WO1999001460A1 - Catalyst for the production of olefin polymers - Google Patents
Catalyst for the production of olefin polymers Download PDFInfo
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- WO1999001460A1 WO1999001460A1 PCT/US1998/013781 US9813781W WO9901460A1 WO 1999001460 A1 WO1999001460 A1 WO 1999001460A1 US 9813781 W US9813781 W US 9813781W WO 9901460 A1 WO9901460 A1 WO 9901460A1
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- 0 C*c1c(*C)c(O)c(*)c(*)c1* Chemical compound C*c1c(*C)c(O)c(*)c(*)c1* 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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
- Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- the invention relates to a family of novel heteroatom-containing catalyst precursors useful for the polymerization of olefins, such as ethylene, higher alpha-olefins, dienes, and mixtures thereof.
- Metallocenes and other single site-like catalysts have been developed to prepare olefin polymers.
- Metallocenes are organometallic coordination complexes containing one or more ⁇ - bonded moieties (i.e., cyclopentadienyl groups) in association with a metal atom.
- Catalyst compositions containing metallocenes and other single site-like catalysts are highly useful in the preparation of polyolefins, producing relatively homogeneous copolymers at excellent polymerization rates while allowing one to tailor closely the final properties of the polymer as desired.
- PCT Application No. WO 96/23101 relates to di(imine) metal complexes that are transition metal complexes of bidentate ligands selected from the group consisting of:
- transition metal is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni, and Pd;
- R2 and R ⁇ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
- R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or ⁇ R and R ⁇ taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
- R44 is hydrocarbyl or substituted hydrocarbyl
- R ⁇ 8 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R ⁇ 4 and R ⁇ 8 taken together form a ring
- R45 is hydrocarbyl or substituted hydrocarbyl, and R ⁇ 9 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R ⁇ 9 taken together form a ring; each R 0 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R ⁇ O taken together form a ring; each R31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- R46 and R ' are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
- R48 and R 9 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl
- R20 and R ⁇ 3 are independently hydrocarbyl or substituted hydrocarbyl
- R21 and R ⁇ 2 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and n is 2 or 3; and provided that: said transition metal also has bonded to it a ligand that may be displaced by or added to the olefin monomer being polymerized; and when the transition metal is Pd, said bidentate ligand is (V), (VII) or (VIII).
- PCT Application No. WO 97/02298 relates to a process for the polymerization of an olefin, comprising contacting a polymerizable monomer consisting essentially of ethylene, a norbornene or a styrene, with a catalyst system comprising the product of mixing in solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand, and all ligands are neutral, an acid of the formula HX (IV), and a first compound selected from the group consisting of:
- X is a noncoordinating anion
- R43 is hydrogen or alkyl; n is 1 or 2;
- Rl 2 , R13 and Rl are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- RU and Rl5 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E s is about
- each Rl6 and Rl7 i s independently hydrogen or acyl containing 1 to 20 carbon atoms;
- Ar3 is an aryl moiety
- Rl and Rl are each independently hydrogen or hydrocarbyl
- Ar is an aryl moiety
- R 22 and R 3 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms;
- R 2 4 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety.
- PCT Application No. WO 96/33202 relates to a transition metal catalyst containing a pyridine or quinoline moiety and having the formula:
- each R is independently selected from hydrogen or Cj to Cg alkyl
- each R' is independently selected from Cj to Cg alkyl, C ⁇ to Cg alkoxy, Cg to Ci aryl, halogen, or CF3
- M is titanium, zirconium, or hafnium
- each X is independently selected from halogen, C ⁇ to Cg alkyl, Cj to Cg alkoxy, or R
- TM TM
- L X
- c clopentadienyl Cj to Cg alkyl substituted cyclopentadienyl, indenyl, fluorenyl, or
- m is 0 to 4
- V is 1 to 4.
- Fuhrmann et al., Inorg. Chem., 35:6742-6745 discloses certain Group 4 metal complexes containing amine, amido, and aminopyridinato ligands such as:
- TMS is trimethylsilyl
- the catalyst composition comprises a heteroatom-containing catalyst precursor having the formula:
- each A has the formula:
- M is a metal selected from the group consisting of Group 3 to 13 elements and Lanthanide series elements; each L is a monovalent, bivalent, or trivalent anion; X and Y are each heteroatoms; Cyclo is a cyclic moiety; each Rl is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R 1 groups may be joined to form a cyclic moiety; each R 2 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R 2 groups may be joined to form a cyclic moiety;
- Q is a bridging group; each m is independently an integer from 0 to 5; n is an integer from 1 to 4; q is 1 or 2; and when q is 2, the A groups are optionally connected by a bridging group Z.
- the catalyst precursor may be conveniently prepared by reacting an organometal compound with a heteroatom-containing ligand of the formula:
- the invention provides a catalyst precursor of the formula:
- each A has the formula:
- M is a metal selected from the group consisting of Group 3 to 13 elements and Lanthanide series elements; each L is a monovalent, bivalent, or trivalent anion; X and Y are each heteroatoms; Cyclo is a cyclic moiety; each Rl is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent Rl groups may be joined to form a cyclic moiety; each R 2 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R 2 groups may be joined to form a cyclic moiety;
- Q is a bridging group; each m is independently an integer from 0 to 5; n is an integer from 1 to 4; q is 1 or 2; and when q is 2, the A groups are optionally connected by a bridging group Z; along with a catalyst composition comprising this catalyst precursor and an activating cocatalyst, as well as a process for the polymerization of olefins, using this catalyst composition.
- the invention also provides a catalyst precursor comprising the reaction product of an organometal compound and heteroatom- containing ligand having a formula selected from the group consisting of:
- X and Y are each heteroatoms; Cyclo is a cyclic moiety; each Rl is a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent Rl groups may be joined to form a cyclic moiety; each R 2 is a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R 2 groups may be joined to form a cyclic moiety;
- Q is a bridging group; and each m is independently an integer from 0 to 5; as well as a catalyst composition comprising this catalyst precursor and an activating cocatalyst, and a process for polymerizing olefins using this catalyst composition.
- each A has the formula:
- M is a metal selected from the group consisting of Group 3 to 13 and Lanthanide series elements, preferably a Group 4 element, more preferably zirconium.
- Each L is a monovalent, bivalent, or trivalent anion, preferably independently selected from the group consisting of halogens; hydrogen; alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarboxy radicals having 1-50 carbon atoms; amides; phosphides; sulfides; silylalkyls; diketonates; and carboxylates. More preferably, each L is selected from the group consisting of halides, alkyl radicals, and arylalkyl radicals. Most preferably, each L is selected from the group consisting of arylalkyl radicals such as benzyl. Each L may contain one or more heteroatoms.
- X and Y are each heteroatoms and are preferably independently selected from the group consisting of N, O, S, and P. More preferably, X and Y are independently selected from the group consisting of N and P. Most preferably, X and Y are both nitrogen.
- Y is contained in a heterocyclic ring containing 2 to 7 carbon atoms, preferably 3 to 6 carbon atoms, more preferably 5 carbon atoms.
- the heterocyclic ring may contain additional heteroatoms (i.e., in addition to Y).
- Cyclo is a cylic moiety.
- Cyclo is a carbocyclic ring containing 3 to 7 carbon atoms. More preferably, Cyclo is an aryl group.
- Each Rl is independently a group containing 1 to 50 carbon atoms selected from the group consisting of hydrogen and Group 13 to
- Rl is an alkyl. More preferably, Rl is isopropyl. Optionally, an Rl group may be joined to Q. It is preferred that at least one Rl is ortho to X.
- Each R 2 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R 2 groups may be joined to form a cyclic moiety such as an aliphatic or aromatic ring.
- R 2 is hydrogen or an aryl. More preferably, R 2 is hydrogen.
- R 2 is an aryl group and Y is N a quinoline group may be formed.
- an R 2 group may be joined to Q.
- Q is a bridging group.
- Q contains one or more Group 13, 14, 15, or 16 elements. More preferably, Q contains one or more Group 14 elements. Most preferably, Q is a substituted carbon.
- Each m is independently an integer from 0 to 5, preferably 2, and n is an integer from 1 to 4, preferably 3.
- Z preferably contains one or more Group IIIA, Group IVA, Group VA, or Group VIA elements. More preferably, Z contains one or more Group IVA elements.
- the catalyst precursor has the formula:
- R a and R D are each independently selected from the group consisting of alkyl, aryl, heterocyclic groups, and hydrogen; R c and R ( j are each independently selected from the group consisting of alkyl, aryl, and hydrogen; and each L has the meaning stated above.
- the catalyst precursor has the formula:
- the catalyst precursor has the formula:
- Ra, Rb, Rc, Rd, and L have the meanings stated above.
- the catalyst precursor has the formula: wherein R a , Rb, Rc d > an ⁇ L have the meanings stated above.
- the catalyst precursor has the formula:
- the catalyst precursor has the formula:
- the catalyst precursor has the formula:
- Yet another preferred catalyst precursor is:
- the catalyst precursor may be made by any method.
- the method of making the catalyst precursor is not critical to the invention. However, one useful method of making the catalyst precursor is by reacting an organometal compound or a metal halide with a heteroatom-containing ligand having a formula selected from the group consisting of:
- the catalyst precursor is made by reacting an organometal compound with the heteroatom-containing ligand.
