited for ethylene/ α-olefin interpolymers, such as wire and cable electrical insulation and extrusion forming process for profiles, pipes, and other applications, while retaining good flexibility and processing properties. Multiple reactor polymerization processes may be suitably employed in the present invention. Examples include such systems as are disclosed in USP 3,914,342, among others. The multiple reactors can be operated in series or in parallel, with at least one catalyst composition according to the present invention employed in at least one of the reactors. One or both reactors may also contain at least two catalysts which have different comonomer incorporation capability and/or different molecular weight capability. In one embodiment, a relatively high molecular weight product (Mw from 100,000 to over 1 ,000,000, more preferably 200,000 to 500,000) is formed while in the second reactor a product of a relatively low molecular weight (Mw 2,000 to 300,000) is formed. Both of these reactor products can have similar or different densities and/or elastomer content. The final product is a mixture of the two reactor effluents which are combined prior to devolatilization to result in a uniform mixing of the two or more polymer products. In another embodiment, one reactor may be used to prepare a high ethylene content copolymer optionally containing diene while the second reactor is employed to prepare a homopolymer of either ethylene or the α-olefin or a copolymer of ethylene and one or more α-olefins. Such a dual reactor process allows for the preparation of products with tailored properties. In one embodiment, the reactors are connected in series, that is, the effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen is optionally added to the second reactor. Reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is ideally in the range from 5:95 to 95:5. It will be appreciated by the skilled artisan that the foregoing dual reactor process is capable of producing polymers having broadened molecular weight distribution or polydispersity index (PDI). Preferred polymers made in the foregoing manner have PDI from 2.8 to 10.0, more preferably from 3.0 to 7.0. In addition, in a desirable embodiment, the high molecular weight component contains higher quantities of α-olefin comonomer (lower density) than the low molecular weight component.
In one embodiment, one of the reactors in the polymerization process, including the first of two reactors operating in series, contains a heterogeneous Ziegler-Natta catalyst or a chromium containing catalyst, such as one of the numerous such catalysts known in the art. Examples of Ziegler-Natta catalysts include, but are not limited to, titanium-based catalysts supported on MgCl2, and additionally comprise compounds of aluminum containing at least one aluminum-alkyl bond. Suitable Ziegler-Natta catalysts and their preparation include, but are not limited to, those disclosed in USP's 4,612,300, 4,330,646, and 5,869,575. Suitable chromium based catalysts are those disclosed in USP's 4,981,927, 4,835,219, 4,564,660, 4,173,548, 3,953,413, and elsewhere.
Single reactor, multiple catalyst processes are also useful in the present invention. In one embodiment, two or more catalysts are introduced into a single reactor at the high monomer conversion conditions that are herein disclosed, wherein each catalyst inherently produces different interpolymer products. In one embodiment, a relatively high molecular weight product (Mw from 100,000 to over 1,000,000, more preferably 200,000 to 500,000) is formed from one catalyst while a product of a relatively low molecular weight (Mw 2,000 to 300,000) is formed from the other catalyst. Both of these catalyst compositions can have similar or different comonomer incorporation ability, at least one of which comprises a metal complex as set forth herein. The resulting polymer will have properties dependant on the ratio of the two catalysts that are employed in the single reactor. Suitable combinations of polymer molecular weight, comonomer incorporation ability, processes, and ratios of catalysts for such products are disclosed in USP 6,924,342. Due to the unique compatibility of the present catalyst compositions with other olefin polymerization catalysts, including Ziegler/Natta catalysts, the second catalyst composition may comprise a metal complex as herein disclosed, a metallocene or other π-bonded ligand group containing metal complex (including constrained geometry metal complexes), or a polyvalent heteroatom ligand group containing metal complex, especially polyvalent pyridylamine or imidizolylamine based complexes and tetradendate oxygen-ligated biphenylphenol based Group 4 metal complexes.
METAL COMPLEXES
Suitable metal complexes for use according to the present invention include compounds corresponding to the formula:
Figure imgf000012_0001
, where: R20 independently each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen; T3 is a divalent hydrocarbon or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof; and
RD independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two RD groups together are a divalent ligand group of from 1 to 20 atoms, not counting hydrogen.
Preferably, such complexes correspond to the formula:
Figure imgf000013_0001
, wherein:
Ar2 independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino- substituted arylene group of from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;
T3 is a divalent hydrocarbon bridging group of from 2 to 20 atoms not counting hydrogen, preferably a divalent substituted or unsubstituted C3-6 aliphatic, cycloaliphatic, or bis(alkylene)- substituted cycloaliphatic group; and
RD independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two RD groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen.
More preferred examples of metal complexes suitable for use herein include compounds of the formula:
Figure imgf000013_0002
, where Ar4 independently each occurrence is Cg-2O aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, 3,5-di(tertbutyl)phenyl, dibenzo-lH- pyrrole-1-yl, πaphthyl, anthracen-5-yl, l,2,3,4,6,7,8,9-octahydroanthraceπ-5-yl; T4 independently each occurrence is a propylene-l,3-diyl group, a cyclohexan-l,2-diyl group, a bis(alkylene)cyclohexan-l,2-diyl group, a cyclohexen-4,5-diyl group, or an inertly substituted derivative thereof;
R21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen; and
RD, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 RD groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.
Especially preferred metal complexes are compounds of the formula:
Figure imgf000014_0001
where, Ar4, independently each occurrence, is 3,5-di(isopropyl)phenyl, 3,5- di(isobutyl)phenyl, 3,5-di(tertbutyl)phenyl, dibenzo-lH-pyrroIe-l-yl, or anthracen-5-yl,
R2' independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen;
T4 is propan-l,3-diyl, cyclohexanediyl, cyclohexen~4,5-diyl, or bis(methylene)cyclohexan- 1,2-diyl; and
RD, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 RD groups together are a hydrocarbylene, hydrocarbadiyl or hydrocarbylsϋanediyl group of up to 40 atoms not counting hydrogen.
Compared to metal complexes comprising a 1 ,4-butandiyl T4 group, the foregoing complexes demonstrate improved catalyst efficiencies, especially at elevated polymerization temperatures. Most highly preferred metal complexes according to the invention correspond to the formulas:
Figure imgf000015_0001
wherein, RD independently each occurrence is chloro, methyl or benzyl.
Specific examples of suitable metal complexes are the following compounds: A) bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3 A6 JΛ^octahydroanthracen-S-yO-SKmethyOphenyl^-phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-ρhenoxy)-l,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3-propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-l H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxy)- 1 ,3-propanediylzirconium (IV) dibenzyl, bis((2-oxoy l-3-(3 ,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l, 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-l ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)- 1,3- propanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-( 1 ,2,3 ,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)- trans-l,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)- trans- 1,2-cycIohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-( 1,2,3 ,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethy I)- trans-],2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoy l-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-l ,2- cyclohexanediyl zirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrτole-l-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-l ,2- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyI)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1, 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-2-phenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethy Iethyl)pheny!)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthraceπ-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-y])-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-]-yl)-5-(methy])phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dirnethylethyl)phenyl)-5-(rnethyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl,
B) bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxy)-l,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l, 2,3,4 ,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-
1 ,3-propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 1 ,3-propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 1 ,3- propaπediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy)-l,3- propanediylzirconium (IV) dichloride, bis((2-oxoyI-3-(dibenzo-lH-pyrroIe-l -yl)-5-(methyI)phenyI)-(4-methyI-2-phenoxy)-l ,3- propanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyI)phenyI)-(4-methyl-2-phenoxy)-l ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyI-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyI)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-l ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyI-3-(3,5-di-( J , 1 -dimethylethy])phenyI)-5-(methy])phenyl)-(4-methyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,S,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyO-trans-l^-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyl)-trans- 1 ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyl)-trans-l ,2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- lH-pyrroIe- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyI-3-(dibenzo-l H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-l, 2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-l H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxymethyl)-trans-l ,2- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxyrnethyl)- trans-1 ,2-cyclohexanediylzirconium (FV) dimethyl, bis((2-oxoyl-3-(3,5-di-(i;l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)- trans-1 ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyI-3-(3,5-di-(l ,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)- trans-l ,2-cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyI-2-ρhenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-l,3- cyclohexanediylzirconiurii (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methy l-2-phenoxy))-cis- 1 ,3- cyciohexanediylzirconJum (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methy l-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(1 , 1 -dimethylethyOphenyO-S^methyOphenyO-^-methyl^-phenoxy^-cis-
1 ,3-cyclohexanediyIzircoπium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
1 ,3-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyI)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 1,3-cyclohexanediylzirconiiJm (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-( l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole-1 -yl)-5-(methyl)ρhenyl)-(4-methyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methy]-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
4,5-cycIohexenediyIzirconium (IV) dibenzyl, C) bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxy)-l,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-
1,3-propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-
1,3-propanediylzirconium (IV) dibenzyl, bis((2-oxoyI-3-(dibenzo-l H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-l ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoy l-3-(dibenzo- 1 H-pyrroIe- 1 -y l)-5-(methyl)phenyI)-(4-t-butyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyI-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyI)-(4-t-buty l-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l, l-dimethylethyI)phenyl)-5-(methyl)ρhenyl)-(4-t-butyl-2-phenoxy)-],3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethyIethyl)pheny])-5-(methy])pheny])-(4-t-butyI-2-phenoxy)-l ,3- propanediylzirconium (TV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-buty]-2-phenoxy)-] ,3- propanediylzirconium (TV) dibenzyl,
bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxymethyl)-trans-l ,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(]l,2)3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-(4-t-buty]-2- phenoxymethyl)-trans-l ,2-cyclohexanediyIzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxymethyl)-trans-l ,2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-l ,2- cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-(l, l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)- trans-l,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethyIethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)- trans- 1 ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)- trans-l,2-cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)ρhenyl)-(4-t-butyl-2-ρhenoxy))- cis-l,3-cyclohexanediylzirconium (TV) dichloride, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-l ,3-cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)pheny I)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (FV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-l ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l, 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-l ,3- cyclohexanediylzirconium (IV) dibenzyl
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-ρhenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yI)-5-(rnethyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dichloride, and bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)pheriyl)-(4-t-butyI-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl.
The foregoing metal complexes may be conveniently prepared by standard metallation and ligaπd exchange procedures involving a source of the transition metal and a neutral polyfunctional ligand source. In addition, the complexes may also be prepared by means of an amide elimination and hydrocarbylation process starting from the corresponding transition metal tetraamide and a hydrocarbylating agent, such as trimethylaluminum. The techniques employed are the same as or analogous to those disclosed in USP's 6,320,005, 6,103,657, WO 02/38628, WO 03/40195, US-A- 2004/0220050, and elsewhere.
The metal complex is activated to form the active catalyst composition by combination with the cocatalyst. The activation may occur prior to addition of the catalyst composition to the reactor with or without the presence of other components of the reaction mixture, or in situ through separate addition of the metal complex and activating cocatalyst to the reactor.
MONOMERS Suitable olefin mixtures for use herein include mixtures of ethylene, one or more 03.30 α- olefins and one or more conjugated or nonconjugated dienes. Suitable α-olefin comonomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, and 1-dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1- eicosene, 3-methyl- 1-butene, 3-methyl-l-pentene, 4-methyl- 1-pentene, 4,6-dimethyl- 1-heptene, and vinylcyclohexane.
Suitable dienes for use herein include straight chain-, branched chain-, cyclic-, and polycyclic hydrocarbon dienes having from 6 to 15 carbon atoms. Examples of suitable non- conjugated dienes include, but are not limited to, straight chain acyclic dienes, such as 1,4- hexadiene, 1 ,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5- methyl- 1 ,4-hexadiene; 3,7-dimethyl-l,6-octadiene; 3,7-dimethyl- 1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1 ,3-cyclopentadiene; 1 ,4-cyclohexadiene; 1 ,5-cyclooctadiene and 1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicydo-(2,2,l)-hepta-2, 5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2- norbornene, 5-(4-cyclopentenyl)-2-norbornene, S-cyclohexylidene-l-norbornene, 5-vinyl-2- norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, the particularly preferred dienes are 1 ,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2- norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). The most especially preferred diene is 5-ethylidene-2-norbornene (ENB).
In general, the polymerization may be accomplished at conditions well known in the prior art for olefin solution polymerization reactions. Preferred polymerization temperatures are from 80 to 250 0C, more preferably from 100-200 0C. Preferred polymerization pressures are from atmospheric to 3000 atmospheres (100 kPa to 300 MPa), more preferably from 1 MPa to 10 MPa. In most polymerization reactions the molar ratio of catalyst: polymerizable compound employed is from 10"12:l to 10 1 :1 , more preferably from 10"": 1 to I0"5: L Highly desirably, the reaction is conducted under continuous, solution polymerization conditions, that is, conditions wherein the monomer or monomers are continuously added to a reactor operating under solution polymerization conditions, and polymerized product is continuously or semi-continuously removed and recovered or forwarded to a second reactor.
Desirably, the polymerization mixture comprises an aliphatic or alicyclic liquid diluent. Examples of such aliphatic or alicyclic liquid diluents include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcyclo- heptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C4.10 alkanes, and the like. Small quantities of aromatic hydrocarbons such as toluene, ethylbenzene or xylene may be included as well, but are not preferred. Mixtures of the foregoing are also suitable. A preferred liquid diluent is a hydrogenated oligomeric aliphatic hydrocarbon mixture having a distillation, ASTM D 86, IBP of 118 0C, distillation, ASTM D 86, Dry Point of 137 0C, and Specific Gravity, 15.6 0C, ASTM D 1250 of 0.72 sold commercially under the trade designation Isopar™ E, available from ExxonMobil Corporation.