- the catalyst precursor comprises the reaction product of an organometal compound and a heteroatom-containing ligand having a formula selected from the group consisting of:
- the metal of the organometal compound may be selected from Group 3 to 13 elements and Lanthanide series elements.
- the metal is a Group 4 element. More preferably the metal is zirconium.
- the organometal compound for example may be a metal hydrocarbyl such as a metal alkyl, metal aryl, or metal arylalkyl. Metal silylalkyls, metal amides, or metal phosphides may also be used.
- the organometal compound is a zirconium hydrocarbyl. More preferably, the organometal compound is a zirconium arylalkyl. Most preferably, the organometal compound is tetrabenzylzirconium.
- organometal compounds examples include tetramethylzirconium, tetraethylzirconium, tetrakis [trimethylsilylmethyl] zirconium, tetrakis [dime th lamino] zirconium, dichlorodibenzylzirconium, chlorotribenzylzirconium, trichlorobenzylzirconium, bis [dimethylaminojbis [benzyl] zirconium, and tetrabenzylzirconium.
- catalyst precursors containing these in a two-step process by first reacting the heteroatom-containing ligand with a lithium alkyl to make a lithium amide, and then reacting with a lanthanide or transition metal halide to generate the amide complex.
- the heteroatom-containing ligand has the formula:
- heteroatom-containing ligand has the formula:
- the heteroatom-containing ligand is a pyridine/imine ligand of the formula:
- R 3 is hydrogen, a hydrocarbon group containing 1 to 20 carbon atoms optionally substituted with one or more heteroatoms, or a heteroatom optionally substituted with a hydrocarbon group.
- Compound 1 may be made by reacting a substituted pyridine/imine ligand with a zirconium aryl such as tetrabenzyl zirconium:
- This reaction is preferably carried out in a suitable solvent such as toluene or benzene at a temperature in the range of -50 to 50°C and a pressure ranging from a vacuum to 1000 psi.
- a suitable solvent such as toluene or benzene
- the catalyst precursor can be made by reacting the heteroatom-containing ligand with a metal halide and then further reacting the product thereof with a Grignard reagent, such as an organomagnesium halide.
- a Grignard reagent such as an organomagnesium halide.
- the same catalyst precursor, Compound 1 may be made by reacting a substituted pyridine/imine ligand with a zirconium halide such as zirconium tetrachloride, and then further reacting the product thereof with PhCH 2 MgCl.
- Another preferred catalyst precursor, Compound 2 may be made by reacting a substituted pyridine/amine ligand with a zirconium aryl such as tetrabenzyl zirconium:
- This reaction is preferably carried out in a suitable solvent such as toluene or benzene at a temperature in the range of -50 to 50°C and a pressure ranging from a vacuum to 1000 psi.
- a suitable solvent such as toluene or benzene
- Another preferred catalyst precursor, Compound 3 may be made by reacting Compound 2 with acetone:
- Compound 4 may be made in a multistep procedure by reacting a substituted pyridine/amine ligand sequentially with methyl lithium, chlorotrimethylsilane, zirconium tetrachloride, and benzyl magnesium chloride as follows:
- This reaction is preferably carried out in a suitable solvent such as toluene or benzene at a temperature in the range of -50 to 50°C and a pressure ranging from a vacuum to 1000 psi.
- a suitable solvent such as toluene or benzene
- the catalyst precursor may be isolated by conventional methods.
- the catalyst composition comprises the catalyst precursor and an activating cocatalyst.
- the activating cocatalyst is capable of activating the catalyst precursor.
- the activating cocatalyst is one of the following: (a) branched or cyclic oligomeric poly(hydrocarbylaluminum oxide)s which contain repeating units of the general formula -(Al(R*)O)-, where R* is hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aryl radical such as a substituted or unsubstituted phenyl or naphthyl group; (b) ionic salts of the general formula [A + ][BR 4 _ ], where A + is a cationic Lewis or Bronsted acid capable of abstracting an alkyl, halogen, or hydrogen from the metallocene catalysts, B is boron, and R is a substituted aromatic hydrocarbon, preferably a perfluorophenyl radical; (c)
- the activating cocatalyst is a branched or cyclic oligomeric poly(hydrocarbylaluminum oxide) or a boron alkyl. More preferably, the activating cocatalyst is an aluminoxane such as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), or a boron alkyl.
- MAO methylaluminoxane
- MMAO modified methylaluminoxane
- Aluminoxanes are well known in the art and comprise oligomeric linear alkyl aluminoxanes represented by the formula:
- s is 1-40, preferably 10-20; p is 3-40, preferably 3-20; and R*** is an alkyl group containing 1 to 12 carbon atoms, preferably methyl.
- Aluminoxanes may be prepared in a variety of ways. Generally, a mixture of linear and cyclic aluminoxanes is obtained in the preparation of aluminoxanes from, for example, trimethylaluminum and water.
- an aluminum alkyl may be treated with water in the form of a moist solvent.
- an aluminum alkyl, such as trimethylaluminum may be contacted with a hydrated salt, such as hydrated ferrous sulfate.
- the latter method comprises treating a dilute solution of trimethylaluminum in, for example, toluene with a suspension of ferrous sulfate heptahydrate.
- methylaluminoxanes by the reaction of a tetraalkyl- dialuminoxane containing C 2 or higher alkyl groups with an amount of trimethylaluminum that is less than a stoichiometric excess.
- the synthesis of methylaluminoxanes may also be achieved by the reaction of a trialkyl aluminum compound or a tetraalkyldialuminoxane containing C 2 or higher alkyl groups with water to form a polyalkyl aluminoxane, which is then reacted with trimethylaluminum.
- methylaluminoxanes which contain both methyl groups and higher alkyl groups, i.e., isobutyl groups, may be synthesized by the reaction of a polyalkyl aluminoxane containing C 2 or higher alkyl groups with trimethylaluminum and then with water as disclosed in, for example, U.S. Patent No. 5,041,584.
- the mole ratio of aluminum atoms contained in the poly(hydrocarbylaluminum oxide) to total metal atoms contained in the catalyst precursor is generally in the range of from about 2:1 to about 100,000:1, preferably in the range of from about 10:1 to about 10,000:1, and most preferably in the range of from about 50:1 to about 2,000:1.
- the mole ratio of boron atoms contained in the ionic salt or the boron alkyl to total metal atoms contained in the catalyst precursor is generally in the range of from about 0.5:1 to about 10:1, preferably in the range of from about 1:1 to about 5:1.
- the catalyst precursor, the activating cocatalyst, or the entire catalyst composition may be impregnated onto a solid, inert support, in liquid form such as a solution, dispersion or neat liquid, spray dried, in the form of a prepolymer, or formed in-situ during polymerization.
- a catalyst composition that is spray dried as described in European Patent Application No. 0 668 295 Al or in liquid form as described in U.S. Patent No. 5,317,036.
- the catalyst composition may be impregnated in or deposited on the surface of an inert substrate such as silica, carbon black, polyethylene, polycarbonate porous crosslinked polystyrene, porous crosslinked polypropylene, alumina, thoria, zirconia, or magnesium halide (e.g., magnesium dichloride), such that the catalyst composition is between 0.1 and 90 percent by weight of the total weight of the catalyst composition and the support.
- an inert substrate such as silica, carbon black, polyethylene, polycarbonate porous crosslinked polystyrene, porous crosslinked polypropylene, alumina, thoria, zirconia, or magnesium halide (e.g., magnesium dichloride), such that the catalyst composition is between 0.1 and 90 percent by weight of the total weight of the catalyst composition and the support.
- the catalyst composition may be used for the polymerization of olefins by any suspension, solution, slurry, or gas phase process, using known equipment and reaction conditions, and is not limited to any specific type of reaction system.
- olefin polymerization temperatures range from about 0°C to about 200°C at atmospheric, subatmospheric, or superatmospheric pressures.
- Slurry or solution polymerization processes may utilize subatmospheric or superatmospheric pressures and temperatures in the range of about 40°C to about 110°C.
- a useful liquid phase polymerization reaction system is described in U.S. Patent 3,324,095.
- Liquid phase reaction systems generally comprise a reactor vessel to which olefin monomer and catalyst composition are added, and which contains a liquid reaction medium for dissolving or suspending the polyolefin.
- the liquid reaction medium may consist of the bulk liquid monomer or an inert liquid hydrocarbon that is nonreactive under the polymerization conditions employed.
- an inert liquid hydrocarbon need not function as a solvent for the catalyst composition or the polymer obtained by the process, it usually serves as solvent for the monomers employed in the polymerization.
- the inert liquid hydrocarbons suitable for this purpose are isopentane, hexane, cyclohexane, heptane, benzene, toluene, and the like.
- Reactive contact between the olefin monomer and the catalyst composition should be maintained by constant stirring or agitation.
- the reaction medium containing the olefin polymer product and unreacted olefin monomer is withdrawn from the reactor continuously.
- the olefin polymer product is separated, and the unreacted olefin monomer and liquid reaction medium are recycled into the reactor.
- gas phase polymerization is employed, with superatmospheric pressures in the range of 1 to 1000 psi, preferably 50 to 400 psi, most preferably 100 to 300 psi, and temperatures in the range of 30 to 130°C, preferably 65 to 110°C.
- Stirred or fluidized bed gas phase reaction systems are particularly useful.
- a conventional gas phase, fluidized bed process is conducted by passing a stream containing one or more olefin monomers continuously through a fluidized bed reactor under reaction conditions and in the presence of catalyst composition at a velocity sufficient to maintain a bed of solid particles in a suspended condition.
- a stream containing unreacted monomer is withdrawn from the reactor continuously, compressed, cooled, optionally fully or partially condensed as disclosed in U.S. Patent Nos. 4,528,790 and 5,462,999, and recycled to the reactor.
- Product is withdrawn from the reactor and make-up monomer is added to the recycle stream.
- any gas inert to the catalyst composition and reactants may also be present in the gas stream.
- a fluidization aid such as carbon black, silica, clay, or talc may be used, as disclosed in U.S. Patent No. 4,994,534.
- Polymerization may be carried out in a single reactor or in two or more reactors in series, and is conducted substantially in the absence of catalyst poisons.
- Organometallic compounds may be employed as scavenging agents for poisons to increase the catalyst activity.
- scavenging agents are metal alkyls, preferably aluminum alkyls, most preferably triisobutylaluminum.
- Hydrogen or a metal or non-metal hydride e.g., a silyl hydride
- Hydrogen may be used as a chain transfer agent in the process. Hydrogen may be used in amounts up to about 10 moles of hydrogen per mole of total monomer feed.
- Olefin polymers that may be produced according to the invention include, but are not limited to, ethylene homopolymers, homopolymers of linear or branched higher alpha-olefins containing 3 to about 20 carbon atoms, and interpolymers of ethylene and such higher alpha-olefins, with densities ranging from about 0.86 to about 0.96.
- Suitable higher alpha-olefins include, for example, propylene, 1- butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 1-octene, and 3,5,5- trimethyl-1-hexene.
- Olefin polymers according to the invention may also be based on or contain conjugated or non-conjugated dienes, such as linear, branched, or cyclic hydrocarbon dienes having from about 4 to about 20, preferably 4 to 12, carbon atoms.
- Preferred dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene, 1,7-octadiene, vinyl cyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidene norbornene and the like.
- Aromatic compounds having vinyl unsaturation such as styrene and substituted styrenes, and polar vinyl monomers such as acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, vinyl trialkyl silanes and the like may be polymerized according to the invention as well.
- Specific olefin polymers that may be made according to the invention include, for example, polyethylene, polypropylene, ethylene/propylene rubbers (EPR's), ethylene/propylene/diene terpolymers (EPDM's), polybutadiene, polyisoprene and the like.
- melt index (dg/min), measured using ASTM D-1238 Condition E at 190° C.
- 121 is flow index (dg/min), measured using ASTM D-1238- Condition F.
- MFR Melt Flow Ratio, 121/12.
- BBF Butyl Branching Frequency, number of butyl branches per 1000 main chain carbon atoms based on infrared measurement techniques.
- Mn is Number Average Molecular Weight, as determined by gel permeation chromatography using crosslinked polystyrene columns; pore size sequence: 1 column less than 1000 A, 3 columns of mixed 5 x 10 ' A; 1,2,4-trichlorobenzene solvent at 140° C with refractive index detection.
- PDI Polydispersity Index, equivalent to Molecular Weight Distribution (M w /M n ).
- the ligand/ZrCl4 mixture was bright yellow.
- the vessel was removed from the dry box and placed under argon beside the vessel containing the Grignard solution.
- the ligand/ZrCl4 solution was covered with foil and chilled to -78 ° C.
- the Grignard solution was slowly transferred via double-ended cannula into the ligand/ZrCl4 solution.
- the reaction mixture turned bright red when the addition was complete.
- the reaction was allowed to slowly warm to room temperature.
- the vessel was returned to the dry box and filtered through a medium porosity frit. Toluene was added to the filtrate to adjust the volume to 500 mL.
- the filtrate was transferred to an amber bottle.
- a 1.0 mL subsample was removed and placed in a tared 10 mL flask. The subsample was vacuum stripped and the mass of the residue was used to determine the molarity of the solution at 0.089M.
- a series of ethylene/hexene copolymers were made in a laboratory scale, slurry phase reactor using a catalyst composition comprising the catalyst precursor of Example 2 with modified methylaluminoxane, MMAO (7.0 wt % Al in heptane, commercially available from Akzo Chemicals, Inc.).
- the catalyst composition was prepared by combining a solution of the catalyst precursor of Example 2 in benzene with the MMAO solution in the presence of 0.1 mL 1-hexene. Reaction conditions and results are shown in Table 1 below.
- a series of ethylene/hexene copolymers were made in a laboratory scale, slurry phase reactor using catalyst compositions comprising various catalyst precursors according to the invention with MMAO cocatalyst.
- the catalyst composition was prepared by contacting the ligand shown below in Table 2 with tetrabenzyl zirconium, dissolving the resulting material in toluene, and then contacting with MMAO solution (7.0 wt % Al in heptane, commercially available from Akzo Chemicals, Inc.) in the presence of 0.1 mL 1- hexene. Polymerization reactions were carried out at 65° C, 85 psi ethylene, 1.0 micromole Zr, and a MMAO/Zr mole ratio of 1,000. Ligands and results are shown in Table 2 below.
- EXAMPLE 6 A series of ethylene/hexene copolymers were made in a laboratory scale, slurry phase reactor using mixed catalyst compositions according to the invention with MMAO cocatalyst.
- the catalyst composition was prepared by contacting mixtures of the ligands shown below in Table 3 with tetrabenzyl zirconium, dissolving the resulting material in toluene, and then contacting with MMAO solution (7.0 wt % Al in heptane, commercially available from Akzo Chemicals, Inc.) in the presence of 0.1 mL 1- hexene.
- MMAO solution 7.0 wt % Al in heptane, commercially available from Akzo Chemicals, Inc.
- Polymerization reaction conditions were 65° C, 85 psi ethylene, 1.0 micromole Zr, and a MMAO/Zr mole ratio of 1,000.
- Ligands and results are shown in Table 3 below. TABLE 3
- An ethylene/hexene copolymer was made in a laboratory scale, slurry phase reactor using a mixed catalyst composition comprising the catalyst precursor of Example 2, biscyclopentadienyl zirconium dichloride, and MMAO.
- the catalyst precursor of Example 3 combined with MMAO was used as the catalyst composition to polymerize an ethylene/1-hexene copolymer (density 0.917, melt index 1.0) in a pilot-scale, fluidized bed, gas phase reactor.
- the reactor was nominally 1 foot in diameter and was operated with a bed height of 8 feet and a superficial gas velocity of approximately 1.8 ft/sec. Total reactor pressure was 350 psig.
- a seed bed was charged to the reactor and it was dried to ⁇ 5 ppm water.
- the reactor was pressurized to 200 psig of ethylene.
- the 1-hexene/ethylene and hydrogen/ethylene mole ratio was established at 0.048 and 0.041.
- the bed temperature was adjusted to 70° C.
- the catalyst composition was employed in liquid form.
- the catalyst composition was made by mixing the catalyst precursor of Example 3 in toluene with MMAO (2.8 wt % Al, commercially available from Akzo Chemicals, Inc.). Additional dilution of the catalyst composition was performed by adding isopentane to the mixture.
- the catalyst composition sprayed into the reactor with the aid of 5.0-7.0 lb/hr of nitrogen gas and a stream of 1950 lbs/hr of recycle gas.
- Reactor static was clearly absent throughout the run.
- the expanded section, recycle line and distributor plate were free from fouling.
- the average particle size (APS) held steady and could be controlled by varying the nitrogen carrier flow and resin density.
- a series of catalyst precursors according to the invention were made using the ligand of Example 9 and a variety of metal compounds. Each catalyst precursor was made by first combining the ligand in ether with methyllithium and then contacting the resulting product with the metal compound shown in Table 4 below. The resulting catalyst precursors were combined with a cocatalyst and used for the slurry homopolymerization of ethylene in a laboratory scale reactor in the manner described in Example 4.
- Example 10 In a darkened room and darkened dry box, 5.0 mmol (1.45 g) of the ligand made in Example 10 were charged to a 100 mL Schlenk tube equipped with a stir bar. The ligand was dissolved in 5 mL of toluene. To a second vessel equipped with a stir bar was charged 5.5 mmol (2.5g) tetrabenzyl zirconium and 10 mL toluene.
- the ligand solution was transferred into the tetrabenzyl zirconium solution.
- the vessel was covered with foil and allowed to stir at room temperature in the dry box. After 6 hours at room temperature 80 mL dry hexane was added to the reaction solution and allowed to stir overnight.
- the reaction mixture was filtered through a medium porosity frit with approximately 2g pale yellow solids collected.
- GC vial To an oven-dried, cooled, purged and sealed GC vial was charged 0.10 mL dried acetone. The GC vial was sealed in a shell vial and taken into the dry box. In a darkened room and darkened dry box 2.0 mmol (1.3g) of the material made in Example 11 and 9 mL toluene were charged to 1 100 mL Schlenk flask equipped with a stir bar. To a second GC vial was charged 2.0 mmol (146 uL) acetone and 1.0 mL toluene.