The use of molecular weight control agents or chain transfer agents in the present process is desired. Examples of such molecular weight control agents include hydrogen, trialkyl aluminum compounds, or other known chain transfer agents. Hydrogen is a most preferred molecular weight control agent or chain transfer agent. A particular benefit of the use of the present invention is the ability (depending on reaction conditions) to produce narrow molecular weight distribution ethylene/ α-olefin interpolymers. Preferred polymers have Mw/Mn of less than 3.0, more preferably less than 2.6. Such narrow molecular weight distribution polymer products are highly desirable due to improved tensile strength properties as well as reduced levels of extractables and metal values. Without limiting in any way the scope of the invention, one means for carrying out the present polymerization process is as follows. In a stirred-tank reactor, the monomers to be polymerized are introduced continuously together with any solvent or diluent. The reactor contains a liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Catalyst along with cocatalyst and optionally chain transfer agent are continuously or intermittently introduced in the reactor liquid phase or any recycled portion thereof. The reactor temperature may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by use of cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. Pressure is controlled by the monomer flow rate and partial pressures of volatile components. The ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The polymer product molecular weight is controlled, optionally, by controlling other polymerization variables such as the temperature, monomer concentration, or by the flow rate of he previously mentioned chain transfer agent. Upon exiting the reactor, the effluent is contacted with a catalyst kill agent such as water, steam or an alcohol. The polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous monomers as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a de volatilizing extruder. In a continuous process, the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, and preferably is from 10 minutes to 6 hours.
Alternatively, the foregoing polymerization may be carried out in a continuous loop reactor with or without a monomer, comonomer, catalyst or cocatalyst gradient established between differing regions thereof, optionally accompanied by separate addition of catalysts and/or chain transfer agent, and operating under adiabatic or non-adiabatic solution polymerization conditions or combinations of the foregoing reactor conditions. Examples of suitable loop reactors and a variety of suitable operating conditions for use therewith are found in USFs 5,977,251 , 6, 319,989 and 6,683, 149.
SPECIFIC EMBODIMENTS The following embodiments are provided for purposes of specific disclosure for the appended claims.
1. A process for polymerization of ethylene, one or more C3-30 α-olefins and one or more conjugated or nonconjugated dienes under continuous, solution polymerization conditions to prepare a high molecular weight interpolymer, said process comprising conducting the polymerization in the presence of a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether corresponding to the formula:
Figure imgf000025_0001
, where:
R20 independently each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen;
T3 is a divalent hydrocarbon or silane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof;
RD independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two RD groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen; and an activating cocatalyst at a temperature from 80 to 250 0C and a pressure from 100 kPa to 300 MPa.
2. The process of embodiment 1 wherein the resulting polymer has a molecular weight distribution, Mw/Mn, less than 3.0. 3. The process of embodiment 1 wherein the catalyst composition additionally comprises a chain transfer agent.
4 The process of embodiment 3 wherein the quantity of chain transfer agent present in the reactor is sufficient to decrease the Mw of the resulting polymer at least 30 percent compared to the molecular weight of the resulting polymer prepared in the absence of a chain transfer agent. 5. The process of embodiment 3 wherein the chain transfer agent is hydrogen, present in an amount from 0.015 to 2.0 mol percent (based on ethylene).
6. The process of embodiment 1 wherein the ethylene conversion is at least 85 mol percent.
7. The process of any one of embodiments 1-6 wherein a monomer mixture consisting essentially of ethylene, propylene, and a diene selected from the group consisting of 1 ,4-hexadiene,
5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene, 5-methylene~2-norbornene, and dicyclopentadiene is polymerized.
8. The process of embodiment 7 wherein a monomer mixture consisting essentially of ethylene, propylene and 5-ethylidene-2-norbornene is polymerized. 9. The process of embodiment 1 conducted at a temperature from 100 to 2000C in the presence of a chain transfer agent to prepare a polymer having a melt index, I2, < 5.0, a molecular weight distribution Mw/Mn < 3.0, and a catalyst efficiency of greater than 0.5 gpoiymer/μgmemi-
10. The process of embodiment 9 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent.
1 1. The process of embodiment 10 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on ethylene.
12. The process of embodiment 1 wherein the cocatalyst is alumoxane present in an amount to provide a molar ratio based on Zr from 20: 1 to 150: 1.
13. The process of embodiment 12 wherein the alumoxane is tri(isobutyl)a!uminum modified methalumoxane or tri(n-octyl)aluminum modified methalumoxane.
14. A process according to any one of embodiments 1-6 wherein the metal complex corresponds to the formula:
Figure imgf000026_0001
, wherein:
Ar2 independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino- substituted arylene group of from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;
T3 is a divalent hydrocarbon bridging group of from 2 to 20 atoms not counting hydrogen, preferably a divalent substituted or unsubstituted C3-6 aliphatic, cycloaliphatic, or bis(alkylene)- substituted cycloaliphatic group; and
RD independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two RD groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen. 15. The process of embodiment 14 wherein the metal complex corresponds to the formula:
Figure imgf000027_0001
, where
Ar4 independently each occurrence is Cβ.2o aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyI)phenyl, dibenzo-lH-pyrrole-1-y], naphthyl, anthracen-5-yl, 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yI ;
T4 independently each occurrence is a propylene- 1 ,3-diyl group, a cyclohexan-l,2-diyl group, a bis(alkylene)cyclohexan-],2-diyl group, a cyclohexen-4,5-diy] group, or an inertly substituted derivative thereof;
R21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen; and
RD, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 RD groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.
16. The process of embodiment 14 wherein the metal complex corresponds to the formula:
Figure imgf000028_0001
wherein, RD independently each occurrence is chloro, methyl or benzyl.
17. The process of embodiment 14 wherein the metal complex is selected from the group consisting of:
A) bis((2-oxoyl-3-( 1 ,2,3 AόJ.S.g-octahydroanthracen-S-yO-S-CrnethyOphenyO-Z-phenoxy)-] ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-l ,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-2-phenoxy)-l ,3-propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3-propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l-dlmethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l ,1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-l ,3- propanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)- trans-l ,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)- trans-1 ,2-cyclohexanediyIzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)- trans-1 ,2-cyclohexanediylzirconiιιm (FV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrroIe-l-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-l ,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (TV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (TV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-l,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-] ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- IH-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-ρhenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo~l H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-l H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- 5 cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , l-dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dichloride,
10 bis((2-oxoyl-3-(3,5-di-(l, l-dimethylethyl)phenyl)-5-(methyl)ρhenyl)-2-phenoxy)-cis-l,3- cyclohexaπediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, )5 bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-y])-5-(methyl)phenyI)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- 20 cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole-1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl 25 bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- 30 cyclohexenediylzirconium (IV) dibenzyl,
B) bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxy)-l,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 35 1,3-propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthfacen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-ρhenoxy)-
1,3-propanediylzirconiurn (IV) dibeπzyl, bis^-oxoyl-S-Cdibenzo-l H-pyrrole-i-yO-S-ζmethy^phenyO^-methyl^-phenoxy)-! ^- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy)-1,3- propanediylzirconium (FV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrroIe- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-(I ,i-dimethyIethyl)phenyl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy)-l ,3- propanediylzirconium (IV) dimethyl, , bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyI)-5-(methyl)phenyI)-(4-methy 1-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-l,3- propanediylzirconium (IV) dibenzyl,
bis^-oxoyl-S^l ^.S.^β.V.S.g-octahydroanthracen-S-yO-S-^ethyOphenylH^methyl^- phenoxymethyl)-trans-l,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyl)-trans-l ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyl)-trans-l,2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (FV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)-trans-1,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-l H-pyrrole- l-yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethyIethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)- trans- 1 ,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)- trans-l ,2-cyclohexanediylzirconium (FV) dichloride, bi s((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methy 1-2-phenoxymethyl)- trans-1 ,2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenylM4-methyl-2-phenoxy))- cis-l ,3-cyclohex.anediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-1 ^-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-1, 3-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoy I-3-(dibenzo- 1 H-pyrroIe- 1 -yI)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyiτole-l-yl)-5-(methyl)phenyl)-(4-rnethyl-2-phenoxy))-cis-l ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-cis-l,3- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyI-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)pheπyI)-(4-methyl-2-phenoxy))-cis-
1, 3-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
1 ,3-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy))-cis-
1, 3-cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (TV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethyIethyl)phenyl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconiutn (IV) dibenzyl,
C) bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxy)- 1 ,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)- 1,3-propanediyIzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)- J ,3-propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-ρhenoxy)-l ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyI)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-l,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenόxy)-l,3- propanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxymethyl)-trans-l,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyI-2- phenoxymethyl)-trans-l ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxymethyl)-trans-l,2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyI)-5-(methyl)phenyI)-(4-t-butyl-2-phenoxymethyl)- trans- 1 ,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)- trans- 1,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)- trans- 1,2-cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyI-3-(I,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-(4-t-butyI-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(],2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-],3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoy]-3-(dibenzo- 1 H-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-l,3- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-l,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-l ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dibenzyl
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (TV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyI-3-(dibenzo- 1 H-pyrrole-1 -yl)-5-(methyI)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyI)-(4-t-butyI-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (FV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dichloride, and bis((2-oxoyI-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl.
It is understood that the present invention is operable in the absence of any component which has not been specifically disclosed and may be combined with any other suitable reaction or process in a multistep polymerization system design. The following examples are provided in order to further illustrate the invention and are not to be construed as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis.
EXAMPLES
Preparation of Metal Complex
The synthetic procedures of US-A-2004/0010103 were substantially repeated to prepare metal complexes Al and Al 1 and Comp.
Figure imgf000035_0001
Al : bis((2-oxoyl-3-(l,2,3A6,7,8,9-octahydro- A2: bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5 anthracen-5-yl)-5-(methyl)phenyl)-2- phenoxy)- (methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,3-propanediyl zirconium (IV) dimethyl 1 ,2-cyclohexanediylzirconium (IV) dimethyl
Figure imgf000036_0001
A3: bis((2-oxoyl-3-(3,5-bis-(l , 1 -dimethylethyl) A4: bis((2-oxoyl-3-(dibenzo-1 H-pyrrole- 1 -yl)-5- phenyl)-5-(methyl)phenyl)-2- phenoxy)- (methyl)phenyl)-2-phenoxy)-
1 ,3-propanediyl zirconium (IV) dimethyl 1 ,3-propanediyl zirconium (IV) dimethyl
Figure imgf000036_0002
A5 : bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5- A6: bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yϊ)-5- (methyI)phenyD-2-phenoxy)-cis- (methyI)ρhenyr)-2-phenoxymethyl)- cis- 1 ,3-cycfohexanediyl zirconium (IV) dimethyl 4,5-cyck)hexenediyl zirconium (IV) dimethyl
Figure imgf000036_0003
A7: bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yI)-5- A8: bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- l-yl)-5- (niethyl)phenyl)-(ΦrrEthyl-2-phenoxyrnethyl))- (methyl)phenyI)-2-ρhenoxy)- trans 1 ^-cyclohexanezirconium (TV) dimethyl 1 ,4-butanediylzirconium QV) dimethyl
Figure imgf000037_0001
A9: bis((2-oxoyl-3-(dibenzo-lH-pyπOle- l-yT)-5- A10: bis((2-oxoyl-3-(dibenzo-lH-pyπOle-l-yI)-5- (rrethyl)phenyI)-(5-(2-iτEthyI)prOpane-2-yl)-2- (methyI)phenyI)-(5-(2-methyl)propane-2-yl)-2- phenoxy)- 1 ,3-propanediyI zirconium (IV) dirrethyl ptenoxy> 1 ,3-propanediyl zirconium (TV) dichloride
Figure imgf000037_0002
Al 1 : bis((2-oxoyl-3-(3,5-bis-(l,l-diπ^thylethyI) Conrp: bis((2-oxoyl-3-(dibenzD- 1 H-pyrrole- 1 -yI)-5- phenyI)-5-(methyI)phenyl)-(5-2-πiethyI)propane (methyl)phenyr>-2-phenoxyπEthyl)-trdns- -2-yj)2- pbsnoxy)- 1 ,3-propanediyl zirconium (IV) 1 ,2-cyctobsxanediylhaϊhium (TV) dimethyl dimethyl
Continuous Polymerization Conditions
Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar™ E available from ExxonMobil, Inc.), ethylene, propylene, 5-ethylidene-2-norbornene, and hydrogen are continuously supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple. The solvent feed to the reactor is measured by a mass-flow controller. A variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At the discharge of the pump, a side stream is taken to provide flush flows for the catalyst and cocatalyst injection lines and the reactor agitator. These flows are measured by mass flow meters and controlled by control valves or by the manual adjustment of needle valves. The remaining solvent is combined with monomers and hydrogen and fed to the reactor. A mass flow controller is used to deliver hydrogen to the reactor as needed. The temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalyst and cocatalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor. The cocatalyst used in runs 1-12 is a long-chain alkyl ammonium borate of approximate stoichiometry equal to methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate (MDB) combined with a tertiary component, tri(isobutyl)aluminum modified methalumoxane (MMAO) containing a molar ratio of i-butyl/methyl groups of about 1/3 in a molar ratio based on transition metal of 5/1. For runs 13-17 the cocatalyst is MAO alone in a molar ratio based on Zr of 50: 1. The reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product is removed through exit lines at the top of the reactor. All exit lines from the reactor are steam traced and insulated. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated by passing through a heat exchanger before devolatilization. The polymer product is recovered by extrusion using a devolatilizing extruder and water cooled pelletizer.
More process details and results are contained in Table 1. Product properties are provided in Table 2. Polymer viscosities are measured at shear rates of 0.1 and 100 radians/second at 190 0C under a nitrogen atmosphere using a dynamic mechanical spectrometer such as a RMS-800™ or ARES™ from Rheometrics Corporation. The viscosities at 0.1 rad/sec and 100 rad/sec may be represented, respectively, as VO.1 and VlOO with a ratio of the two referred to as RR and expressed as V0.1/V100. Table 1
C2H4 C3H6 ENB Solvent H2
T Flow Flow Flow Flow Flow1 C2H4.
Run Cat AkZr B:Zr (kg/h) (kg/h) ikg/h) (kg/h) (seem) Con v. Eff.3
1 Al 30 1.5 133 0.49 0.33 0.07 8.35 13.0 87.6 0.54
2 20 125 0.31 0.06 17.7 87.8 0.83
3* Comp 25 127 0.32 0.07 54.1 87.5 0.28
4 Al 75 0 124 0.47 0.20 0.01 7.26 23.5 88.9 1.98
5 15 1.5 101 0.33 0.40 0.43 8.35 1.7 90.5 0.51
6 10 0.41 0.55 1.3 91.0 0.31
7 25 1 15 0.15 0.73 0.27 0 90.7 0.47
8 114 0.72 0.39 0 90.0 0.38
9* Comp 1 15 0.14 0.83 0.06 7.7 87.9 0.12
10 Al 75 101 0.84 0.13 0 88.1 0.78
1 1 0.1 1 0.92 0.09 0 85.9 0.69
12 20 103 0.12 1.00 0.03 0 87.9 0.95
* Comparative, not an example of the invention
L standard cmVmin
2' percent ethylene conversion in reactor
3" efficiency, g polymer/μg Metal Table 2
Run Mooπev Percent Co Percent Ci Percent ENB RR
1 44.02 71.27 28.25 0.48 61
2 41.11 70.36 29.19 0.44 44
3* 43.04 67.19 32.30 0.51 10
4 13.9 73.79 25.20 1.01 -
5 59.35 51.81 44.51 3.68 68
6 54.48 50.50 44.60 4.90 88
7 17.88 22.60 74.10 3.30
8 14.98 22.00 75.60 2.40 -
9* 19.53 20.19 79.40 0.41 -
10 17.27 17.22 80.80 1.98 44
1 1 17.81 16.92 81.40 1.68 -
12 16.90 16.21 82.75 1.04
* Comparative, not an example of the invention '• Mooney viscosity (ML 1+4 @ 1000C)
Table 3 C2H4 C3H6 ENB Solvent C2H4
Temp flow flow flow flow H2 Coπv. Cat.
Run Cat. (0C) (kg/hri (kg/hr) (kg/hr) (kg/hr) (mol %) £%}' Eff.2
13 Al 153 1.08 0.71 0.03 10.4 0.013 88.2 2.29
14 A7 150 10.5 0.070 88.1 2.01
15 A5 120 c« 0.77 0.02 1 1.1 0.001 87.5 2.00
16 Al l 150 0.94 0.03 10.5 0.009 88.2 1.72
17 A9 120 0.91 10.1 0.003 87.7 0.86 l- percent ethylene conversion in reactor z efficiency, g PE/μg Zr
Table 4
Percent Percent Percent
Run Moonev1 C2 C3 ENB RR
13 43 71.0 28.1 0.9 123.6
14 46 71.8 27.2 1.0 122.9
15 40 71.5 27.4 1.0 40.3
16 44 71.7 27.3 0.9 52.9
17 10 72.6 26.4 1.0 6.7
Mooney viscosity (ML 1+4 @ 1000C)