- the acetone/toluene solution was transferred dropwise via syringe into the stirred solution of [l-(2pyridyl) N-l-methylethyl][l-N- 2,6-diisopropylphenylamido] zirconoum tribenzyl.
- the vessel was covered with foil and allowed to stir at room temperature in the dry box overnight.
- reaction solution was vacuum stripped to a tacky orange residue. Dry hexane (20 mL) was added and the residue stirred vigorously, then vacuum stripped again to a yellow-orange glass. Hexane was added again and vigorously stirred. The vessel was placed in a freezer (-24° C) for approximately 2 hours. The mixture was filtered through a medium porosity frit. Pale yellow solids (0.8 g) were collected.
- Hexane (600mL), triisobutylaluminum (100 ⁇ moles of a 1.0M solution in toluene) and 1-hexene (43 mis, alumina dried) were charged to a 1 liter slurry reactor.
- Example 11 The complex from Example 11 (2.46 ⁇ moles) and trityl(tetraperfluorophenyl)borate (2.33 ⁇ moles) were weighed into an oven dried, glass vial. Toluene (1.0 ml) was added and the mixture was stirred for 5 minutes resulting in a yellow solution. Triisobutylaluminum (10 ⁇ moles of a 1.0M solution in toluene) was added to the solution to make a reaction solution. An aliquot of the reaction solution (0.20 mis, 0.5 ⁇ moles Zr) was charged to the reactor 4 minutes after the triisobutylaluminum addition and the reaction was started. The reactor was run at 75°C and 85 psia ethylene pressure for 30 minutes.
- the polyethylene resin produced weighed 76.5g.
- the calculated activity was 360000 g/ mole Zr/ lOOpsi ethylene/ hour.
- the molecular weight of the resin was too high to obtain an 121 or 12.
- Trityl(tetraperfluorophenyl)borate (1.89 ⁇ moles, Akzo) was weighed into an oven dried, glass vial. Toluene (1.0 ml) was added resulting in a dark yellow solution. The complex described in Example 12, (2.0 ⁇ moles, 0.025 mis of an 80 ⁇ mole/ml solution in deuterated benzene) was added to the dark yellow solution resulting in an immediate pale yellow solution. After 5 minutes of stirring tiisobutylaluminum (10 ⁇ moles of a 1.0M solution in toluene) was added to the solution to make a reaction solution.
- EXAMPLE 15 In each of Examples 15a-15f, in a darkened dry box and darkened room, 0.100 mmol of [l-(2-pyridyl)N-l-methylethyl][l-N-2,6- diisopropylphenylamido] zirconium tribenzyl was dissolved in 1.0 mL of benzene-dg in a 10 mL Schlenk flask. To a second vessel was charged 0.100 mmol of the desired reactant described in Table 5 and 0.5 mL benzene-dg. The second solution was transferred into the first solution dropwise. The vessel was sealed, covered with foil and allowed to stir overnight.
- ethylene/hexene copolymers were made in a laboratory scale, slurry phase reactor using products described in Table 5 with MMAO (7.0 wt % Al in heptane, commercially available from Akzo Chemicals, Inc.).
- the catalyst composition was prepared by combining a benzene solution of the product described in Table 5 with the MMAO solution in the presence of 0.1 mL 1-hexene. Reaction conditions were 85° C, 85 psi ethylene, 0.5 micro moles of zirconium complex, 43mL 1-hexene, and 1000 equivalents of MMAO per zirconium. The results are shown in Table 5.
- reaction mixture was vacuum stripped to a powdery, pale yellow residue which was taken into the dry box.
- the resulting ligand was dissolved in 20 mL toluene.
- 10 mmol (2.33g) of zirconium (IV) chloride was slurried in 10 mL toluene.
- the ligand solution was added to the ZrCl4 slurry with vigorous stirring. The yellow slurry was allowed to stir overnight in the dry box.
- a series of ethylene/hexene copolymers were made in a laboratory scale, slurry phase reactor using a catalyst composition comprising the catalyst precursor of Example 17 with MMAO (7.0 wt % Al in heptane, commercially available from Akzo Chemicals, Inc.).
- MMAO 7.0 wt % Al in heptane
- the catalyst composition was prepared by combining a solution of the catalyst precursor of Example 17 in benzene with the MMAO solution in the presence of 0.1 L 1-hexene. Reaction conditions and results are shown in Table 6 below.
- 2,6-Diisopropyl aniline (50 mmol, 8.86g Aldrich, 90%) was charged to an oven-dried, cooled Schlenk flask equipped with a stir bar and septa. The flask was placed under a nitrogen purge and 20 mL of dry tetrahydrofuran was added. The flask was chilled to 0° C and n- butyl lithium (50 mmol, 17.8 mL, Aldrich, 2.81M solution in hexane) was added dropwise via syringe. The mixture was allowed to slowly warm to room temperature.
- Tetrabenzyl zirconium (0.200 mmol, 0.091g) was charged to a 7 mL amber bottle equipped with a stir bar and screw-cap. Dried benzene-d6
- a series of ethylene/hexene copolymers were made in a laboratory scale, slurry phase reactor using a catalyst composition comprising the catalyst precursor of Example 19 with MMAO (7.0 wt % Al in heptane, commercially available from Akzo Chemicals, Inc.).
- MMAO 7.0 wt % Al in heptane
- the catalyst composition was prepared by combining a solution of the catalyst precursor in benzene with the MMAO solution in the presence of 0.1 mL 1-hexene. Polymerization reactions were carried out at 85 psi ethylene, 0.5 micromole Zr, and a MMAO/Zr mole ratio of 1,000. Reaction conditions and results are shown in Table 7 below.
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Abstract
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AU83806/98A AU735915B2 (en) | 1997-07-02 | 1998-07-01 | Catalyst for the production of olefin polymers |
CA002295215A CA2295215C (en) | 1997-07-02 | 1998-07-01 | Catalyst for the production of olefin polymers |
JP50737199A JP3491761B2 (en) | 1997-07-02 | 1998-07-01 | Catalyst for olefin polymer production |
DE69813556T DE69813556T2 (en) | 1997-07-02 | 1998-07-01 | CATALYSTS FOR THE PRODUCTION OF OLEFIN POLYMERS |
EP98934238A EP0993464B1 (en) | 1997-07-02 | 1998-07-01 | Catalyst for the production of olefin polymers |
BRPI9810213-3A BR9810213B1 (en) | 1997-07-02 | 1998-07-01 | catalyst for the production of olefin polymers. |
AT98934238T ATE237622T1 (en) | 1997-07-02 | 1998-07-01 | CATALYSTS FOR THE PRODUCTION OF OLEFIN POLYMERS |
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EP (1) | EP0993464B1 (en) |
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AT (1) | ATE237622T1 (en) |
AU (1) | AU735915B2 (en) |
BR (1) | BR9810213B1 (en) |
CA (1) | CA2295215C (en) |
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EP1308450A3 (en) * | 2001-11-06 | 2003-10-01 | Symyx Technologies, Inc. | Titanium substituted pyridyl amine complexes, catalysts and processes for polymerizing ethylene and styrene |
US6927256B2 (en) * | 2001-11-06 | 2005-08-09 | Dow Global Technologies Inc. | Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent |
US6911506B2 (en) * | 2001-12-10 | 2005-06-28 | Chevron Phillips Chemical Company Lp | Catalyst composition and olefin polymerization using same |
US6864205B2 (en) * | 2001-12-18 | 2005-03-08 | Univation Technologies, Llc | Heterocyclic-amide catalyst compositions for the polymerization of olefins |
US6831187B2 (en) * | 2001-12-18 | 2004-12-14 | Univation Technologies, Llc | Multimetallic catalyst compositions for the polymerization of olefins |
US6919467B2 (en) * | 2001-12-18 | 2005-07-19 | Univation Technologies, Llc | Imino-amide catalyst compositions for the polymerization of olefins |
US7199255B2 (en) * | 2001-12-18 | 2007-04-03 | Univation Technologies, Llc | Imino-amide catalysts for olefin polymerization |
US7166553B2 (en) * | 2002-05-06 | 2007-01-23 | Union Carbide Chemicals & Plastics Technology Corporation | Mixed catalyst compositions for the production of polyolefins |
US7105672B2 (en) * | 2002-08-19 | 2006-09-12 | The University Of Hong Kong | Cyclometallated catalysts |
WO2004026925A1 (en) | 2002-09-17 | 2004-04-01 | Dow Global Technologies Inc. | Improved process for manufacture of polymers |
US20080153997A1 (en) * | 2006-12-20 | 2008-06-26 | Exxonmobil Research And Engineering | Polymer production at supercritical conditions |
US8008412B2 (en) * | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