Claims

CLAIMS:
1. A process for polymerization of ethylene, one or more C3-30 α-olefins and one or more conjugated or nonconjugated dienes under continuous, solution polymerization conditions to prepare a high molecular weight interpolymer, said process comprising conducting the polymerization in the presence of a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether corresponding to the formula:
Figure imgf000040_0001
, where:
R20 independently each occurrence is a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms not counting hydrogen;
T3 is a divalent hydrocarbon or siJane group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof;
RD independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two RD groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen; and an activating cocatalyst at a temperature from 80 to 250 0C and a pressure from 100 kPa to 300 MPa.
2. The process of claim 1 wherein the resulting polymer has a molecular weight distribution, Mw/Mn, less than 3.0.
3. The process of claim 1 wherein the catalyst composition additionally comprises a chain transfer agent.
4 The process of claim 3 wherein the quantity of chain transfer agent present in the reactor is sufficient to decrease the Mw of the resulting polymer at least 30 percent compared to the molecular weight of the resulting polymer prepared in the absence of a chain transfer agent.
5. The process of claim 3 wherein the chain transfer agent is hydrogen, present in an amount from 0.015 to 2.0 mol percent (based on ethylene).
6. The process of claim 1 wherein the ethylene conversion is at least 85 mol percent.
7. The process of any one of claims 1 -6 wherein a monomer mixture consisting essentially of ethylene, propylene, and a diene selected from the group consisting of 1 ,4-hexadiene, 5-ethyIidene-2-norbornene, 5-vinylidene-2-norborneτie, 5-methylene-2-norbornene, and dicyclopentadiene is polymerized.
8. The process of claim 7 wherein a monomer mixture consisting essentially of ethylene, propylene and 5-ethylidene-2-norbornene is polymerized.
9. The process of claim 1 conducted at a temperature from 100 to 2000C in the presence of a chain transfer agent to prepare a polymer having a melt index, I2, < 5.0, a molecular weight distribution Mw/Mn < 3.0, and a catalyst efficiency of greater than 0.5 gpoiymer/μgmetai-
10. The process of claim 9 wherein the chain transfer agent is present in a quantity such that the decrease in Mw of the resulting polymer is >30 percent compared to the Mw of the resulting polymer made in the absence of chain transfer agent.
1 1. The process of claim 10 wherein the chain transfer agent is hydrogen present in the reactor in an amount of from 0.015 to 2 mol percent based on ethylene.
12. The process of claim 1 wherein the cocatalyst is alumoxaπe present in an amount to provide a molar ratio based on Zr from 20: 1 to 150: 1.
13. The process of claim 12 wherein the alumoxane is tri(isobutyl)aluminum modified methalumoxane or tri(n-octyl)alurninum modified methalumoxane.
14. A process according to any one of claims 1 -6 wherein the metal complex corresponds to the formula:
Figure imgf000041_0001
, wherein:
Ar2 independently each occurrence is an arylene or an alkyl-, aryl-, alkoxy- or amino- substituted arylene group of from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;
T3 is a divalent hydrocarbon bridging group of from 2 to 20 atoms not counting hydrogen, and
RD independently each occurrence is a monovalent ligand group of from 1 to 20 atoms, not counting hydrogen, or two RD groups together are a divalent ligand group of from 1 to 40 atoms, not counting hydrogen.
15. The process of claim 14 wherein the metal complex corresponds to the formula:
Figure imgf000042_0001
, where
Ar4 independently each occurrence is Cύ-20 aryl or inertly substituted derivatives thereof;
T4 independently each occurrence is a propylene- 1 ,3-diyl group, a cyclohexan-l,2-diyl group, a bis(alkylene)cyclohexan-l,2-diyl group, a cyclohexen-4,5-diyl group, or an inertly substituted derivative thereof;
R21 independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino of up to 50 atoms not counting hydrogen; and
RD, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 RD groups together are a divalent hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.
16. The process of claim 14 wherein the metal complex corresponds to the formula:
Figure imgf000043_0001
wherein, RD independently each occurrence is chloro, methyl or benzyl.
17. The process of claim 14 wherein the metal complex is selected from the group consisting of:
A) bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyI)-2-phenoxy)-l,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3 ,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methy l)phenyl)-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyI-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-l ,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrroIe-l-yl)-5-(methyl)phenyl)-2-phenoxy)-l ,3-propanediyIzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-:phenoxy)-l,3-propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-l,3-propanediylzirconium (IV) di benzyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , l-dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-l ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l ,1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-l ,3- propanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyI)-2-phenoxymethyl)- trans-1 ^-cyclohexanediylzirconium (FV) dimethyl, bis((2-oxoyl-3-( 1,2,3 Aό.y.S^-octahydroanthracen-S-ylJ-S^methyOphenyO-Z-phenoxynnethyl)- trans-1 ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)pheπyI)-2-phenoxymethyl)- trans-l ,2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyI-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-2-phenoxymethyI)-trans-l,2- cyclohexanediylzirconium (TV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l -yI)-5-(methyl)phenyl)-2-phenoxymethyI)-trans- 1 ,2- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxymethyI)-trans- 1 ,2- cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-( 1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-( 1 ,2,3,4,6,7, 8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3-
•cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyI-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxy)-ci s- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-l H-pyrrole-l-yl)~5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexaπediylzirconium (IV) dichloride, bis((2-oxoyI-3-(dibenzo-lH-pyrrole-I-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethyJethyl)phenyI)-5-(methyI)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyI-3-(3,5-di-(l, 1 -dimethylethyl)phenyl)-5-(methyl)phenyI)-2-phenoxy)-cis-l ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoy l-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyI)-5-(methyl)phenyl)-2-phenoxy)-cis- 1 ,3- cyclohexaπediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (W) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(rnethyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (W) dimethyl, bis((2-oxoyI-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (W) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , l-dimethylethyl)phenyl)-5-(methyl)phenyl)-2-phenoxy)-cis-4,5- cyclohexenediylzirconium (W) dibenzyl,
B) bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methyl)phenyl)-(4-methyl-2- phenoxy)-l ,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)phenyl)-(4-methyl-2-phenoxy)-
1,3-propanediylzirconium (W) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 1 ,3-propanediyIzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyI)-(4-methyl-2-phenoxy)-l,3- propanediylzinconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-l,3- propanediylzirconium (JTV) dichloride, bis((2-oxoy]-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-l,3- propanediylzirconium (TV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyI)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyI-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy)-l ,3- propanediylzirconium (IV) dibenzyl,
bis((2-oxoyI-3-(1 ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyl)-trans-l ,2-cyclohexanediylzircoπium (IV) dimethyl, bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyl)-trans-l ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2- phenoxymethyO-trans-l^-cycIohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-(4-methyI-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)pheπyl)-(4-methyl-2-ρhenoxymethyl)-trans- 1 ,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyI-3-(dibenzo-lH-pyrroIe-l-yl)-5-(methyI)phenyl)-(4-methyl-2--phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)- trans-l,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethyIethyl)phenyl)-5-(methyl)phenyI)-(4-methyl-2-phenoxymethyl)- trans- 1 ,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxymethyl)- trans-l,2-cyclohexaπediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yI)-5-(methy])phenyl)-(4-methyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyI-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-πiethyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(],2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-l,3-cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-cis-l,3- cyclohexanediylzirconium (IV) dimethyl, bis^-oxoyl-S^dibeπzo-lH-pyrroIe-l-yO-S^methyOphenyO^-methyl^-phenoxy^-cis-I.S- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoy]-3-(dibenzo- 1 H-pyrroIe- 1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (W) dibenzyl, bis((2-oxoyl-3-(3,5-d i-( 1 , 1 -dimethylethyl)pheπyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
1 ,3-cyclohexanediyIzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))-cis-
1 ,3-cyclohexanediylzirconium (FV) dichloride, bis((2-oxoyl-3-(3,5-di-(l , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
1,3-cyclohexanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-4,5-cyclohexenediyIzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-methyI-2-phenoxy))- cis-4,5-cydohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-methy l-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pytτole-l-yl)-5-(methyl)phenyl)-(4-tnethyl-2-phenoxy))-cis-4>5- cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo- 1 H-pyrroIe-1 -yl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l ,l-dimethylethyI)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis-
4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethyIethyI)phenyI)-5-(methyI)phenyl)-(4-methyl-2-phenoxy))-cis-
4,5-cycIohexenediylzirconium (IV) dichloride, bis((2-oxoy l-3~(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-methyl-2-phenoxy))-cis- 4,5-cyclohexenediylzirconium (IV) dibenzyl,
C) bis((2-oxoyI-3-(1 , 2,3,4,6,7.S^-octahydroanthracen-S-yO-S-Cmethy^phenylX^t-butyl-l- phenoxy)-l,3-propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l, 2,3,4,6, 7,8,9-octahydroanthracen-5-yl)-5-(methyl)ρhenyl)-(4-t-butyl-2-phenoxy)-
1,3-propanediylzirconram (TV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyI)ρhenyI)-(4-t-buty]-2-ρhenoxy)-
1 ,3-propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyI)-(4-t-butyl-2-phenoxy)-l,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-l H-pyrrole-1 -yl)-5-(methyl)phenyI)-(4-t-butyl-2-ρhenoxy)-l ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yI)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy)-l,3- propanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l ,l-dimethylethyl)phenyl)-5-(methy])phenyl)-(4-t-buty]-2-phenoxy)-l,3- propanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l , l-dimethyIethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-ρhenoxy)- 1 ,3- propanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(3,5-di-(l ,l-dimethylethyl)phenyI)-5-(methyl)phenyl)-(4-t-butyl-2-ρhenoxy)-l,3- propanediylzirconium (IV) dibenzyl,
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxymethyl)-trans-l,2-cyclohexanediylzircoπium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxymethyl)-trans-l,2-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2- phenoxymethyl)-trans-l,2-cyclohexanediylzirconium (IV) dibenzyl, bis((2-ox.oyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-l ,2- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoy l-3-(dibenzo- 1 H-pyrrole- 1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy methy l)-trans-l ,2- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrroIe-l-yI)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)-trans-l,2- cyclohexanediylzirconium (IV) dibenzyl bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethy!)phenyl)-5-(methyI)phenyl)-(4-t-butyl-2-phenoxymethyl)- trans- 1 ,2-cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l ,l-dimethylethyl)phenyI)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy methyl)- trans- 1 ^-cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyI-3-(3,5-di-(l ,l-dimethylethyl)phenyI)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxymethyl)- trans- 1 ,2-cyclohexanediylzirconium (FV) dibenzyl,
bis((2-oxoyl-3-(l ,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-l,3-cyclohexanedϊylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-l,3-cyclohexaπediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyI-2-phenoxy))- cis-],3-cyclohexanediylzirconium (IV) dibenzyJ bis((2-oxoyI-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyI)phenyl)-(4-t-butyl-2-phenoxy))-cis-l,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-l H-pyrrole-1 -yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)pheπyl)-(4-t-butyl-2-phenoxy))-cis-l,3- cyclohexanediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l ,l-dimethylethyl)phenyl)-5-(methyl)phenyI)-(4-t-butyI-2-phenoxy))-cis-l ,3- cyclohexanediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyI)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (FV) dichloride, bis((2-oxoyl-3-(3,5-di-( 1 , 1 -dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis- 1 ,3- cyclohexanediylzirconium (IV) dibenzyl
bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-ρhenoxy))- cis-4,5-cyclohexenediylzirconium (IV) dichloride, bis((2-oxoyl-3-(l,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))- cis-4,5-cycIohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(dibenzo-lH-ρyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (FV) dichloride, bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l-yl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dimethyl, bis((2-oxoyl-3-(3,5-di-(l,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyciohexenediylzirconium (IV) dichloride, and bis((2-oxoyl-3-(3,5-di-(1 ,l-dimethylethyl)phenyl)-5-(methyl)phenyl)-(4-t-butyl-2-phenoxy))-cis-4,5- cyclohexenediylzirconium (IV) dibenzyl.
PCT/US2007/009842 2006-05-17 2007-04-24 Ethylene/ alpha-olefin/ diene solution polymerization process Ceased WO2007136494A2 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
CA002652456A CA2652456A1 (en) 2006-05-17 2007-04-24 Ethylene/ .alpha.-olefin/ diene solution polymerization process and polymer
EP07755918.5A EP2024399B1 (en) 2006-05-17 2007-04-24 Ethylene/ alpha-olefin/ diene solution polymerization process
CN2007800233160A CN101472952B (en) 2006-05-17 2007-04-24 Ethylene/α-olefin/diene solution polymerization
ES07755918.5T ES2475159T3 (en) 2006-05-17 2007-04-24 Polymerization procedure in ethylene / alpha-olefin / diene solution
AU2007254428A AU2007254428A1 (en) 2006-05-17 2007-04-24 Ethylene/ alpha-olefin/ diene solution polymerization process
JP2009510950A JP5603595B2 (en) 2006-05-17 2007-04-24 Ethylene / α-olefin / diene solution polymerization method and polymer
US12/300,863 US8299189B2 (en) 2006-05-17 2007-04-24 Ethylene/α-olefin/diene solution polymerization process and polymer
MX2008014668A MX2008014668A (en) 2006-05-17 2007-04-24 Ethylene/ alpha-olefin/ diene solution polymerization process.
KR1020087030629A KR101401785B1 (en) 2006-05-17 2007-04-24 Ethylene/α-Olefin/Diene Solution Polymerization Process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80118206P 2006-05-17 2006-05-17
US60/801,182 2006-05-17

Publications (2)

Publication Number Publication Date
WO2007136494A2 true WO2007136494A2 (en) 2007-11-29
WO2007136494A3 WO2007136494A3 (en) 2008-01-10

Family

ID=38572813

Family Applications (6)

Application Number Title Priority Date Filing Date
PCT/US2007/009842 Ceased WO2007136494A2 (en) 2006-05-17 2007-04-24 Ethylene/ alpha-olefin/ diene solution polymerization process
PCT/US2007/010070 Ceased WO2007136506A2 (en) 2006-05-17 2007-04-24 Polyolefin solution polymerization process and polymer
PCT/US2007/009845 Ceased WO2007136497A2 (en) 2006-05-17 2007-04-24 High temperature solution polymerization process
PCT/US2007/009843 Ceased WO2007136495A2 (en) 2006-05-17 2007-04-24 High efficiency solution polymerization process
PCT/US2007/009841 Ceased WO2007136493A2 (en) 2006-05-17 2007-04-24 Polypropylene solution polymerization process
PCT/US2007/009844 Ceased WO2007136496A2 (en) 2006-05-17 2007-04-24 High temperature polyethylene solution polymerization process

Family Applications After (5)

Application Number Title Priority Date Filing Date
PCT/US2007/010070 Ceased WO2007136506A2 (en) 2006-05-17 2007-04-24 Polyolefin solution polymerization process and polymer
PCT/US2007/009845 Ceased WO2007136497A2 (en) 2006-05-17 2007-04-24 High temperature solution polymerization process
PCT/US2007/009843 Ceased WO2007136495A2 (en) 2006-05-17 2007-04-24 High efficiency solution polymerization process
PCT/US2007/009841 Ceased WO2007136493A2 (en) 2006-05-17 2007-04-24 Polypropylene solution polymerization process
PCT/US2007/009844 Ceased WO2007136496A2 (en) 2006-05-17 2007-04-24 High temperature polyethylene solution polymerization process

Country Status (14)

Country Link
US (7) US8354484B2 (en)
EP (8) EP2024402B2 (en)
JP (6) JP5645400B2 (en)
KR (6) KR101384380B1 (en)
CN (8) CN101472952B (en)
AR (6) AR060642A1 (en)
AU (1) AU2007254428A1 (en)
BR (3) BRPI0711018A8 (en)
CA (5) CA2652551A1 (en)
ES (7) ES2534469T3 (en)
MX (4) MX2008014668A (en)
RU (4) RU2008149712A (en)
SG (1) SG158102A1 (en)
WO (6) WO2007136494A2 (en)

Cited By (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010079906A3 (en) * 2009-01-06 2010-08-26 에스케이에너지 주식회사 Ethylene-propylene-diene copolymer production method
WO2011025784A1 (en) 2009-08-31 2011-03-03 Dow Global Technologies Inc. Catalyst and process for polymerizing an olefin and polyolefin prepared thereby
WO2011066469A1 (en) 2009-11-24 2011-06-03 Dow Global Technologies Inc. Extrusion coating composition
WO2011079207A1 (en) 2009-12-24 2011-06-30 Dow Global Technologies Llc Polymer compositions, methods of making the same, and articles prepared from the same
WO2011146291A1 (en) 2010-05-17 2011-11-24 Dow Global Technologies Llc Process for selectively polymerizing ethylene and catalyst therefor
WO2012064630A2 (en) 2010-11-08 2012-05-18 Dow Global Technologies Llc Solution polymerization process and procatalyst carrier systems useful therein
WO2012074812A1 (en) 2010-12-03 2012-06-07 Dow Global Technologies Llc Processes to prepare ethylene-based polymer compositions
WO2012088235A2 (en) 2010-12-21 2012-06-28 Dow Global Technologies Llc Olefin-based polymers and dispersion polymerizations
WO2012088217A1 (en) 2010-12-21 2012-06-28 Dow Global Technologies Llc Polymerization process and raman analysis for olefin-based polymers
WO2012092491A2 (en) 2010-12-30 2012-07-05 Dow Global Technologies Llc Compositions, methods of making the same, and articles prepared from the same
WO2013039739A1 (en) 2011-09-07 2013-03-21 Dow Global Technologies Llc Polymer compositions and articles prepared from the same
WO2013039850A1 (en) 2011-09-12 2013-03-21 Dow Global Technologies Llc Compositions and articles formed from the same
WO2013055642A1 (en) 2011-10-10 2013-04-18 Dow Global Technologies Llc Polymer compositions with improved retention of properties under mechanical and thermal stresses
WO2013059391A1 (en) 2011-10-20 2013-04-25 Dow Global Technologies Llc Ethylene-based polymer compositions and articles prepared therefrom
JP2013521382A (en) * 2010-03-02 2013-06-10 ダウ グローバル テクノロジーズ エルエルシー Ethylene polymer composition
WO2013096418A1 (en) 2011-12-19 2013-06-27 Dow Global Technologies Llc Ethylene-based polymers prepared by dispersion polymerization
WO2013096573A1 (en) 2011-12-20 2013-06-27 Dow Global Technologies Llc Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same
WO2013043796A3 (en) * 2011-09-23 2013-07-04 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
JP2013528689A (en) * 2010-06-14 2013-07-11 ダウ グローバル テクノロジーズ エルエルシー Ethylene-based polymer composition for use as a blend component in shrink film applications
WO2014084893A1 (en) 2012-11-30 2014-06-05 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene based compositions
US8784996B2 (en) 2009-11-24 2014-07-22 Dow Global Technologies Llc Extrusion coating composition
WO2014113046A1 (en) 2013-01-18 2014-07-24 Dow Global Technologies Llc Polymerization processes for high molecular weight polyolefins
CN104628920A (en) * 2013-11-08 2015-05-20 中国石油天然气股份有限公司 A kind of preparation method of solution polymerization ethylene propylene rubber
WO2015116381A1 (en) * 2014-01-30 2015-08-06 Exxonmobil Chemical Patents Inc. Crack-resistant polyethylene composiitions
WO2015116382A1 (en) * 2014-01-30 2015-08-06 Exxonmobil Chemical Patents Inc. Foamed polyethylene compositions
WO2016014749A1 (en) 2014-07-24 2016-01-28 Dow Global Technologies Llc Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers
WO2016209807A1 (en) 2015-06-22 2016-12-29 Dow Global Technologies Llc Process for making ethylene-based polymers using carbon-carbon free radical initiators
US9605098B2 (en) 2013-06-28 2017-03-28 Dow Global Technologies Llc Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts
WO2017210201A1 (en) 2016-05-30 2017-12-07 Dow Global Technologies Llc Ethylene/alpha-olefin/diene interpolymers compositions
WO2017210195A1 (en) 2016-05-30 2017-12-07 Dow Global Technologies Llc Ethylene/alpha-olefin/diene interpolymer
WO2018005852A1 (en) 2016-06-30 2018-01-04 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene based compositions
WO2018005789A1 (en) 2016-06-30 2018-01-04 Dow Global Technologies Llc Procatalyst compositions useful for low comonomer incorporation and process for preparing the same
WO2018005922A1 (en) 2016-06-30 2018-01-04 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same
WO2018013283A2 (en) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Dual metallocene catalyst copolymer compositions
WO2018013284A2 (en) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Dual metallocene catalyst copolymer compositions
WO2018013286A1 (en) 2016-07-14 2018-01-18 Exxonmobil Chemical Patents Inc. Lubricating oil compositions comprising dual metallocene-catalyzed bimodal copolymer compositions useful as viscosity modifiers
EP2523983B1 (en) * 2010-01-14 2018-03-21 ExxonMobil Chemical Patents Inc. Processes and apparatus for continuous solution polymerization
WO2018063900A1 (en) 2016-09-29 2018-04-05 Dow Global Technologies Llc Method of polymerizing an olefin
WO2018063898A1 (en) 2016-09-29 2018-04-05 Dow Global Technologies Llc Modified ziegler-natta (pro)catalyst and system
WO2018080690A1 (en) 2016-10-27 2018-05-03 Univation Technologies, Llc Method of preparing a molecular catalyst
US10059787B2 (en) 2012-12-27 2018-08-28 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
WO2018231224A1 (en) 2017-06-14 2018-12-20 Exxonmobil Chemical Patents Inc. Ethylene copolymer blends for cross-linking applications
US10214602B2 (en) 2012-12-27 2019-02-26 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US10214622B2 (en) 2012-12-27 2019-02-26 Dow Global Technologies Llc Catalyst systems for olefin polymerization
WO2019040845A1 (en) 2017-08-24 2019-02-28 Dow Global Technologies Llc Ethylene/c5-c10 alpha-olefin/ polyene interpolymers
US10336846B2 (en) 2015-05-28 2019-07-02 Dow Global Technologies Llc Process to form ethylene/α-olefin interpolymers
WO2019157687A1 (en) 2018-02-14 2019-08-22 Dow Global Technologies Llc Ethylene/alpha-olefin interpolymer compositions with improved long term heat aging performance
US10487200B2 (en) 2015-10-29 2019-11-26 Dow Global Technologies Llc Crosslinkable polymeric compositions for flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
US10490319B2 (en) 2015-09-02 2019-11-26 Dow Global Technologies Llc Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
WO2020046597A1 (en) 2018-08-29 2020-03-05 Exxonmobil Chemical Patents Inc. Methods of making polymer compositions with enhanced elasticity by employing vtp and hmp catalyst systems in parallel processes
US10597473B2 (en) 2015-06-30 2020-03-24 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US10647797B2 (en) 2015-09-30 2020-05-12 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US10822479B2 (en) 2012-09-20 2020-11-03 Exxonmobil Chemical Patents Inc. Foamed polyethylene compositions
US10836853B2 (en) 2012-09-20 2020-11-17 Exxonmobil Chemical Patents Inc. Crack-resistant polyethylene compositions
US10870713B2 (en) 2015-09-30 2020-12-22 Dow Global Technologies Llc Procatalyst and polymerization process using the same
WO2021022014A1 (en) 2019-07-31 2021-02-04 Dow Global Technologies Llc Polymerization of ethylene in solution processes using a ziegler-natta catalyst and a hydrogenation procatalyst
WO2021041562A1 (en) 2019-08-30 2021-03-04 Dow Global Technologies Llc Polyolefin compositions having improved electrical properties
WO2021061577A1 (en) 2019-09-24 2021-04-01 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene interpolymer compositions
WO2021061580A1 (en) 2019-09-24 2021-04-01 Dow Global Technologies Llc Polymer compositions for extruded profiles
US11041027B2 (en) 2015-06-30 2021-06-22 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US11066489B2 (en) 2017-09-29 2021-07-20 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility
US11066428B2 (en) 2017-09-29 2021-07-20 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility
WO2021202091A1 (en) 2020-03-30 2021-10-07 Exxonmobil Chemical Patents Inc. Comb-block copolymers and methods thereof
US11155693B2 (en) 2015-09-02 2021-10-26 Dow Global Technologies Llc Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
US11180644B2 (en) 2011-09-23 2021-11-23 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions with enhanced melt strength
WO2022015370A1 (en) 2020-07-17 2022-01-20 Dow Global Technologies Llc Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxy metal-ligand complexes
WO2022015368A1 (en) 2020-07-17 2022-01-20 Dow Global Technologies Llc Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes
WO2022015369A1 (en) 2020-07-17 2022-01-20 Dow Global Technologies Llc Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes
US11242415B2 (en) 2017-09-29 2022-02-08 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility
US11447584B2 (en) 2018-03-30 2022-09-20 Dow Global Technologies Llc Olefin polymerization activators
US11447586B2 (en) 2018-03-30 2022-09-20 Dow Global Technologies Llc Olefin polymerization activators
US11542350B2 (en) 2018-03-30 2023-01-03 Dow Global Technologies Llc Binuclear olefin polymerization activators
US11787880B2 (en) 2018-03-30 2023-10-17 Dow Global Technologies Llc Highly soluble alkyl substituted carbenium borate as co-catalysts for olefin polymerizations
US12037440B2 (en) 2018-03-30 2024-07-16 Dow Global Technologies Llc Highly soluble bis-borate as binuclear co-catalysts for olefin polymerization
US12252574B2 (en) 2018-08-30 2025-03-18 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin procatalysts having two anthracenyl ligands
WO2025117273A1 (en) 2023-12-01 2025-06-05 ExxonMobil Technology and Engineering Company Support-bound activators, supported catalyst systems, and processes for use thereof
US12378391B2 (en) 2019-03-29 2025-08-05 Dow Global Technologies Llc Oil-extended pellet form ethylene alpha-olefin diene interpolymers for thermoplastic vulcanizates
US12384909B2 (en) 2019-09-24 2025-08-12 Dow Global Technologies Llc Polymer compositions with excellent electrical and mechanical properties
US12497414B2 (en) 2020-01-31 2025-12-16 Dow Global Technologies Llc Group III and Lanthanide bis-phenyl-phenoxy metal-ligand complexes
US12552885B2 (en) 2020-01-31 2026-02-17 Dow Global Technologies Llc Polymerization process that include group III and lanthanide bis-phenyl-phenoxy metal-ligand complexes and chain transfer agents