US7459500B2 (en) * | 2002-11-05 | 2008-12-02 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
US7579407B2 (en) * | 2002-11-05 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
BRPI0408967B8 (en) | 2003-03-31 | 2021-07-27 | Hoffmann La Roche | kit and methods for detecting a nucleic acid from various members of the Japanese encephalitis virus serogroup in a biological sample under stringent hybridization conditions |
US6953764B2 (en) * | 2003-05-02 | 2005-10-11 | Dow Global Technologies Inc. | High activity olefin polymerization catalyst and process |
US7094848B2 (en) * | 2003-05-13 | 2006-08-22 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system |
JP2005152889A (en) * | 2003-11-06 | 2005-06-16 | Sumitomo Chemical Co Ltd | Trimerization catalyst for olefin and method for trimerizing olefin by using the same |
US7119153B2 (en) * | 2004-01-21 | 2006-10-10 | Jensen Michael D | Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength |
WO2005073283A1 (en) * | 2004-01-22 | 2005-08-11 | Dow Global Technologies Inc. | Functionalized elastomer compositions |
SG151301A1 (en) | 2004-03-17 | 2009-04-30 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene multi- block copolymer formation |
BRPI0508173B1 (en) | 2004-03-17 | 2016-03-15 | Dow Global Technologies Inc | multiblock copolymers, polymer, copolymer, a functional derivative, homogeneous polymer blend, process for preparing a propylene-containing multiblock copolymer and process for preparing a 4-methyl-1-pentene multiblock copolymer |
AU2005224258B2 (en) | 2004-03-17 | 2010-09-02 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
US7598328B2 (en) * | 2004-04-07 | 2009-10-06 | Dow Global Technologies, Inc. | Supported catalysts for manufacture of polymers |
US7939251B2 (en) | 2004-05-06 | 2011-05-10 | Roche Molecular Systems, Inc. | SENP1 as a marker for cancer |
WO2006007094A2 (en) | 2004-06-16 | 2006-01-19 | Dow Global Technologies Inc. | Technique for selecting polymerization modifiers |
US7459510B2 (en) * | 2004-06-21 | 2008-12-02 | Exxonmobil Chemical Patents Inc. | Polymerization process |
EP1805226A1 (en) * | 2004-10-29 | 2007-07-11 | Exxonmobil Chemical Patents Inc. | Catalyst compound containing divalent tridentate ligand |
WO2006099053A1 (en) * | 2005-03-09 | 2006-09-21 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins |
US7414006B2 (en) * | 2005-03-09 | 2008-08-19 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins |
WO2006101596A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
US9410009B2 (en) | 2005-03-17 | 2016-08-09 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
EP2894176B1 (en) | 2005-03-17 | 2022-06-01 | Dow Global Technologies LLC | Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation |
CN100441602C (en) * | 2005-04-22 | 2008-12-10 | 中国石油化工股份有限公司 | Composite catalytic system for preparing wide/dual-peak distributed high density polyethylene |
CN100441603C (en) * | 2005-04-22 | 2008-12-10 | 中国石油化工股份有限公司 | Composite catalytic system for preparing wide/dual-peak distributed high density polyethylene |
US7301040B2 (en) * | 2005-08-18 | 2007-11-27 | Fina Technology, Inc. | Bidentate catalyst for olefin polymerization, methods of forming such and products therefrom |
BR122017016853B1 (en) * | 2005-09-15 | 2018-05-15 | Dow Global Technologies Inc. | PROCESS FOR POLYMERIZING ONE OR MORE POLYMERIZABLE MONOMERS BY ADDITION |
CA2622720A1 (en) | 2005-09-15 | 2007-03-29 | Dow Global Technologies Inc. | Catalytic olefin block copolymers via polymerizable shuttling agent |
CN101312980B (en) | 2005-09-28 | 2016-01-20 | 陶氏环球技术有限责任公司 | High reactivity, low molecular weight olefin polymerization process |
US7439205B2 (en) * | 2005-11-21 | 2008-10-21 | Fina Technology, Inc. | Tridentate metal catalyst for olefin polymerization |
US20070117713A1 (en) * | 2005-11-21 | 2007-05-24 | Abbas Razavi | Tridentate metal catalyst for olefin polymerization |
WO2007092136A2 (en) * | 2006-02-03 | 2007-08-16 | Exxonmobil Chemical Patents, Inc. | Process for generating alpha olefin comonomers |
US7982085B2 (en) * | 2006-02-03 | 2011-07-19 | Exxonmobil Chemical Patents Inc. | In-line process for generating comonomer |
US8003839B2 (en) * | 2006-02-03 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Process for generating linear apha olefin comonomers |
US8362265B2 (en) * | 2006-05-05 | 2013-01-29 | Dow Global Technologies, Llc | Hafnium complexes of heterocyclic organic ligands |
WO2007130306A2 (en) * | 2006-05-05 | 2007-11-15 | Dow Global Technologies Inc. | Ortho-metallated hafnium complexes of imidazole ligands |
US8354484B2 (en) * | 2006-05-17 | 2013-01-15 | Dow Global Technologies, Llc | High temperature solution polymerization process |
US8404915B2 (en) * | 2006-08-30 | 2013-03-26 | Exxonmobil Chemical Patents Inc. | Phosphine ligand-metal compositions, complexes, and catalysts for ethylene trimerizations |
US8242237B2 (en) * | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
WO2008085659A1 (en) * | 2007-01-08 | 2008-07-17 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine ether catalysts |
US20080182951A1 (en) * | 2007-01-08 | 2008-07-31 | Ackerman Lily J | Chromium Pyridine Bis(Oxazoline) And Related Catalysts For Ethylene Dimerization |
US8067609B2 (en) * | 2007-01-08 | 2011-11-29 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine thioether catalysts |
WO2008085655A1 (en) * | 2007-01-08 | 2008-07-17 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins with chromium pyridine mono-oxazoline catalysts |
WO2008109212A1 (en) * | 2007-03-06 | 2008-09-12 | Exxonmobil Chemical Patents Inc. | Polymer production under supersolution conditions |
KR20100015391A (en) * | 2007-03-07 | 2010-02-12 | 다우 글로벌 테크놀로지스 인크. | Tethered supported transition metal complex |
ITMI20070878A1 (en) * | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | PROCESS FOR POLYMERIZZAINE OF TACTICAL POLYMERS USING CHIRAL CATALYSTS |
ITMI20070877A1 (en) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | PROCESS FOR THE PRODUCTION OF MULTI-BLOCKED COPOLYMERS WITH THE USE OF POLAR SOLVENTS |
US8281332B2 (en) * | 2007-05-02 | 2012-10-02 | Google Inc. | Animated video overlays |
JP2010529253A (en) * | 2007-06-04 | 2010-08-26 | エクソンモービル・ケミカル・パテンツ・インク | Very homogeneous solution polymerization of propylene |
CA2711162A1 (en) * | 2007-12-31 | 2009-07-16 | Dow Global Technologies Inc. | Process for polymerizing olefin-based polymers |
US8318875B2 (en) * | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
US8674040B2 (en) * | 2008-07-25 | 2014-03-18 | Exxonmobil Chemical Patents Inc. | Pyridyldiamido transition metal complexes, production and use thereof |
US8394902B2 (en) | 2008-07-25 | 2013-03-12 | Exxonmobil Chemical Patents Inc. | Pyridyldiamido transition metal complexes, production and use thereof |
US7973116B2 (en) * | 2008-07-25 | 2011-07-05 | Exxonmobil Chemical Patents Inc. | Pyridyldiamido transition metal complexes, production and use thereof |
US8710163B2 (en) | 2008-07-25 | 2014-04-29 | Exxonmobil Chemical Patents Inc. | Pyridyldiamido transition metal complexes, production and use thereof |
JP2012506329A (en) * | 2008-10-23 | 2012-03-15 | バーゼル・ポリオレフィン・ゲーエムベーハー | Injection stretch blow molding process for the production of polyethylene containers, preforms and bottles |
WO2010110801A1 (en) | 2009-03-27 | 2010-09-30 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization reaction processes exhibiting reduced fouling |
US8318874B2 (en) | 2009-06-26 | 2012-11-27 | Dow Global Technologies Llc | Process of selectively polymerizing ethylene and catalyst therefor |
KR101741855B1 (en) | 2009-06-29 | 2017-05-30 | 셰브론 필립스 케미컬 컴퍼니 엘피 | Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates |
ES2547867T3 (en) | 2009-06-29 | 2015-10-09 | Chevron Phillips Chemical Company Lp | The use of hydrogen elimination catalysts to control the molecular weight of the polymer and hydrogen levels in a polymerization reactor |
US7858718B1 (en) | 2009-07-22 | 2010-12-28 | Equistar Chemicals, Lp | Catalysts based on 2-aryl-8-anilinoquinoline ligands |
US8158733B2 (en) | 2009-07-22 | 2012-04-17 | Equistar Chemicals, Lp | Catalysts based on 2-(2-aryloxy)quinoline or 2-(2-aryloxy)dihydroquinoline ligands |