Families Citing this family (162)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1243641A (en) 1984-09-07 1988-10-25 Bell & Howell Company Method and apparatus for controlling the actuation of gripper arms
DE19711948C2 (en) 1997-03-21 1999-05-20 Roland Man Druckmasch Device in a printing machine for applying glue
ES2534469T3 (en) * 2006-05-17 2015-04-23 Dow Global Technologies Llc Polymerization process of polyethylene in high temperature solution
ES2435568T3 (en) * 2007-11-19 2013-12-20 Dow Global Technologies Llc Propylene-alpha-olefin copolymers with long chain branching
EP2438093B1 (en) * 2009-06-05 2013-07-24 Dow Global Technologies LLC Process to make long chain branched (lcb), block, or interconnected copolymers of ethylene
US8722817B2 (en) 2009-06-05 2014-05-13 Dow Global Technologies Llc Process to make long chain branched (LCB), block, or interconnected copolymers of ethylene
US9243087B2 (en) 2009-06-11 2016-01-26 Dow Global Technologies Llc LDPE enabling high output and good optics when blended with other polymers
SG178222A1 (en) 2009-07-01 2012-03-29 Dow Global Technologies Llc Ethylenic polymer and its use
US8629214B2 (en) 2009-07-01 2014-01-14 Dow Global Technologies Llc. Ethylene-based polymer compositions for use as a blend component in shrinkage film applications
US20110003940A1 (en) * 2009-07-01 2011-01-06 Dow Global Technologies Inc. Ethylene-based polymer compositions for use as a blend component in shrinkage film applications
SG10201403765WA (en) * 2009-07-01 2014-09-26 Dow Global Technologies Llc Ethylenic Polymer And Its Use
MX2012001837A (en) 2009-08-10 2012-02-29 Dow Global Technologies Llc Ldpe for use as a blend component in shrinkage film applications.
JP5623043B2 (en) * 2009-09-04 2014-11-12 出光興産株式会社 Polyolefin production method, production apparatus thereof, and polymerization apparatus
BR112012005695A2 (en) 2009-09-14 2020-10-13 Dow Global Technologies Inc polymer, composition, article and process to form a polymer
CN102695734B (en) 2009-09-14 2015-05-06 陶氏环球技术有限责任公司 Polymers comprising units derived from ethylene and polyalkene
JP5764561B2 (en) 2009-09-14 2015-08-19 ダウ グローバル テクノロジーズ エルエルシー Polymers containing units derived from ethylene and siloxane
US20110290317A1 (en) * 2010-05-26 2011-12-01 John Naumovitz Electronic device module comprising polyolefin copolymer with low unsaturation and optional vinyl silane
US20130233383A1 (en) 2010-06-04 2013-09-12 John A. Naumovitz Electronic Device Module Comprising Film of Homogeneous Polyolefin Copolymer and Grafted Silane
CN102918098A (en) 2010-06-04 2013-02-06 陶氏环球技术有限公司 Electronic device module comprising film of homogeneous polyolefin copolymer and adhesive property enhancing graft polymer
US8722819B2 (en) * 2010-07-06 2014-05-13 Ticona Gmbh Process for producing high molecular weight polyethylene
KR101849188B1 (en) 2010-11-02 2018-04-17 다우 글로벌 테크놀로지스 엘엘씨 A sealant composition, method of producing the same
JP6336908B2 (en) * 2011-10-05 2018-06-06 ダウ グローバル テクノロジーズ エルエルシー Spunbond nonwoven fabric
BR112014009439A2 (en) * 2011-10-21 2017-04-11 Dow Global Technologies Llc shrinkable multilayer film
ES2625475T3 (en) * 2011-10-24 2017-07-19 Dow Global Technologies Llc  Strand of artificial grass
EP2791190B1 (en) 2011-12-13 2016-07-06 Dow Global Technologies LLC Ethylene-propylene-diene interpolymer composition
EP2797962B1 (en) * 2011-12-29 2015-11-18 Dow Global Technologies LLC Process for producing low molecular weight ethylene- and alpha-olefin-based materials
EP2797963B1 (en) * 2011-12-29 2019-07-03 Dow Global Technologies LLC Hyperbranched olefin oil-based dielectric fluid
EP2617741B1 (en) * 2012-01-18 2016-01-13 Borealis AG Process for polymerizing olefin polymers in the presence of a catalyst system and a method of controlling the process
CN108384033B (en) * 2012-02-03 2021-11-12 陶氏环球技术有限责任公司 Film comprising silane-containing ethylene interpolymer formulation and electronic device module comprising same
SG11201407355VA (en) 2012-05-09 2014-12-30 Dow Global Technologies Llc Polyolefin polymerization process, semi-crystalline ethylene-based polymer made therefrom, and articles made from the polymer
CN104583304B (en) * 2012-06-29 2017-06-16 陶氏环球技术有限责任公司 For the ethylene/alpha-olefin/unconjugated polyene based composition and use thereof in packaging of TPV
JP2015523446A (en) * 2012-07-20 2015-08-13 ダウ グローバル テクノロジーズ エルエルシー Linear low density polyethylene composition suitable for cast film
US9382349B2 (en) 2012-08-03 2016-07-05 Exxonmobil Chemical Patents Inc. Polyalphaolefins prepared using modified Salan catalyst compounds
CN104364321A (en) 2012-08-03 2015-02-18 埃克森美孚化学专利公司 Halogenated catalysts comprising Salan ligands
WO2014022008A1 (en) 2012-08-03 2014-02-06 Exxonmobil Chemical Patents Inc. Catalysts comprising salan ligands
EP2880097B1 (en) 2012-08-03 2023-10-18 ExxonMobil Chemical Patents Inc. Process to prepare a vinyl terminated polyethylene with long chain branching
US8957172B2 (en) 2012-08-03 2015-02-17 Exxonmobil Chemical Patents Inc. Nonsymmetric catalysts comprising salan ligands
WO2014022013A1 (en) 2012-08-03 2014-02-06 Exxonmobil Chemical Patents Inc. Polyalphaolefins prepared using modified salan catalyst compounds
CN104428324B (en) 2012-11-02 2018-08-17 埃克森美孚化学专利公司 Support type Salan catalyst
JP6207336B2 (en) * 2012-11-12 2017-10-04 日本ポリプロ株式会社 Diol compound, catalyst for olefin polymerization, and method for producing olefin polymer
WO2014105413A1 (en) 2012-12-27 2014-07-03 Dow Global Technologies Llc An ethylene based polymer
CN104854144B (en) 2012-12-27 2018-08-07 陶氏环球技术有限责任公司 Polyvinyls
EP3312200B1 (en) 2013-02-08 2019-06-19 Mitsui Chemicals, Inc. Solid polyaluminoxane composition, olefin polymerization catalyst, olefin polymer production method and solid polyaluminoxane composition production method
CN105121558B (en) 2013-03-13 2017-09-26 埃克森美孚化学专利公司 diphenylamine SALAN catalyst
KR101657262B1 (en) * 2013-04-05 2016-09-13 한화케미칼 주식회사 Catalyst for olefin polymerization and method for preparing polyolefin using the same
WO2014204681A1 (en) 2013-06-20 2014-12-24 Exxonmobil Chemical Patents Inc. Long-bridged salen catalyst
CN105392776B (en) 2013-06-20 2019-02-12 埃克森美孚化学专利公司 Thio-Salalen catalyst
US9200099B2 (en) 2013-06-20 2015-12-01 Exxonmobil Chemical Patents Inc. Salenol catalyst
CN105339327B (en) * 2013-06-28 2020-01-21 陶氏环球技术有限责任公司 Ethylene-based hyperbranched oligomers
EP2883889A4 (en) 2013-06-28 2016-06-01 Lg Chemical Ltd Trinary elastic copolymer comprising diene and method for preparing same
KR101585204B1 (en) 2013-06-28 2016-01-13 주식회사 엘지화학 Elastic diene terpolymer and preparation method thereof
IN2015DN02232A (en) 2013-06-28 2015-08-21 Lg Chemical Ltd
US9650460B2 (en) 2013-06-28 2017-05-16 Lg Chem, Ltd. Elastic diene terpolymer and preparation method thereof
US10155831B2 (en) * 2013-09-05 2018-12-18 Univation Technologies, Llc Process control for long chain branching control in polyethylene production
US9290589B2 (en) 2013-12-13 2016-03-22 Exxonmobil Chemical Patents Inc. Cyclopentadienyl-substituted salan catalysts
US9382361B2 (en) 2014-03-21 2016-07-05 Exxonmobil Chemical Patents Inc. Process to produce ethylene propylene copolymers
CN106132924B (en) 2014-03-31 2019-03-19 埃克森美孚化学专利公司 Phenylene Bridged SALALEN Catalyst
WO2015158790A2 (en) * 2014-04-17 2015-10-22 Borealis Ag Improved catalyst system for producing polyethylene copolymers in a high temperature solution polymerization process
EP3161021B1 (en) * 2014-06-30 2019-11-20 Dow Global Technologies LLC Process for olefin polymerization
ES2949011T3 (en) * 2014-06-30 2023-09-25 Dow Global Technologies Llc Catalyst systems for olefin polymerization
WO2016089935A1 (en) * 2014-12-04 2016-06-09 Dow Global Technologies Llc Five-coordinate bis-phenylphenoxy catalysts for the preparation of ethylene-based polymers
CN107108804B (en) * 2014-12-31 2020-07-24 陶氏环球技术有限责任公司 Polyolefin composition and process for producing the same
CN107428878B (en) * 2015-03-31 2020-08-28 陶氏环球技术有限责任公司 Process for preparing high molecular weight ethylene/alpha-olefin/non-conjugated interpolymers with low levels of long chain branching
KR102617008B1 (en) * 2015-06-17 2023-12-26 다우 글로벌 테크놀로지스 엘엘씨 Process for producing crosslinked cable insulation using high melt strength ethylene-based polymers prepared in a tubular reactor and optionally modified with a branching agent.
US10800865B2 (en) 2015-09-14 2020-10-13 Exxonmobil Chemical Patents Inc. Process for making branched EPDM and the EPDM therefrom
WO2017058910A1 (en) 2015-09-30 2017-04-06 Dow Global Technologies Llc Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same
CN108137738B (en) 2015-09-30 2020-11-06 陶氏环球技术有限责任公司 Process for preparing functional polymers by addition of amino groups and polymer groups to aldehyde moieties
AU2016383056B2 (en) 2015-12-29 2020-11-19 Dow Global Technologies Llc Highly grafted ethylene-based polymers, highly grafted ethylene-based polymer compositions, and processes for forming the same
EP3214115B1 (en) 2016-03-03 2018-10-03 Dow Global Technologies LLC Polyethylene composition, method of making the same, and films made therefrom
BR112018077058A2 (en) 2016-07-21 2019-04-02 Dow Global Technologies Llc composite padding structures and manufacturing methods thereof
SG11201900653RA (en) 2016-07-29 2019-02-27 Dow Global Technologies Llc Silyl-bridged bis-biphenyl-phenoxy catalysts for olefin polymerization
BR112019001249B1 (en) 2016-07-29 2022-10-18 Dow Global Technologies Llc MULTIMODAL ELASTOMER, THERMOPLATIC OLEFIN AND METHOD TO PRODUCE A MULTIMODAL ELASTOMER
JP7157049B2 (en) 2016-09-29 2022-10-19 ダウ グローバル テクノロジーズ エルエルシー Magnesium halide-supported titanium (precursor) catalyst
TWI756272B (en) 2016-09-30 2022-03-01 美商陶氏全球科技有限責任公司 Capped multi- or dual-headed compositions useful for chain shuttling and process to prepare the same
KR102444560B1 (en) 2016-09-30 2022-09-20 다우 글로벌 테크놀로지스 엘엘씨 Multi- or dual-head components useful for chain shuttling and the process of preparing them
JP7123040B2 (en) 2016-09-30 2022-08-22 ダウ グローバル テクノロジーズ エルエルシー Method for preparing multi-headed or double-headed compositions useful for chain shuttling
US10280234B2 (en) 2016-11-11 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst compositions and use thereof
WO2018089165A1 (en) * 2016-11-11 2018-05-17 Exxonmobil Chemical Patents Inc. Catalyst compositions and use thereof
TW201829574A (en) 2016-11-16 2018-08-16 美商陶氏全球科技有限責任公司 Tie layer compositions and multilayer films incorporating same
EP3589665B1 (en) 2017-02-28 2023-09-13 Dow Global Technologies LLC Phosphoramidate catalysts for ethylene-based interpolymers
SG11201908518VA (en) 2017-03-15 2019-10-30 Dow Global Technologies Llc Catalyst system for multi-block copolymer formation
JP7028885B2 (en) 2017-03-15 2022-03-02 ダウ グローバル テクノロジーズ エルエルシー Catalyst system for forming multi-block copolymers
SG11201908414YA (en) 2017-03-15 2019-10-30 Dow Global Technologies Llc Catalyst system for multi-block copolymer formation
US11208502B2 (en) 2017-03-15 2021-12-28 Dow Global Technologies Llc Catalyst system for multi-block coploymer formation
EP3596146B1 (en) 2017-03-15 2023-07-19 Dow Global Technologies LLC Catalyst system for multi-block copolymer formation
JP2018162231A (en) * 2017-03-27 2018-10-18 三井化学株式会社 Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer
EP3409697A1 (en) 2017-05-28 2018-12-05 SABIC Global Technologies B.V. Preparation of polymer dispersions
US10995166B2 (en) 2017-11-07 2021-05-04 Nova Chemicals (International) S.A. Ethylene interpolymer products and films
US10683376B2 (en) 2017-11-07 2020-06-16 Nova Chemicals (International) S.A. Manufacturing ethylene interpolymer products at higher production rate
EP3732215B8 (en) 2017-12-26 2022-04-27 Dow Global Technologies LLC Dual reactor solution process for the production of multimodal ethylene-based polymer
JP7278286B2 (en) 2017-12-26 2023-05-19 ダウ グローバル テクノロジーズ エルエルシー Multimodal ethylene-based polymer composition with improved toughness
BR112020012842B1 (en) 2017-12-26 2024-01-02 Dow Global Technologies Llc METHOD FOR PRODUCING A TRIMODAL POLYMER IN A SOLUTION POLYMERIZATION PROCESS
KR102647144B1 (en) 2017-12-26 2024-03-15 다우 글로벌 테크놀로지스 엘엘씨 Composition comprising multimodal ethylene-based polymer and low-density polyethylene (LDPE)
ES2946586T3 (en) 2017-12-26 2023-07-21 Dow Global Technologies Llc Procedure for the production of multimodal ethylene-based polymers
EP3732214B1 (en) 2017-12-26 2023-11-01 Dow Global Technologies LLC Compositions with multimodal ethylene-based polymers having improved toughness at low temperatures
SG11202005532YA (en) 2017-12-29 2020-07-29 Dow Global Technologies Llc Capped dual-headed organoaluminum compositions
CN111448200A (en) 2017-12-29 2020-07-24 陶氏环球技术有限责任公司 Dual head organoaluminum compositions
US20190248934A1 (en) 2018-02-09 2019-08-15 Exxonmobil Chemical Patents Inc. Ethylene-a-olefin-diene Elastomers and Methods of Making Them
KR20200133354A (en) 2018-03-19 2020-11-27 다우 글로벌 테크놀로지스 엘엘씨 Silicon-terminated organo-metal compound and preparation method thereof
KR102742384B1 (en) 2018-03-19 2024-12-16 다우 글로벌 테크놀로지스 엘엘씨 Hot melt adhesive composition containing polyolefin-polydiorganosiloxane copolymer, method for producing same, and use thereof
SG11202008429TA (en) 2018-03-19 2020-10-29 Dow Global Technologies Llc Process for functionalization of organo-zinc compounds with halosilanes using basic nitrogen containing heterocycles and silyl-functionalized compounds prepared thereby
CA3093558A1 (en) 2018-03-19 2019-09-26 Dow Silicones Corporation Polyorganosiloxane hot melt adhesive compositions containing polyolefin - polydiorganoosiloxane copolymers and methods for the preparation and use thereof
KR102693602B1 (en) 2018-03-19 2024-08-12 다우 실리콘즈 코포레이션 Polyolefin-polydiorganosiloxane block copolymer and hydrosilylation reaction method for its synthesis
BR112020019180A2 (en) 2018-03-19 2021-01-05 Dow Global Technologies Llc ORGANOMETAL COMPOUNDS FINISHED IN SILICON AND PROCESSES TO PREPARE THE SAME
TW201938602A (en) 2018-03-19 2019-10-01 美商陶氏全球科技有限責任公司 Silicon-terminated telechelic polyolefin compositions and processes for preparing the same
US20210002467A1 (en) 2018-03-19 2021-01-07 Dow Global Technologies Llc Process for functionalization of organo-metal compounds with silyl-based functionalization agents and silyl-functionalized compounds prepared thereby
KR102724168B1 (en) 2018-03-19 2024-11-01 다우 글로벌 테크놀로지스 엘엘씨 Polyolefin-polydiorganosiloxane block copolymer and method for synthesizing the same
WO2019183871A1 (en) 2018-03-29 2019-10-03 Dow Global Technologies Llc Resins for use as tie layer in multilayer structure and multilayer structures comprising the same
WO2019231916A1 (en) 2018-05-31 2019-12-05 E. I. Du Pont De Nemours And Company Molded articles, and methods thereof
US11873377B2 (en) 2018-06-15 2024-01-16 Dow Global Technologies Llc Blown films comprising bimodal ethylene-based polymers having high molecular weight high density fractions
ES3035268T3 (en) 2018-06-15 2025-09-01 Dow Global Technologies Llc Process for the production of bimodal ethylene-based polymers having high molecular weight high density fractions
CN112469742B (en) 2018-06-15 2023-10-20 陶氏环球技术有限责任公司 Bimodal ethylene-based polymers with high molecular weight high density fraction
MX2020013370A (en) 2018-06-15 2021-03-09 Dow Global Technologies Llc CAST FILMS COMPRISING ETHYLENE-BASED BIMODAL POLYMERS HAVING HIGH DENSITY AND HIGH MOLECULAR WEIGHT FRACTIONS.
CN112334515B (en) 2018-07-17 2022-08-09 美国陶氏有机硅公司 Polysiloxane resin-polyolefin copolymers and methods of making and using the same
TWI839414B (en) 2018-11-30 2024-04-21 美商陶氏全球科技有限責任公司 Polymer-based film with balanced properties
US12098160B2 (en) 2018-12-28 2024-09-24 Dow Global Technologies Llc Organometallic chain transfer agents
EP3902867A4 (en) 2018-12-28 2022-09-14 Dow Global Technologies LLC Curable compositions comprising unsaturated polyolefins
SG11202107057WA (en) 2018-12-28 2021-07-29 Dow Global Technologies Llc Curable compositions comprising unsaturated polyolefins
US12590174B2 (en) 2018-12-28 2026-03-31 Dow Global Technologies Llc Curable compositions comprising telechelic polyolefins
CN113454130B (en) 2018-12-28 2024-12-13 陶氏环球技术有限责任公司 Telechelic polyolefins and methods for preparing telechelic polyolefins
US12202920B2 (en) 2019-01-08 2025-01-21 ExxonMobil Engineering & Technology Company Olefin polymerization processes featuring in situ blending of an oil extension
US11028805B2 (en) 2019-01-09 2021-06-08 Saudi Arabian Oil Company System and method for on-board catalytic upgrading of hydrocarbon fuels
KR101995951B1 (en) * 2019-03-12 2019-07-03 주식회사 라이온켐텍 A continuous method for manufacturing polyolefin copolymer
SG11202110448UA (en) 2019-03-28 2021-10-28 Dow Global Technologies Llc Anionic group iii complexes as weakly coordinating anions for olefin polymerization catalyst activators
WO2020223488A1 (en) 2019-04-30 2020-11-05 Dow Global Technologies Llc Alkene functionalized activators
US11866530B2 (en) 2019-04-30 2024-01-09 Dow Global Technologies Llc Ethylene/propylene/nonconjugated diene interpolymer composition
CN113874439B (en) 2019-04-30 2024-03-29 陶氏环球技术有限责任公司 Ethylene/propylene/non-conjugated diene interpolymer compositions
US11945888B2 (en) 2019-05-15 2024-04-02 Exxonmobil Chemical Patents Inc. Solution polymerization process and product control using effluent density
CN114127158B (en) 2019-06-26 2025-02-07 陶氏环球技术有限责任公司 Controlling long-chain branching in EPDM via post-reactor modification
CN114127175A (en) 2019-06-26 2022-03-01 陶氏环球技术有限责任公司 EPDM blends with long chain branching
EP3763745A1 (en) 2019-07-10 2021-01-13 Borealis AG High temperature solution process for the copolymerization of alpha-olefins
ES2967889T3 (en) * 2019-10-01 2024-05-06 Nova Chem Int Sa High Productivity Polymerization with Aryloxy Ether Ligand Catalyst
KR20220097897A (en) * 2019-11-04 2022-07-08 다우 글로벌 테크놀로지스 엘엘씨 Titanium Biphenylphenol Polymerization Catalyst
KR20220120654A (en) 2019-12-30 2022-08-30 다우 글로벌 테크놀로지스 엘엘씨 Method for making alpha-substituted acrylates
EP4085042B1 (en) 2019-12-30 2025-09-03 Dow Global Technologies LLC Process for preparing an alpha-substituted acrylate
JP2021147420A (en) * 2020-03-16 2021-09-27 三井化学株式会社 Method for producing olefin-cyclic olefin copolymer
JP7777079B2 (en) 2020-03-27 2025-11-27 ダウ グローバル テクノロジーズ エルエルシー Long-chain branched ethylene polymer
WO2021195505A1 (en) 2020-03-27 2021-09-30 Dow Global Technologies Llc Long-chain branched ethylene-based polymers
CN115397875B (en) 2020-03-27 2025-03-11 陶氏环球技术有限责任公司 Process for producing long chain branched ethylene-based polymers
CN115298234B (en) 2020-03-27 2024-10-18 陶氏环球技术有限责任公司 Long chain branched ethylene-based polymers
JP7714576B2 (en) 2020-04-29 2025-07-29 ダウ グローバル テクノロジーズ エルエルシー High flow propylene-based interpolymer composition
CN111662403B (en) * 2020-07-14 2022-08-05 万华化学集团股份有限公司 Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same
CN111909196B (en) * 2020-08-10 2023-05-26 万华化学集团股份有限公司 IVB-group-containing bimetallic complex catalyst, and preparation method and application thereof
WO2022073805A1 (en) 2020-10-05 2022-04-14 Borealis Ag High temperature solution process for the copolymerization of ethylene with one ore more α-Olefin comonomer(s)
US20230399450A1 (en) 2020-11-10 2023-12-14 Dow Global Technologies Llc Preparation of non-polar-polar block copolymers via vinyl-terminated polyolefins
WO2022103800A1 (en) 2020-11-10 2022-05-19 Dow Global Technologies Llc Preparation of polyolefin-polyacrylate block copolymers additives for increasing surface energy of polyethylene
CN116438211B (en) * 2020-11-23 2026-04-07 Sabic环球技术有限责任公司 Solution method for producing halogenated or tertiary amine-functionalized polyolefins
KR20230110318A (en) 2020-11-24 2023-07-21 다우 글로벌 테크놀로지스 엘엘씨 Process for creating long chain branches in EPDM and products
US20230303597A1 (en) * 2020-12-28 2023-09-28 Sabic Sk Nexlene Company Pte. Ltd. Metal-ligand complex, catalyst composition for preparing ethylene-based polymer containing the same, and preparation method of ethylene -based polymer using the same
JP2024506482A (en) * 2021-01-25 2024-02-14 ダウ グローバル テクノロジーズ エルエルシー Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes
CN116897168A (en) * 2021-02-26 2023-10-17 陶氏环球技术有限责任公司 Bis-phenoxy-ether ligands for Group IV polyolefin catalysis
EP4382568A4 (en) 2021-08-04 2025-07-09 China Petroleum & Chem Corp Flexible polypropylene-modified insulation material, manufacturing process therefor and application thereof
EP4512834A3 (en) 2021-09-10 2025-05-14 Dow Global Technologies LLC Borate cocatalysts for polyolefin production
EP4399231A1 (en) 2021-09-10 2024-07-17 Dow Global Technologies LLC Hydrocarbon soluble borate cocatalysts for olefin polymerization
EP4424722A4 (en) 2021-10-26 2025-11-12 China Petroleum & Chem Corp METHOD FOR PROMOTING PHASE SEPARATION OF A POLYMER SOLUTION AND METHOD FOR PRODUCING AN OLEFIN POLYMER
CN114957530B (en) * 2022-06-28 2023-09-29 杭州双安科技有限公司 A solution polymerization method of ethylene and α-olefins
CN115160472B (en) * 2022-08-09 2023-07-11 万华化学集团股份有限公司 High insertion rate ethylene copolymer solution polymerization method
EP4688882A1 (en) * 2023-03-28 2026-02-11 Dow Global Technologies Llc Process for producing branched polyolefin
CN121693523A (en) 2023-08-28 2026-03-17 陶氏环球技术有限责任公司 Polymer blends comprising post-consumer recycle (PCR) ethylene-based polymers
WO2025072678A1 (en) 2023-09-29 2025-04-03 Dow Global Technologies Llc Process for preparing an olefin-acrylate block copolymer
CN117343226B (en) 2023-12-04 2024-04-09 万华化学集团股份有限公司 Ethylene/α-olefin copolymer and its application
CN119798506A (en) * 2025-01-02 2025-04-11 万华化学集团股份有限公司 Olefin polymer and preparation method thereof

Family Cites Families (155)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485706A (en) * 1968-01-18 1969-12-23 Du Pont Textile-like patterned nonwoven fabrics and their production
US3914342A (en) * 1971-07-13 1975-10-21 Dow Chemical Co Ethylene polymer blend and polymerization process for preparation thereof
US3953413A (en) * 1974-06-13 1976-04-27 Chemplex Company Supported chromium-containing catalyst and process of polymerizing 1-olefins
US4173548A (en) 1977-02-02 1979-11-06 Chemplex Company Ethylene polymerization catalyst and method
US4330646A (en) 1979-08-13 1982-05-18 Asahi Kasei Kogyo Kabushiki Kaisha Polymerization of an α-olefin
US4322027A (en) * 1980-10-02 1982-03-30 Crown Zellerbach Corporation Filament draw nozzle
US4413110A (en) * 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
US4543399A (en) 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
DZ520A1 (en) 1982-03-24 2004-09-13 Union Carbide Corp Improved process for increasing the space-time yield of an exothermic polymerization reaction in a fluidized bed.
US4430563A (en) * 1982-04-30 1984-02-07 Minnesota Mining And Manufacturing Company Data processing form
US4564660A (en) 1983-06-30 1986-01-14 Union Carbide Corporation Use of alkylaluminum compounds and hydroxyl-containing compounds to initiate polymerization of ethylene with chromium oxide catalysts
US4612300A (en) * 1985-06-06 1986-09-16 The Dow Chemical Company Novel catalyst for producing relatively narrow molecular weight distribution olefin polymers
US4665208A (en) 1985-07-11 1987-05-12 Exxon Chemical Patents Inc. Process for the preparation of alumoxanes
US4663220A (en) 1985-07-30 1987-05-05 Kimberly-Clark Corporation Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers
US4668566A (en) * 1985-10-07 1987-05-26 Kimberly-Clark Corporation Multilayer nonwoven fabric made with poly-propylene and polyethylene
EP0812862B1 (en) 1986-09-24 2002-11-13 Mitsui Chemicals, Inc. Process for polymerizing olefins
JPH0780933B2 (en) 1986-11-20 1995-08-30 三井石油化学工業株式会社 Olefin Polymerization Method
JPS63154753A (en) 1986-12-18 1988-06-28 Nippon Oil Co Ltd Polyethylene composition
US5241025A (en) * 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
IL85097A (en) 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
US5384299A (en) 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
PL276385A1 (en) 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
JPH0742301B2 (en) 1987-02-14 1995-05-10 三井石油化学工業株式会社 Particulate aluminoxane, its manufacturing method and its use
JP2538588B2 (en) 1987-04-03 1996-09-25 三井石油化学工業株式会社 Method for producing solid catalyst for olefin polymerization
US5206199A (en) 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
US4981927A (en) 1987-05-20 1991-01-01 National Distillers And Chemical Corporation Chromium catalyst compositions and polymerization utilizing same
FR2634212B1 (en) * 1988-07-15 1991-04-19 Bp Chimie Sa APPARATUS AND METHOD FOR POLYMERIZATION OF GASEOUS OLEFINS IN A FLUIDIZED BED REACTOR
US5091352A (en) 1988-09-14 1992-02-25 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins
US4908463A (en) * 1988-12-05 1990-03-13 Ethyl Corporation Aluminoxane process
US5103031A (en) 1989-02-21 1992-04-07 Ethyl Corporation Falling film aluminoxane process
US4968827A (en) * 1989-06-06 1990-11-06 Ethyl Corporation Alkylaluminoxane process
US4924018A (en) 1989-06-26 1990-05-08 Ethyl Corporation Alkylaluminoxane process
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5066741A (en) 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
US5763549A (en) 1989-10-10 1998-06-09 Fina Technology, Inc. Cationic metallocene catalysts based on organoaluminum anions
ATE120768T1 (en) 1989-10-30 1995-04-15 Fina Technology PRODUCTION OF METALLOCE CATALYSTS FOR OLEFIN POLYMERIZATION.
US5387568A (en) 1989-10-30 1995-02-07 Fina Technology, Inc. Preparation of metallocene catalysts for polymerization of olefins
FR2656314B1 (en) * 1989-12-22 1992-04-17 Bp Chemicals Snc ZIRCONIUM CATALYST SUPPORTED ON MAGNESIUM CHLORIDE, PROCESS FOR THE PREPARATION AND USE OF THE CATALYST IN OLEFIN POLYMERIZATION.
US5032562A (en) 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
JP2545006B2 (en) 1990-07-03 1996-10-16 ザ ダウ ケミカル カンパニー Addition polymerization catalyst
JP3115595B2 (en) 1990-07-24 2000-12-11 三井化学株式会社 Polymerization catalyst for α-olefin and method for producing poly-α-olefin using the same
US5189192A (en) 1991-01-16 1993-02-23 The Dow Chemical Company Process for preparing addition polymerization catalysts via metal center oxidation
US5296443A (en) * 1991-03-01 1994-03-22 Dai Nippon Printing Co., Ltd. Thermal transfer image receiving sheet
US5206197A (en) 1991-03-04 1993-04-27 The Dow Chemical Company Catalyst composition for preparation of syndiotactic vinyl aromatic polymers
US5721185A (en) 1991-06-24 1998-02-24 The Dow Chemical Company Homogeneous olefin polymerization catalyst by abstraction with lewis acids
US5308815A (en) 1991-07-26 1994-05-03 Ethyl Corporation Heterogeneous methylaluminoxane catalyst system
US5157137A (en) 1991-07-26 1992-10-20 Ethyl Corporation Method of making gel free alkylaluminoxane solutions
US5235081A (en) * 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
US6448355B1 (en) * 1991-10-15 2002-09-10 The Dow Chemical Company Elastic fibers, fabrics and articles fabricated therefrom
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5525695A (en) * 1991-10-15 1996-06-11 The Dow Chemical Company Elastic linear interpolymers
US5674342A (en) * 1991-10-15 1997-10-07 The Dow Chemical Company High drawdown extrusion composition and process
DE69224287T2 (en) * 1992-01-06 1998-08-27 The Dow Chemical Co., Midland, Mich. Catalyst composition
US5329032A (en) 1992-03-18 1994-07-12 Akzo Chemicals Inc. Polymethylaluminoxane of enhanced solution stability
US5436304A (en) 1992-03-19 1995-07-25 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5352749A (en) 1992-03-19 1994-10-04 Exxon Chemical Patents, Inc. Process for polymerizing monomers in fluidized beds
US5296433A (en) 1992-04-14 1994-03-22 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
US5288933A (en) * 1992-04-16 1994-02-22 Union Carbide Chemicals & Plastics Technology Corporation Process for the production of polyethylene
US5350723A (en) * 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
US5434115A (en) 1992-05-22 1995-07-18 Tosoh Corporation Process for producing olefin polymer
BE1005957A5 (en) 1992-06-05 1994-04-05 Solvay Preparation method of catalyst system, process (co) polymerization of olefins and (co) polymer at least one olefine.
ES2137266T3 (en) 1992-07-01 1999-12-16 Exxon Chemical Patents Inc OLEPHINE POLYMERIZATION CATALYSTS BASED ON TRANSITIONAL METALS.
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
RU95110681A (en) 1992-09-29 1997-01-10 Эксон Кемикэл Пейтентс Инк. (US) Long-chain branched polymers and process for preparing long-chain branched polymers
EP0662979B1 (en) 1992-10-02 1997-07-16 The Dow Chemical Company Supported homogeneous catalyst complexes for olefin polymerization
DE4322884A1 (en) * 1992-10-09 1994-04-14 Bayer Ag Biologically active polymers
US5939346A (en) 1992-11-02 1999-08-17 Akzo Nobel N.V. Catalyst system comprising an aryloxyaluminoxane containing an electron withdrawing group
US5391793A (en) 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes
US5420220A (en) * 1993-03-25 1995-05-30 Mobil Oil Corporation LLDPE films
US5332706A (en) 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
US5608019A (en) * 1992-12-28 1997-03-04 Mobil Oil Corporation Temperature control of MW in olefin polymerization using supported metallocene catalyst
US5391529A (en) * 1993-02-01 1995-02-21 Albemarle Corporation Siloxy-aluminoxane compositions, and catalysts which include such compositions with a metallocene
TW298593B (en) 1993-02-12 1997-02-21 Hoechst Ag
US6313240B1 (en) 1993-02-22 2001-11-06 Tosoh Corporation Process for producing ethylene/α-olefin copolymer
KR100311244B1 (en) 1993-02-22 2001-12-15 가지와라 야스시 Process for producing ethylene / α-olefin copolymer
US5462999A (en) * 1993-04-26 1995-10-31 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
JP3077940B2 (en) 1993-04-26 2000-08-21 エクソン・ケミカル・パテンツ・インク A method for determining stable operating conditions for fluidized bed polymerization.
EP0696300B1 (en) * 1993-04-28 1998-12-23 The Dow Chemical Company Fabricated articles made from ethylene polymer blends
BE1007148A3 (en) 1993-05-17 1995-04-11 Solvay Support for catalyst, method for producing gel precursor media for catalyst, method for preparing a catalyst support, catalyst for olefin polymerization and method for olefin polymerization using the catalyst .
FR2705252B1 (en) 1993-05-19 1995-07-21 Bp Chemicals Snc Process for introducing a solid into a reactor and apparatus.
ZA943399B (en) 1993-05-20 1995-11-17 Bp Chem Int Ltd Polymerisation process
BR9407034A (en) 1993-06-24 1996-03-19 Dow Chemical Co Titanium (I) or zirconium (II) complexes and polymerization catalysts by adding them
US5372682A (en) 1993-06-24 1994-12-13 The Dow Chemical Company Electrochemical preparation of addition polymerization catalysts
EP0729477B1 (en) 1993-11-19 1999-10-27 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
JPH07144455A (en) * 1993-11-25 1995-06-06 Canon Inc Inkjet recording device
US5672669A (en) 1993-12-23 1997-09-30 Union Carbide Chemicals & Plastics Technology Corporation Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture
US5648310A (en) 1993-12-23 1997-07-15 Union Carbide Chemicals & Plastics Technology Corporation Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture
US5461123A (en) * 1994-07-14 1995-10-24 Union Carbide Chemicals & Plastics Technology Corporation Gas phase fluidized bed polyolefin polymerization process using sound waves
US5453471B1 (en) 1994-08-02 1999-02-09 Carbide Chemicals & Plastics T Gas phase polymerization process
US5625087A (en) 1994-09-12 1997-04-29 The Dow Chemical Company Silylium cationic polymerization activators for metallocene complexes
DE4436392C2 (en) * 1994-10-12 2002-10-31 Fraunhofer Ges Forschung Metal niobates and / or tantalates, processes for their preparation and their further processing into perovskites
US5616661A (en) 1995-03-31 1997-04-01 Union Carbide Chemicals & Plastics Technology Corporation Process for controlling particle growth during production of sticky polymers
UA47394C2 (en) 1995-05-16 2002-07-15 Юнівейшн Текнолоджіз, Ллс Ethylene polymer with improved processability and an article containing the ethylene polymer
JP3281389B2 (en) 1995-06-08 2002-05-13 昭和電工株式会社 Ionic compounds and catalysts for olefin polymerization using the compounds
US5731253A (en) 1995-07-27 1998-03-24 Albemarle Corporation Hydrocarbylsilloxy - aluminoxane compositions
US5869575A (en) 1995-08-02 1999-02-09 The Dow Chemical Company Ethylene interpolymerizations
US5767208A (en) 1995-10-20 1998-06-16 Exxon Chemical Patents Inc. High temperature olefin polymerization process
US5693838A (en) 1995-11-13 1997-12-02 Albemarle Corporation Aluminoxane process and product
US5814714A (en) * 1995-11-30 1998-09-29 The Dow Chemical Company Mono-olefin/polyene interpolymers, method of preparation, compositions containing the same, and articles made thereof
DE69720823T2 (en) 1996-01-25 2004-01-22 Tosoh Corp., Shinnanyo Process for olefin polymerization using a transition metal catalyst.
ES2161444T3 (en) * 1996-03-05 2001-12-01 Dow Chemical Co POLYOLEFINS WITH MODIFIED REOLOGY.
RU2178422C2 (en) 1996-03-27 2002-01-20 Дзе Дау Кемикал Компани Olefin polymerization catalyst activator, catalytic system, and polymerization process
JP2000517349A (en) 1996-03-27 2000-12-26 ザ ダウ ケミカル カンパニー Solution polymerization with dispersed catalytic activators.
US5977251A (en) * 1996-04-01 1999-11-02 The Dow Chemical Company Non-adiabatic olefin solution polymerization
US5731451A (en) 1996-07-12 1998-03-24 Akzo Nobel Nv Modified polyalkylauminoxane composition formed using reagent containing aluminum trialkyl siloxide
US5854166A (en) 1996-08-19 1998-12-29 Northwestern University Synthesis and use of (perfluoroaryl) fluoro-aluminate anion
WO1998009996A1 (en) 1996-09-06 1998-03-12 Hyundai Petrochemical Co., Ltd. Catalyst system for (co)polymerization of olefins and process for the preparation of olefin (co)polymers using the catalyst system
US5744656A (en) * 1996-10-25 1998-04-28 Boulder Scientific Company Conversion of hexafluorobenzene to bromopentafluorobenzene
US5783512A (en) 1996-12-18 1998-07-21 The Dow Chemical Company Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same
FI970349A7 (en) 1997-01-28 1998-07-29 Borealis As New activator systems for metallocene compounds
EP0975641A4 (en) 1997-04-03 2003-03-12 Univ Colorado State Res Found COMPOSITIONS WITH POLYHALOGENATED MONOHETEROBORANE ANIONS
US6420507B1 (en) * 1997-05-01 2002-07-16 The Dow Chemical Company Olefin polymers prepared with substituted indenyl containing metal complexes
US6103657A (en) 1997-07-02 2000-08-15 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
US6319989B1 (en) 1997-07-21 2001-11-20 The Dow Chemical Company Broad MWD, compositionally uniform ethylene interpolymer compositions, process for making the same and article made therefrom
EP1019415A1 (en) 1997-09-19 2000-07-19 The Dow Chemical Company Modified alumoxane catalyst activator
US6696379B1 (en) 1997-09-19 2004-02-24 The Dow Chemical Company Supported modified alumoxane catalyst activator
AR012518A1 (en) 1997-09-19 2000-10-18 Dow Global Technologies Inc COMPOSITION OF POLYMERS THAT INCLUDES ETHYLENE INTERPOLYMERIZED WITH AT LEAST ONE UNSATURATED COMONOMER, PROCESS TO PREPARE IT AND MANUFACTURED ARTICLE THAT INCLUDES IT
DE19744102A1 (en) 1997-10-06 1999-04-15 Targor Gmbh Metallocene catalyst system useful in (co)polyolefin production
ATE243700T1 (en) 1998-02-20 2003-07-15 Dow Global Technologies Inc CATALYST ACTIVATORS CONTAINING EXPANDED ANIONS
US6262202B1 (en) 1998-03-04 2001-07-17 Univation Technologies, Llc Noncoordinating anions for olefin polymerization
US6827976B2 (en) 1998-04-29 2004-12-07 Unaxis Trading Ag Method to increase wear resistance of a tool or other machine component
ATE217318T1 (en) 1998-08-11 2002-05-15 Dow Chemical Co ANSA BIS(.MU.-ALUMINUM)-SUBSTITUTED GROUP-4 METAL COMPLEXES
DE69902548T2 (en) 1998-08-11 2003-04-10 The Dow Chemical Co., Midland catalyst activator
ES2233109T3 (en) * 1998-10-23 2005-06-01 Exxonmobil Chemical Patents Inc. METALOCENE BRIDGES FOR COPOLYMERIZATION OF OLEFINS.
JP2000129045A (en) * 1998-10-27 2000-05-09 Asahi Chem Ind Co Ltd Clean vessel made of polyethylene
DE69943133D1 (en) * 1998-11-02 2011-02-24 Dow Global Technologies Inc COATABLE ETHYLENE / ALPHA-OLEFIN / DIEN POLYMERS AND THEIR PREPARATION
US6500135B2 (en) * 1998-12-31 2002-12-31 Homedics, Inc. Percussive massager
CN1334817A (en) 1999-02-19 2002-02-06 陶氏化学公司 Process for preparing trifluoroarylaluminum etherates
US6420298B1 (en) * 1999-08-31 2002-07-16 Exxonmobil Oil Corporation Metallocene catalyst compositions, processes for making polyolefin resins using such catalyst compositions, and products produced thereby
JP2001098028A (en) * 1999-09-29 2001-04-10 Japan Polychem Corp Polyethylene resin for medical and medical container
US6750302B1 (en) * 1999-12-16 2004-06-15 Phillips Petroleum Company Organometal catalyst compositions
US6686490B1 (en) * 2000-11-06 2004-02-03 Ramot University Authority For Applied Research & Industrial Development Ltd. Active non-metallocene pre-catalyst and method for tactic catalytic polymerization of alpha-olefin monomers
EP1334139A2 (en) 2000-11-07 2003-08-13 Symyx Technologies, Inc. Substituted pyridyl amine ligands, complexes and catalysts therefrom. processes for producing polyolefins therewith
AU1790702A (en) * 2000-12-04 2002-06-18 Univaton Technologies Llc Polimerization process
JP3549868B2 (en) * 2001-02-08 2004-08-04 三井化学株式会社 Ethylene polymer, method for producing the same, and molded article using the same
MY137183A (en) 2001-03-16 2009-01-30 Dow Global Technologies Inc Method of making interpolymers and products made therefrom
WO2003010171A1 (en) 2001-07-23 2003-02-06 Dow Global Technologies, Inc. Salt of lewis acid/acid adducts and catalyst activators therefrom
US6960635B2 (en) 2001-11-06 2005-11-01 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
US6908972B2 (en) * 2002-04-16 2005-06-21 Equistar Chemicals, Lp Method for making polyolefins
US6897276B2 (en) * 2002-04-24 2005-05-24 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US6756455B2 (en) 2002-05-31 2004-06-29 Equistar Chemicals, Lp High-temperature solution process for polyolefin manufacture
US6794908B2 (en) 2002-05-31 2004-09-21 Honeywell International Inc. Radiation-hard circuit
US6953764B2 (en) 2003-05-02 2005-10-11 Dow Global Technologies Inc. High activity olefin polymerization catalyst and process
NZ549262A (en) * 2004-03-17 2010-08-27 Dow Global Technologies Inc Catalyst composition comprising shuttling agent for higher olefin multi-block copolymer formation
JP5255833B2 (en) 2004-03-24 2013-08-07 エクソンモービル・ケミカル・パテンツ・インク Method for producing ethylene interpolymer, interpolymer produced by the method, composition, and electrical device comprising the interpolymer
US20050288461A1 (en) 2004-06-25 2005-12-29 Jensen Michael D Polymerization catalysts for producing polymers with low levels of long chain branching
WO2006020624A1 (en) 2004-08-09 2006-02-23 Dow Global Technologies Inc. Supported bis(hydroxyarylaryloxy) catalysts for manufacture of polymers
CA2479704C (en) * 2004-08-31 2013-08-13 Nova Chemicals Corporation High density homopolymer blends
WO2006052427A1 (en) * 2004-11-05 2006-05-18 Dow Global Technologies Inc. Highly soluble ferrocenyl compounds
KR100639696B1 (en) * 2005-07-01 2006-10-30 에스케이 주식회사 Arylphenoxy Catalyst System for Making Ethylene Homopolymer or Copolymer with α-olefin
ES2534469T3 (en) * 2006-05-17 2015-04-23 Dow Global Technologies Llc Polymerization process of polyethylene in high temperature solution