US8153544B2 (en) | 2009-07-22 | 2012-04-10 | Equistar Chemicals, Lp | Method for preparing non-metallocene catalysts |
BR112012001942B1 (en) | 2009-07-29 | 2019-10-22 | Dow Global Technologies Llc | multifunctional chain exchange agent, process for preparing a multifunctional chain exchange agent, process for preparing a multifunctional composition, multifunctional composition, process for preparing a multifunctional chain exchange agent containing poly radical polyolefin, telequel polyolefin, process for preparing a terminal functionality polyolefin with battery separator |
US20110054122A1 (en) * | 2009-08-31 | 2011-03-03 | Jerzy Klosin | Catalyst and process for polymerizing an olefin and polyolefin prepared thereby |
US8716400B2 (en) * | 2009-10-02 | 2014-05-06 | Dow Global Technologies Llc | Block composites and impact modified compositions |
BR112012007271B1 (en) | 2009-10-02 | 2021-03-23 | Dow Global Technologies Llc | ELASTOMER COMPOSITION AND ARTICLE |
JP5806218B2 (en) | 2009-10-02 | 2015-11-10 | ダウ グローバル テクノロジーズ エルエルシー | Block composite and impact-resistant modified composition |
US8563658B2 (en) | 2009-10-02 | 2013-10-22 | Dow Global Technologies, Llc | Block composites in thermoplastic vulcanizate applications |
KR101827023B1 (en) * | 2010-02-19 | 2018-02-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Metal-ligand complexes and catalysts |
EP3549960B1 (en) | 2010-02-19 | 2021-03-24 | Dow Global Technologies LLC | Process for polymerizing an olefin monomer and catalyst therefor |
SG183230A1 (en) | 2010-03-09 | 2012-09-27 | Exxonmobil Chem Patents Inc | System and method for selective trimerization |
MX350592B (en) | 2010-05-17 | 2017-09-11 | Dow Global Tech Llc * | Process for selectively polymerizing ethylene and catalyst therefor. |
KR101826210B1 (en) | 2010-06-21 | 2018-02-06 | 다우 글로벌 테크놀로지스 엘엘씨 | Crystalline block composites as compatibilizers |
KR101820183B1 (en) | 2010-06-21 | 2018-01-18 | 다우 글로벌 테크놀로지스 엘엘씨 | Crystalline block composites as compatibilizers |
US8822599B2 (en) | 2010-06-21 | 2014-09-02 | Dow Global Technologies Llc | Crystalline block composites as compatibilizers |
JP5792294B2 (en) | 2010-06-21 | 2015-10-07 | ダウ グローバル テクノロジーズ エルエルシー | Crystalline block composites as compatibilizers |
US20120016092A1 (en) | 2010-07-14 | 2012-01-19 | Sandor Nagy | Catalysts based on quinoline precursors |
CA2713042C (en) | 2010-08-11 | 2017-10-24 | Nova Chemicals Corporation | Method of controlling polymer architecture |
KR20180066258A (en) | 2010-08-25 | 2018-06-18 | 다우 글로벌 테크놀로지스 엘엘씨 | Process for polymerizing a polymerizable olefin and catalyst therefor |
WO2012061706A1 (en) | 2010-11-04 | 2012-05-10 | Dow Global Technologies Llc | Double shuttling of polyolefin polymeryl chains |
WO2012103080A1 (en) | 2011-01-26 | 2012-08-02 | Dow Global Technologies Llc | Process for making a polyolefin-polysiloxane block copolymer |
US8907031B2 (en) | 2011-04-20 | 2014-12-09 | Chevron Phillips Chemical Company Lp | Imino carbene compounds and derivatives, and catalyst compositions made therefrom |
CA2739969C (en) | 2011-05-11 | 2018-08-21 | Nova Chemicals Corporation | Improving reactor operability in a gas phase polymerization process |
US9296836B2 (en) * | 2011-05-12 | 2016-03-29 | Dow Global Technologies Llc | Non-cyclopentadienyl-based chromium catalysts for olefin polymerization |
CN103890023B (en) | 2011-10-24 | 2016-11-16 | 三菱化学株式会社 | Composition for thermoplastic elastomer and manufacture method thereof |
CA2760264C (en) | 2011-12-05 | 2018-08-21 | Nova Chemicals Corporation | Passivated supports for use with olefin polymerization catalysts |
SG11201402933PA (en) | 2011-12-14 | 2014-07-30 | Dow Global Technologies Llc | Functionalized block composite and crystalline block composite compositions as compatibilizers |
BR112014014508B1 (en) | 2011-12-14 | 2020-12-01 | Dow Global Technologies Llc | composition |
US9522855B2 (en) | 2011-12-29 | 2016-12-20 | Dow Global Technologies Llc | Process for producing low molecular weight ethylene- and alpha-olefin-based materials |
WO2013101376A1 (en) | 2011-12-29 | 2013-07-04 | Dow Global Technologies Llc | Hyperbranched olefin oil-based dielectric fluid |
US8524972B1 (en) | 2012-04-18 | 2013-09-03 | Exxonmobil Chemical Patents Inc. | Low temperature steam stripping for byproduct polymer and solvent recovery from an ethylene oligomerization process |
US8691916B2 (en) | 2012-05-07 | 2014-04-08 | Dow Global Technologies Llc | Retortable easy opening seals for film extrusion |
CA2783494C (en) | 2012-07-23 | 2019-07-30 | Nova Chemicals Corporation | Adjusting polymer composition |
SG11201505073SA (en) | 2012-12-27 | 2015-07-30 | Dow Global Technologies Llc | A polymerization process for producing ethylene based polymers |
WO2014105413A1 (en) | 2012-12-27 | 2014-07-03 | Dow Global Technologies Llc | An ethylene based polymer |
US20150337062A1 (en) | 2012-12-27 | 2015-11-26 | Dow Global Technologies Llc | Ethylene Based Polymer |
JP6393693B2 (en) | 2012-12-27 | 2018-09-19 | ダウ グローバル テクノロジーズ エルエルシー | Catalytic system for olefin polymerization. |
EP2938649B1 (en) | 2012-12-27 | 2019-04-10 | Dow Global Technologies LLC | A polymerization process for producing ethylene based polymers |
US9102773B2 (en) | 2013-02-06 | 2015-08-11 | Exxonmobil Chemical Patents Inc. | Process for controlling molecular weight of polyolefins prepared using pyridyl diamide catalyst systems |
CN105339334B (en) | 2013-06-28 | 2017-10-24 | 陶氏环球技术有限责任公司 | The method of Slight branching hydrophobe and corresponding surfactant and its application for preparing |
SG11201510689SA (en) | 2013-06-28 | 2016-01-28 | Dow Global Technologies Llc | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
ES2750647T3 (en) | 2013-10-15 | 2020-03-26 | Dow Global Technologies Llc | Mixtures of compatible polyolefins |
WO2015061440A1 (en) | 2013-10-25 | 2015-04-30 | Dow Global Technologies Llc | Polyethylene and polypropylene composition suitable for the use as retortable easy opening seals |
US9315593B2 (en) | 2013-11-15 | 2016-04-19 | Exxonmobil Chemical Patents Inc. | Catalyst systems comprising pyridyldiamido transition metal complexes and chain transfer agent and use thereof |
US9260552B2 (en) | 2013-11-15 | 2016-02-16 | Exxonmobil Chemical Patents Inc. | Process to produce polymers from pyridyldiamido transition metal complexes and use thereof |
WO2015073157A1 (en) | 2013-11-15 | 2015-05-21 | Exxonmobil Chemical Patents Inc. | Process to produce polymers from pyridyldiamido transition metal complexes and use thereof |
US9290519B2 (en) | 2013-11-15 | 2016-03-22 | Exxonmobil Chemical Patents Inc. | Pyridyldiamido transition metal complexes, production and use thereof |
JP6549578B2 (en) | 2013-12-19 | 2019-07-24 | ダウ グローバル テクノロジーズ エルエルシー | Metal-ligand complex, olefin polymerization catalyst derived therefrom, and olefin polymerization method using the catalyst |
US9315526B2 (en) | 2014-03-03 | 2016-04-19 | Exxonmobil Chemical Patents Inc. | Pyridyldiamido transition metal complexes, production and use thereof |
US20170152377A1 (en) | 2014-06-26 | 2017-06-01 | Dow Global Technologies Llc | Breathable films and articles incorporating same |
CA2952031C (en) | 2014-06-26 | 2022-10-04 | Dow Global Technologies Llc | Cast films with improved toughness |
BR112016029163B8 (en) | 2014-06-26 | 2022-07-26 | Dow Global Technologies Llc | BLOWN FILM, ARTICLE AND FOAM FILM |
WO2016003878A1 (en) | 2014-06-30 | 2016-01-07 | Dow Global Technologies Llc | Catalyst systems for olefin polymerization |
BR112016029439B1 (en) | 2014-06-30 | 2022-01-04 | Dow Global Technologies Llc | PROCESS TO FORM AN OLEFIN-BASED POLYMER |
EP3453452A3 (en) | 2015-03-13 | 2019-06-05 | Dow Global Technologies Llc | Phosphacycle-containing ligand for chromium complex and olefin oligomerisation catalyst therefrom |
CN107636027B (en) | 2015-04-20 | 2023-01-03 | 埃克森美孚化学专利公司 | Supported catalyst system and method of use |
US10533063B2 (en) | 2015-04-20 | 2020-01-14 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
US10647786B2 (en) | 2015-04-20 | 2020-05-12 | Exxonmobil Chemical Patents, Inc. | Supported catalyst systems and processes for use thereof |