Cited By (115)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010079906A3 (en) * 2009-01-06 2010-08-26 에스케이에너지 주식회사 Ethylene-propylene-diene copolymer production method
US8222361B2 (en) 2009-01-06 2012-07-17 Sk Innovation Co., Ltd. Ethylene-propylene-diene copolymer production method
WO2011025784A1 (en) 2009-08-31 2011-03-03 Dow Global Technologies Inc. Catalyst and process for polymerizing an olefin and polyolefin prepared thereby
WO2011066469A1 (en) 2009-11-24 2011-06-03 Dow Global Technologies Inc. Extrusion coating composition
US8679639B2 (en) 2009-11-24 2014-03-25 Dow Global Technologies Llc Extrusion coating composition
US8784996B2 (en) 2009-11-24 2014-07-22 Dow Global Technologies Llc Extrusion coating composition
WO2011079207A1 (en) 2009-12-24 2011-06-30 Dow Global Technologies Llc Polymer compositions, methods of making the same, and articles prepared from the same
EP2523983B1 (en) * 2010-01-14 2018-03-21 ExxonMobil Chemical Patents Inc. Processes and apparatus for continuous solution polymerization
JP2013521382A (en) * 2010-03-02 2013-06-10 ダウ グローバル テクノロジーズ エルエルシー Ethylene polymer composition
WO2011146291A1 (en) 2010-05-17 2011-11-24 Dow Global Technologies Llc Process for selectively polymerizing ethylene and catalyst therefor
US8609794B2 (en) 2010-05-17 2013-12-17 Dow Global Technologies, Llc. Process for selectively polymerizing ethylene and catalyst therefor
JP2013528689A (en) * 2010-06-14 2013-07-11 ダウ グローバル テクノロジーズ エルエルシー Ethylene-based polymer composition for use as a blend component in shrink film applications
WO2012064630A2 (en) 2010-11-08 2012-05-18 Dow Global Technologies Llc Solution polymerization process and procatalyst carrier systems useful therein
US9045628B2 (en) 2010-12-03 2015-06-02 Dow Global Technologies Llc Processes to prepare ethylene-based polymer compositions
WO2012074812A1 (en) 2010-12-03 2012-06-07 Dow Global Technologies Llc Processes to prepare ethylene-based polymer compositions
EP2813545A1 (en) 2010-12-03 2014-12-17 Dow Global Technologies LLC Processes to prepare ethylene-based polymer compositions
US20130253126A1 (en) * 2010-12-03 2013-09-26 Dow Global Technologies Llc Processes to prepare ethylene-based polymer compositions
EP3091038B1 (en) 2010-12-21 2019-09-18 Dow Global Technologies LLC Olefin-based polymers and dispersion polymerizations
CN103391948B (en) * 2010-12-21 2016-04-13 陶氏环球技术有限责任公司 Based on polymerization process and the Raman analysis of the polymkeric substance of alkene
WO2012088217A1 (en) 2010-12-21 2012-06-28 Dow Global Technologies Llc Polymerization process and raman analysis for olefin-based polymers
CN103391948A (en) * 2010-12-21 2013-11-13 陶氏环球技术有限责任公司 Polymerization process and Raman analysis for olefin-based polymers
EP3091038A1 (en) 2010-12-21 2016-11-09 Dow Global Technologies LLC Olefin-based polymers and dispersion polymerizations
WO2012088235A2 (en) 2010-12-21 2012-06-28 Dow Global Technologies Llc Olefin-based polymers and dispersion polymerizations
WO2012092491A2 (en) 2010-12-30 2012-07-05 Dow Global Technologies Llc Compositions, methods of making the same, and articles prepared from the same
WO2013039739A1 (en) 2011-09-07 2013-03-21 Dow Global Technologies Llc Polymer compositions and articles prepared from the same
US9133327B2 (en) 2011-09-12 2015-09-15 Dow Global Technologies Llc Compositions and articles formed from the same
WO2013039850A1 (en) 2011-09-12 2013-03-21 Dow Global Technologies Llc Compositions and articles formed from the same
WO2013043796A3 (en) * 2011-09-23 2013-07-04 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
US11180644B2 (en) 2011-09-23 2021-11-23 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions with enhanced melt strength
US9580533B2 (en) 2011-09-23 2017-02-28 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
WO2013055642A1 (en) 2011-10-10 2013-04-18 Dow Global Technologies Llc Polymer compositions with improved retention of properties under mechanical and thermal stresses
WO2013059391A1 (en) 2011-10-20 2013-04-25 Dow Global Technologies Llc Ethylene-based polymer compositions and articles prepared therefrom
WO2013096418A1 (en) 2011-12-19 2013-06-27 Dow Global Technologies Llc Ethylene-based polymers prepared by dispersion polymerization
US9422383B2 (en) * 2011-12-20 2016-08-23 Dow Global Technologies Llc Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same
WO2013096573A1 (en) 2011-12-20 2013-06-27 Dow Global Technologies Llc Ethylene/alpha-olefin/nonconjugated polyene interpolymers and processes to form the same
US10836853B2 (en) 2012-09-20 2020-11-17 Exxonmobil Chemical Patents Inc. Crack-resistant polyethylene compositions
US10822479B2 (en) 2012-09-20 2020-11-03 Exxonmobil Chemical Patents Inc. Foamed polyethylene compositions
US10160819B2 (en) 2012-11-30 2018-12-25 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene based compositions
WO2014084893A1 (en) 2012-11-30 2014-06-05 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene based compositions
US10214622B2 (en) 2012-12-27 2019-02-26 Dow Global Technologies Llc Catalyst systems for olefin polymerization
US10214602B2 (en) 2012-12-27 2019-02-26 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US10059787B2 (en) 2012-12-27 2018-08-28 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US9534070B2 (en) 2013-01-18 2017-01-03 Dow Global Technologies Llc Polymerization processes for high molecular weight polymers
WO2014113046A1 (en) 2013-01-18 2014-07-24 Dow Global Technologies Llc Polymerization processes for high molecular weight polyolefins
US10144791B2 (en) 2013-06-28 2018-12-04 Dow Global Technologies Llc Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts
EP3925989A1 (en) 2013-06-28 2021-12-22 Dow Global Technologies LLC Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts
US9605098B2 (en) 2013-06-28 2017-03-28 Dow Global Technologies Llc Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts
CN104628920A (en) * 2013-11-08 2015-05-20 中国石油天然气股份有限公司 A kind of preparation method of solution polymerization ethylene propylene rubber
WO2015116381A1 (en) * 2014-01-30 2015-08-06 Exxonmobil Chemical Patents Inc. Crack-resistant polyethylene composiitions
WO2015116382A1 (en) * 2014-01-30 2015-08-06 Exxonmobil Chemical Patents Inc. Foamed polyethylene compositions
US9975975B2 (en) 2014-07-24 2018-05-22 Dow Global Technologies Llc Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers
WO2016014749A1 (en) 2014-07-24 2016-01-28 Dow Global Technologies Llc Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers
EP3578578A1 (en) 2014-07-24 2019-12-11 Dow Global Technologies Llc Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers
US10336846B2 (en) 2015-05-28 2019-07-02 Dow Global Technologies Llc Process to form ethylene/α-olefin interpolymers
WO2016209807A1 (en) 2015-06-22 2016-12-29 Dow Global Technologies Llc Process for making ethylene-based polymers using carbon-carbon free radical initiators
CN107735414A (en) * 2015-06-22 2018-02-23 陶氏环球技术有限责任公司 The method that the polymer based on ethene is prepared using carbon carbon radicals initiator
US10647789B2 (en) 2015-06-22 2020-05-12 Dow Global Technologies Llc Process for making ethylene-based polymers using carbon-carbon free radical initiators
US11041027B2 (en) 2015-06-30 2021-06-22 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US10597473B2 (en) 2015-06-30 2020-03-24 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US11155693B2 (en) 2015-09-02 2021-10-26 Dow Global Technologies Llc Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
US10490319B2 (en) 2015-09-02 2019-11-26 Dow Global Technologies Llc Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
US10870713B2 (en) 2015-09-30 2020-12-22 Dow Global Technologies Llc Procatalyst and polymerization process using the same
US10647797B2 (en) 2015-09-30 2020-05-12 Dow Global Technologies Llc Polymerization process for producing ethylene based polymers
US10487200B2 (en) 2015-10-29 2019-11-26 Dow Global Technologies Llc Crosslinkable polymeric compositions for flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation
WO2017210201A1 (en) 2016-05-30 2017-12-07 Dow Global Technologies Llc Ethylene/alpha-olefin/diene interpolymers compositions
WO2017210195A1 (en) 2016-05-30 2017-12-07 Dow Global Technologies Llc Ethylene/alpha-olefin/diene interpolymer
WO2018005852A1 (en) 2016-06-30 2018-01-04 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene based compositions
WO2018005922A1 (en) 2016-06-30 2018-01-04 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same
US11981802B2 (en) 2016-06-30 2024-05-14 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene based compositions
EP4029886A2 (en) 2016-06-30 2022-07-20 Dow Global Technologies LLC Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same
EP3805277A1 (en) 2016-06-30 2021-04-14 Dow Global Technologies LLC Procatalyst compositions useful for low comonomer incorporation and process for preparing the same
WO2018005789A1 (en) 2016-06-30 2018-01-04 Dow Global Technologies Llc Procatalyst compositions useful for low comonomer incorporation and process for preparing the same
WO2018013283A2 (en) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Dual metallocene catalyst copolymer compositions
WO2018013284A2 (en) 2016-07-13 2018-01-18 Exxonmobil Chemical Patents Inc. Dual metallocene catalyst copolymer compositions
WO2018013286A1 (en) 2016-07-14 2018-01-18 Exxonmobil Chemical Patents Inc. Lubricating oil compositions comprising dual metallocene-catalyzed bimodal copolymer compositions useful as viscosity modifiers
WO2018013285A1 (en) 2016-07-14 2018-01-18 Exxonmobil Chemical Patents Inc. Dual metallocene-catalyzed bimodal copolymer compositions
WO2018063898A1 (en) 2016-09-29 2018-04-05 Dow Global Technologies Llc Modified ziegler-natta (pro)catalyst and system
US11091572B2 (en) 2016-09-29 2021-08-17 Dow Global Technologies Llc Modified Ziegler-Natta (pro) catalysts and system
US11649307B2 (en) 2016-09-29 2023-05-16 Dow Global Technologies Llc Modified Ziegler-Natta (pro) catalysts and system
US11649306B2 (en) 2016-09-29 2023-05-16 Dow Global Technologies Llc Modified Ziegler-Natta (pro) catalysts and system
WO2018063900A1 (en) 2016-09-29 2018-04-05 Dow Global Technologies Llc Method of polymerizing an olefin
US11008412B2 (en) 2016-09-29 2021-05-18 Dow Global Technologies Llc Method of polymerizing an olefin
US11123726B2 (en) 2016-10-27 2021-09-21 Univation Technologies, Lle Method of preparing a molecular catalyst
WO2018080690A1 (en) 2016-10-27 2018-05-03 Univation Technologies, Llc Method of preparing a molecular catalyst
WO2018231224A1 (en) 2017-06-14 2018-12-20 Exxonmobil Chemical Patents Inc. Ethylene copolymer blends for cross-linking applications
WO2019040845A1 (en) 2017-08-24 2019-02-28 Dow Global Technologies Llc Ethylene/c5-c10 alpha-olefin/ polyene interpolymers
US11066489B2 (en) 2017-09-29 2021-07-20 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility
US11066428B2 (en) 2017-09-29 2021-07-20 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility
US11242415B2 (en) 2017-09-29 2022-02-08 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility
WO2019157687A1 (en) 2018-02-14 2019-08-22 Dow Global Technologies Llc Ethylene/alpha-olefin interpolymer compositions with improved long term heat aging performance
US11970602B2 (en) 2018-02-14 2024-04-30 Dow Global Technologies Llc Ethylene/alpha-olefin interpolymer compositions with improved long term heat aging performance
US11447584B2 (en) 2018-03-30 2022-09-20 Dow Global Technologies Llc Olefin polymerization activators
US11542350B2 (en) 2018-03-30 2023-01-03 Dow Global Technologies Llc Binuclear olefin polymerization activators
US12037440B2 (en) 2018-03-30 2024-07-16 Dow Global Technologies Llc Highly soluble bis-borate as binuclear co-catalysts for olefin polymerization
US11787880B2 (en) 2018-03-30 2023-10-17 Dow Global Technologies Llc Highly soluble alkyl substituted carbenium borate as co-catalysts for olefin polymerizations
US11447586B2 (en) 2018-03-30 2022-09-20 Dow Global Technologies Llc Olefin polymerization activators
WO2020046597A1 (en) 2018-08-29 2020-03-05 Exxonmobil Chemical Patents Inc. Methods of making polymer compositions with enhanced elasticity by employing vtp and hmp catalyst systems in parallel processes
US12252574B2 (en) 2018-08-30 2025-03-18 Dow Global Technologies Llc Bis-phenyl-phenoxy polyolefin procatalysts having two anthracenyl ligands
US12378391B2 (en) 2019-03-29 2025-08-05 Dow Global Technologies Llc Oil-extended pellet form ethylene alpha-olefin diene interpolymers for thermoplastic vulcanizates
WO2021022014A1 (en) 2019-07-31 2021-02-04 Dow Global Technologies Llc Polymerization of ethylene in solution processes using a ziegler-natta catalyst and a hydrogenation procatalyst
US12466901B2 (en) 2019-07-31 2025-11-11 Dow Global Technologies Llc Polymerization of ethylene in solution processes using a Ziegler-Natta catalyst and a hydrogenation procatalyst
WO2021041562A1 (en) 2019-08-30 2021-03-04 Dow Global Technologies Llc Polyolefin compositions having improved electrical properties
US12448506B2 (en) 2019-09-24 2025-10-21 Dow Global Technologies Llc Polymer compositions for extruded profiles
WO2021061580A1 (en) 2019-09-24 2021-04-01 Dow Global Technologies Llc Polymer compositions for extruded profiles
WO2021061577A1 (en) 2019-09-24 2021-04-01 Dow Global Technologies Llc Ethylene/alpha-olefin/polyene interpolymer compositions
US12384909B2 (en) 2019-09-24 2025-08-12 Dow Global Technologies Llc Polymer compositions with excellent electrical and mechanical properties
US12565508B2 (en) 2020-01-31 2026-03-03 Dow Global Technologies Llc Group III and lanthanide bis-phenyl-phenoxy metal-ligand complexes
US12552885B2 (en) 2020-01-31 2026-02-17 Dow Global Technologies Llc Polymerization process that include group III and lanthanide bis-phenyl-phenoxy metal-ligand complexes and chain transfer agents
US12497414B2 (en) 2020-01-31 2025-12-16 Dow Global Technologies Llc Group III and Lanthanide bis-phenyl-phenoxy metal-ligand complexes
WO2021202091A1 (en) 2020-03-30 2021-10-07 Exxonmobil Chemical Patents Inc. Comb-block copolymers and methods thereof
WO2022015368A1 (en) 2020-07-17 2022-01-20 Dow Global Technologies Llc Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes
WO2022015369A1 (en) 2020-07-17 2022-01-20 Dow Global Technologies Llc Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes
WO2022015370A1 (en) 2020-07-17 2022-01-20 Dow Global Technologies Llc Hydrocarbyl-modified methylaluminoxane cocatalyst for bis-phenylphenoxy metal-ligand complexes
US12606647B2 (en) 2020-07-17 2026-04-21 Dow Global Technologies Llc Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes
WO2025117273A1 (en) 2023-12-01 2025-06-05 ExxonMobil Technology and Engineering Company Support-bound activators, supported catalyst systems, and processes for use thereof