CA2891693C (en) | 2015-05-21 | 2022-01-11 | Nova Chemicals Corporation | Controlling the placement of comonomer in an ethylene copolymer |
CA2892552C (en) | 2015-05-26 | 2022-02-15 | Victoria Ker | Process for polymerization in a fluidized bed reactor |
CA2892882C (en) | 2015-05-27 | 2022-03-22 | Nova Chemicals Corporation | Ethylene/1-butene copolymers with enhanced resin processability |
KR102620055B1 (en) | 2015-06-30 | 2024-01-03 | 다우 글로벌 테크놀로지스 엘엘씨 | Polypropylene/inorganic particle blend composition for PVC-free wear layer in resilient flooring |
WO2017003565A1 (en) | 2015-06-30 | 2017-01-05 | Exxonmobil Chemical Patents Inc. | Transition metal complexes of tridentate dianionic cnn ligands, production and use thereof |
ES2811135T3 (en) | 2015-06-30 | 2021-03-10 | Dow Global Technologies Llc | A polymerization process to produce ethylene-based polymers |
US9598444B2 (en) | 2015-06-30 | 2017-03-21 | Exxonmobil Chemical Patents Inc. | Transition metal complexes of tridentate dianionic CNN ligands, production and use thereof |
CN107787336B (en) | 2015-06-30 | 2021-05-28 | 陶氏环球技术有限责任公司 | Polymerization process for preparing ethylene-based polymers |
US11041029B2 (en) | 2015-08-31 | 2021-06-22 | Exxonmobil Chemical Patents Inc. | Aluminum alkyls with pendant olefins for polyolefin reactions |
CN107922528B (en) | 2015-08-31 | 2020-11-03 | 埃克森美孚化学专利公司 | Polymers produced by using vinyl transfer agents |
US10618988B2 (en) | 2015-08-31 | 2020-04-14 | Exxonmobil Chemical Patents Inc. | Branched propylene polymers produced via use of vinyl transfer agents and processes for production thereof |
EP3344385A4 (en) | 2015-08-31 | 2019-08-14 | ExxonMobil Chemical Patents Inc. | Aluminum alkyls with pendant olefins on clays |
US9982067B2 (en) | 2015-09-24 | 2018-05-29 | Exxonmobil Chemical Patents Inc. | Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports |
CN108026115B (en) | 2015-09-30 | 2021-11-09 | 陶氏环球技术有限责任公司 | Multi-head or double-head composition capable of being used for chain shuttling and preparation method thereof |
US10870713B2 (en) | 2015-09-30 | 2020-12-22 | Dow Global Technologies Llc | Procatalyst and polymerization process using the same |
CN108377649B (en) | 2015-09-30 | 2021-04-23 | 陶氏环球技术有限责任公司 | Polymerization process for producing ethylene-based polymers |
US9975973B2 (en) | 2015-10-02 | 2018-05-22 | Exxonmobil Chemical Patents Inc. | Asymmetric fluorenyl-substituted salan catalysts |
US10000593B2 (en) | 2015-10-02 | 2018-06-19 | Exxonmobil Chemical Patents Inc. | Supported Salan catalysts |
US9994657B2 (en) | 2015-10-02 | 2018-06-12 | Exxonmobil Chemical Patents Inc. | Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports |
US9982076B2 (en) | 2015-10-02 | 2018-05-29 | Exxonmobil Chemical Patents Inc. | Supported bis phenolate transition metals complexes, production and use thereof |
US9994658B2 (en) | 2015-10-02 | 2018-06-12 | Exxonmobil Chemical Patents Inc. | Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports |
US10414887B2 (en) | 2015-10-02 | 2019-09-17 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and methods of using same |
MX2018004335A (en) | 2015-10-29 | 2018-05-22 | Dow Global Technologies Llc | Crosslinkable polymeric compositions for flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation. |
EP3214124B2 (en) | 2016-03-02 | 2022-06-08 | Dow Global Technologies LLC | An ethylene/alpha-olefin copolymer composition, and articles comprising the same |
ES2703602T3 (en) | 2016-03-03 | 2019-03-11 | Dow Global Technologies Llc | Polyethylene composition, method for manufacturing it, and films made from it |
ES2849149T3 (en) | 2016-03-03 | 2021-08-16 | Dow Global Technologies Llc | Artificial grasses and method of making them |
EP3214116B1 (en) | 2016-03-03 | 2021-06-23 | Dow Global Technologies LLC | Breathable films and method of making the same |
WO2017173074A1 (en) | 2016-03-31 | 2017-10-05 | Dow Global Technologies Llc | An olefin polymerization catalyst |
CN108884196B (en) | 2016-03-31 | 2021-06-18 | 陶氏环球技术有限责任公司 | Olefin polymerization catalyst system and method of using same |
US10968289B2 (en) | 2016-03-31 | 2021-04-06 | Dow Global Technologies Llc | Olefin polymerization catalyst systems and methods of use thereof |
US10927196B2 (en) | 2016-06-30 | 2021-02-23 | Exxonmobil Chemical Patents Inc. | Long chain branched polypropylene via polymerization with aluminum vinyl transfer agent |
US10208140B2 (en) | 2016-06-30 | 2019-02-19 | Exxonmobil Chemical Patents Inc. | Quinolinyldiamido transition metal complexes, production and use thereof |
US10562987B2 (en) | 2016-06-30 | 2020-02-18 | Exxonmobil Chemical Patents Inc. | Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents |
WO2018005201A1 (en) | 2016-06-30 | 2018-01-04 | Exxonmobil Chemical Patents Inc. | Quinolinyldiamido transition metal complexes, production and use thereof |
WO2018022871A1 (en) | 2016-07-29 | 2018-02-01 | Dow Global Technologies Llc | SYNTHESIS OF m-TERPHENYL PENDANT BIS-ETHER LIGANDS AND METAL COMPLEX AND THEIR USE IN OLEFIN POLYMERIZATION |
US10150821B2 (en) | 2016-07-29 | 2018-12-11 | Exxonmobil Chemical Patents Inc. | Heterocyclic amido transition metal complexes, production and use thereof |
WO2018022249A1 (en) | 2016-07-29 | 2018-02-01 | Exxonmobil Chemical Patents Inc. | Heterocyclic amido transition metal complexes, production and use thereof |
MX2019003247A (en) | 2016-09-28 | 2019-08-05 | Dow Global Technologies Llc | Blown films with improved properties. |
MX2019003242A (en) | 2016-09-30 | 2019-08-05 | Dow Global Technologies Llc | Resin for use as tie layers in multilayer films and multilayer films comprising the same. |
WO2018064553A1 (en) | 2016-09-30 | 2018-04-05 | Dow Global Technologies Llc | Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same |
EP3519474A1 (en) | 2016-09-30 | 2019-08-07 | Dow Global Technologies LLC | Process for preparing multi- or dual-headed compositions useful for chain shuttling |
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WO2018064493A1 (en) | 2016-09-30 | 2018-04-05 | Dow Global Technologies Llc | Phosphaguanidine group iv metal olefin polymerization catalysts |
KR102459739B1 (en) | 2016-09-30 | 2022-10-28 | 다우 글로벌 테크놀로지스 엘엘씨 | Double-linked phosphoguanidine Group 4 metal complex and olefin polymerization catalyst produced therefrom |
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US10626200B2 (en) | 2017-02-28 | 2020-04-21 | Exxonmobil Chemical Patents Inc. | Branched EPDM polymers produced via use of vinyl transfer agents and processes for production thereof |
US10676551B2 (en) | 2017-03-01 | 2020-06-09 | Exxonmobil Chemical Patents Inc. | Branched ethylene copolymers produced via use of vinyl transfer agents and processes for production thereof |
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EP3596146B1 (en) | 2017-03-15 | 2023-07-19 | Dow Global Technologies LLC | Catalyst system for multi-block copolymer formation |
US20200247936A1 (en) | 2017-03-15 | 2020-08-06 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
KR102648625B1 (en) | 2017-03-15 | 2024-03-19 | 다우 글로벌 테크놀로지스 엘엘씨 | Catalyst system for forming multi-block copolymers |
CN110582518B (en) | 2017-03-15 | 2022-08-09 | 陶氏环球技术有限责任公司 | Catalyst system for forming multi-block copolymers |
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CN112236505A (en) | 2018-03-08 | 2021-01-15 | 埃克森美孚化学专利公司 | Ethylene-propylene branched copolymers as viscosity modifiers with enhanced fuel economy |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996033202A2 (en) * | 1995-04-17 | 1996-10-24 | Lyondell Petrochemical Company | Transition metal catalyst based on bidentate ligands containing pyridine or quinoline moiety |
EP0803520A1 (en) * | 1996-04-25 | 1997-10-29 | Basf Aktiengesellschaft | Polymerization catalysts containing beta-diketiminate-ligands |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB880998A (en) | 1962-01-01 | 1961-11-01 | Dunlop Rubber Co | Polymerisation of unsaturated aliph atic compounds and catalyst therefor |
GB1400453A (en) | 1971-07-21 | 1975-07-16 | Ici Ltd | Copolymerisation of olefins |