Also Published As

Publication number Publication date
US8101696B2 (en) 2012-01-24
WO2007136493A2 (en) 2007-11-29
MX2008014669A (en) 2009-01-26
CN101484475A (en) 2009-07-15
BRPI0711819A2 (en) 2011-12-13
WO2007136496A2 (en) 2007-11-29
US8202953B2 (en) 2012-06-19
CN101472952B (en) 2012-10-03
MX2008014667A (en) 2009-01-26
CN101472952A (en) 2009-07-01
US8450438B2 (en) 2013-05-28
ES2524779T3 (en) 2014-12-12
BRPI0711018A2 (en) 2011-08-23
CN101490095A (en) 2009-07-22
EP2492287B1 (en) 2017-05-31
JP2009537656A (en) 2009-10-29
EP2492287A2 (en) 2012-08-29
SG158102A1 (en) 2010-01-29
CN101472951B (en) 2014-07-02
CN101490096A (en) 2009-07-22
RU2463311C2 (en) 2012-10-10
US20090299116A1 (en) 2009-12-03
KR20090026147A (en) 2009-03-11
MX2008014671A (en) 2009-01-26
ES2394225T3 (en) 2013-01-23
RU2450026C2 (en) 2012-05-10
RU2008149712A (en) 2010-06-27
AR060642A1 (en) 2008-07-02
US20110313119A1 (en) 2011-12-22
BRPI0711029A2 (en) 2011-05-31
WO2007136493A3 (en) 2008-01-10
EP2024399A2 (en) 2009-02-18
KR20090026151A (en) 2009-03-11
US8058373B2 (en) 2011-11-15
WO2007136495A3 (en) 2008-01-17
RU2008149709A (en) 2010-06-27
ES2634440T3 (en) 2017-09-27
EP2024402A2 (en) 2009-02-18
WO2007136506A2 (en) 2007-11-29
KR101397337B1 (en) 2014-05-19
KR20090024159A (en) 2009-03-06
US20100036069A1 (en) 2010-02-11
CN101472951A (en) 2009-07-01
EP2021378A2 (en) 2009-02-11
EP2024399B1 (en) 2014-04-09
JP2009537654A (en) 2009-10-29
EP2024401B1 (en) 2015-02-25
EP2024402B1 (en) 2017-10-25
US8354484B2 (en) 2013-01-15
RU2008149711A (en) 2010-06-27
CA2652460A1 (en) 2007-11-29
RU2008149714A (en) 2010-06-27
KR101396058B1 (en) 2014-05-15
JP5666129B2 (en) 2015-02-12
JP2015071786A (en) 2015-04-16
CN102786619A (en) 2012-11-21
KR101352674B1 (en) 2014-01-16
CN102786619B (en) 2015-01-07
JP5623738B2 (en) 2014-11-12
JP5603595B2 (en) 2014-10-08
EP2024403A2 (en) 2009-02-18
CN101484475B (en) 2013-04-03
KR101395970B1 (en) 2014-05-21
CN101490094A (en) 2009-07-22
CA2652465A1 (en) 2007-11-29
JP5583402B2 (en) 2014-09-03
JP5645400B2 (en) 2014-12-24
ES2567140T3 (en) 2016-04-20
ES2475159T3 (en) 2014-07-10
ES2651590T3 (en) 2018-01-29
ES2534469T3 (en) 2015-04-23
MX2008014668A (en) 2009-01-26
WO2007136497A3 (en) 2008-01-31
KR20090026150A (en) 2009-03-11
AR060643A1 (en) 2008-07-02
US20090312509A1 (en) 2009-12-17
KR20090027212A (en) 2009-03-16
ES2651590T5 (en) 2023-05-05
AU2007254428A1 (en) 2007-11-29
AR060639A1 (en) 2008-07-02
WO2007136495A2 (en) 2007-11-29
CA2652551A1 (en) 2007-11-29
WO2007136494A3 (en) 2008-01-10
EP2024402B2 (en) 2023-01-25
EP2021378B1 (en) 2016-03-09
US20120101241A1 (en) 2012-04-26
US20120088894A1 (en) 2012-04-12
KR101401785B1 (en) 2014-05-30
CN101490096B (en) 2012-06-13
AR060641A1 (en) 2008-07-02
JP2009537655A (en) 2009-10-29
CA2652456A1 (en) 2007-11-29
WO2007136497A2 (en) 2007-11-29
CA2653534A1 (en) 2007-11-29
AR060640A1 (en) 2008-07-02
US8349984B2 (en) 2013-01-08
KR101384380B1 (en) 2014-04-10
EP2787013A1 (en) 2014-10-08
US8299189B2 (en) 2012-10-30
EP2024401A2 (en) 2009-02-18
JP2009537657A (en) 2009-10-29
EP2492287A3 (en) 2012-11-07
CN101490094B (en) 2013-06-26
WO2007136496A3 (en) 2008-01-31
EP2024403B1 (en) 2014-09-17
EP2024400A2 (en) 2009-02-18
EP2024400B1 (en) 2012-09-12
CN104725535A (en) 2015-06-24
KR20090026149A (en) 2009-03-11
AR060638A1 (en) 2008-07-02
BRPI0711018A8 (en) 2017-09-19
JP6001042B2 (en) 2016-10-05
WO2007136506A3 (en) 2008-01-24
JP2009537653A (en) 2009-10-29
US20120108770A1 (en) 2012-05-03

Similar Documents

Publication Publication Date Title
US8299189B2 (en) Ethylene/α-olefin/diene solution polymerization process and polymer

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780023316.0

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07755918

Country of ref document: EP

Kind code of ref document: A2

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2007755918

Country of ref document: EP

Ref document number: MX/A/2008/014668

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2652456

Country of ref document: CA

Ref document number: 2009510950

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2007254428

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1020087030629

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2007254428

Country of ref document: AU

Date of ref document: 20070424

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12300863

Country of ref document: US