US4508842A (en) | 1983-03-29 | 1985-04-02 | Union Carbide Corporation | Ethylene polymerization using supported vanadium catalyst |
US4897455A (en) | 1985-06-21 | 1990-01-30 | Exxon Chemical Patents Inc. | Polymerization process |
US4808561A (en) | 1985-06-21 | 1989-02-28 | Exxon Chemical Patents Inc. | Supported polymerization catalyst |
US4791180A (en) | 1985-12-12 | 1988-12-13 | Exxon Chemical Patents Inc. | New polymerization catalyst |
US4752597A (en) | 1985-12-12 | 1988-06-21 | Exxon Chemical Patents Inc. | New polymerization catalyst |
US5077255A (en) | 1986-09-09 | 1991-12-31 | Exxon Chemical Patents Inc. | New supported polymerization catalyst |
JP2618384B2 (en) | 1986-12-27 | 1997-06-11 | 三井石油化学工業株式会社 | Solid catalyst for olefin polymerization and its preparation |
WO1988008432A1 (en) | 1987-04-20 | 1988-11-03 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for polymerizing olefin |
US5206199A (en) | 1987-04-20 | 1993-04-27 | Mitsui Petrochemical Industries, Ltd. | Catalyst for polymerizing an olefin and process for polymerizing an olefin |
US5026797A (en) | 1987-10-22 | 1991-06-25 | Mitsubishi Petrochemical Co., Ltd. | Process for producing ethylene copolymers |
JPH0669244B2 (en) | 1987-11-06 | 1994-08-31 | 住友電気工業株式会社 | Magnetic levitation transfer system |
AU608945B2 (en) * | 1987-11-30 | 1991-04-18 | Dow Chemical Company, The | Catalysts prepared from tetrakis(dialkylamide or diarylamide)derivatives of titanium and polymerization of olefins therewith |
US5340786A (en) | 1988-02-12 | 1994-08-23 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for the polymerization of olefins |
US5008228A (en) | 1988-03-29 | 1991-04-16 | Exxon Chemical Patents Inc. | Method for preparing a silica gel supported metallocene-alumoxane catalyst |
US5147949A (en) | 1988-03-29 | 1992-09-15 | Exxon Chemical Patents Inc. | Polymerization process using a silica gel supported metallocene-alumoxane catalyst |
US5086025A (en) | 1988-03-29 | 1992-02-04 | Exxon Chemical Patents Inc. | Method for preparing a silica gel supported metallocene-alumoxane catalyst |
US5039766A (en) * | 1988-06-28 | 1991-08-13 | Sumitomo Chemical Company, Limited | Liquid catalyst component, catalyst system containing said component and process for producing ethylene-alpha-olefin copolymer using said catalyst system |
US4845067A (en) | 1988-07-01 | 1989-07-04 | Union Carbide Corporation | Catalyst for regulating the molecular weight distribution of ethylene polymers |
US4914253A (en) | 1988-11-04 | 1990-04-03 | Exxon Chemical Patents Inc. | Method for preparing polyethylene wax by gas phase polymerization |
US5086024A (en) | 1988-12-02 | 1992-02-04 | Texas Alkyls, Inc. | Catalyst system for polymerization of olefins |
US4999327A (en) | 1988-12-30 | 1991-03-12 | Union Carbide Chemicals And Plastics Company Inc. | Catalyst for regulating the molecular weight distribution of ethylene polymers |
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. |
JPH0445110A (en) | 1990-06-12 | 1992-02-14 | Japan Synthetic Rubber Co Ltd | Production of ethylenic copolymer |
EP0569388B1 (en) * | 1990-12-27 | 1996-03-13 | Exxon Chemical Patents Inc. | An amido transition metal compound and a catalyst system for the production of isotactic polypropylene |
JPH04285607A (en) * | 1991-03-15 | 1992-10-09 | Sumitomo Chem Co Ltd | Production of ethylene-alpha-olefin copolymer |
DE59204800D1 (en) | 1991-05-27 | 1996-02-08 | Hoechst Ag | Process for the production of syndiotactic polyolefins with a broad molecular weight distribution |
EP0702030B1 (en) | 1991-05-27 | 2001-03-21 | TARGOR GmbH | Process for preparing olefin polymers with large molecular weight distribution |
US5155079A (en) | 1991-06-07 | 1992-10-13 | Quantum Chemical Corporation | Multiple site olefin polymerization catalysts |
US5308815A (en) | 1991-07-26 | 1994-05-03 | Ethyl Corporation | Heterogeneous methylaluminoxane catalyst system |
DE69310390T2 (en) | 1992-01-23 | 1997-10-23 | Mitsui Petrochemical Ind | Process for producing a polyolefin |
EP0578838A1 (en) | 1992-04-29 | 1994-01-19 | Hoechst Aktiengesellschaft | Olefin polymerization catalyst, process for its preparation, and its use |
US5240894A (en) | 1992-05-18 | 1993-08-31 | Exxon Chemical Patents Inc. | Method for making and using a supported metallocene catalyst system |
DE59305691D1 (en) | 1992-05-26 | 1997-04-17 | Hoechst Ag | Process for the production of polyolefin waxes |
US5434116A (en) | 1992-06-05 | 1995-07-18 | Tosoh Corporation | Organic transition metal compound having π-bonding heterocyclic ligand and method of polymerizing olefin by using the same |
US5332706A (en) | 1992-12-28 | 1994-07-26 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
US5420220A (en) | 1993-03-25 | 1995-05-30 | Mobil Oil Corporation | LLDPE films |
GB9300934D0 (en) | 1993-01-19 | 1993-03-10 | Bp Chem Int Ltd | Metallocene complexes |
EP0619325B1 (en) | 1993-04-07 | 2001-08-29 | ATOFINA Research | Process for preparing polyolefin catalysts |
WO1994025495A1 (en) | 1993-05-20 | 1994-11-10 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
US5422325A (en) | 1993-09-17 | 1995-06-06 | Exxon Chemical Patents Inc. | Supported polymerization catalysts, their production and use |
US5466649A (en) | 1993-10-15 | 1995-11-14 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
WO1995011264A1 (en) * | 1993-10-21 | 1995-04-27 | Mobil Oil Corporation | Polyolefin blends of bimodal molecular weight distribution |
US5595950A (en) | 1993-12-20 | 1997-01-21 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
US5468702A (en) | 1994-07-07 | 1995-11-21 | Exxon Chemical Patents Inc. | Method for making a catalyst system |
FI97632B (en) | 1995-01-23 | 1996-10-15 | Ev Group Oy | Method for washing tissues, especially paper machine tissues |
PL322446A1 (en) * | 1995-01-24 | 1998-02-02 | Du Pont | Alpha-olefines and olefinic polymers and methods of obtaining them |
DE69600841T2 (en) | 1995-03-08 | 1999-03-18 | Shell Int Research | BRIDGED TO AMIDO COMPOUNDS OF A GROUP IV METAL IN A CATALYTIC COMPOSITION |
US5519099A (en) | 1995-06-07 | 1996-05-21 | Industrial Technology Research Institute | Organometallic catalysts containing hydrotris(pyrazolyl) borate and cyclopentadienyl groups, and processes of employing the same |
US5714556A (en) * | 1995-06-30 | 1998-02-03 | E. I. Dupont De Nemours And Company | Olefin polymerization process |
IT1275777B1 (en) | 1995-07-06 | 1997-10-17 | Enichem Spa | METALLOCENIC CATALYST FOR THE (CO) POLYMERIZATION OF OLEFINS |
ID16442A (en) * | 1996-01-22 | 1997-10-02 | Dow Chemical Co | WEIGHT POLYMER ETHYLENE ULTRA LOW MOLECULES |
FI102476B1 (en) * | 1996-05-31 | 1998-12-15 | Borealis As | New transition metal complexes and method for their preparation |
GB9708487D0 (en) | 1997-04-25 | 1997-06-18 | Bp Chem Int Ltd | Novel catalysts for olefin polymerisation |
US6103657A (en) | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
US6136748A (en) * | 1997-07-02 | 2000-10-24 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for the polymerization of olefins |
US6117959A (en) * | 1998-09-02 | 2000-09-12 | Eastman Chemical Company | Polyolefin catalysts |
-
1998
- 1998-06-23 US US09/103,620 patent/US6103657A/en not_active Expired - Lifetime
- 1998-07-01 CA CA002295215A patent/CA2295215C/en not_active Expired - Fee Related
- 1998-07-01 DE DE69813556T patent/DE69813556T2/en not_active Expired - Lifetime
- 1998-07-01 JP JP50737199A patent/JP3491761B2/en not_active Expired - Fee Related
- 1998-07-01 AT AT98934238T patent/ATE237622T1/en not_active IP Right Cessation
- 1998-07-01 ZA ZA985782A patent/ZA985782B/en unknown
- 1998-07-01 AR ARP980103187A patent/AR016297A1/en not_active Application Discontinuation
- 1998-07-01 ES ES98934238T patent/ES2191946T3/en not_active Expired - Lifetime
- 1998-07-01 WO PCT/US1998/013781 patent/WO1999001460A1/en active IP Right Grant
- 1998-07-01 EP EP98934238A patent/EP0993464B1/en not_active Expired - Lifetime
- 1998-07-01 AU AU83806/98A patent/AU735915B2/en not_active Ceased
- 1998-07-01 BR BRPI9810213-3A patent/BR9810213B1/en not_active IP Right Cessation
- 1998-07-16 TW TW087111591A patent/TW467921B/en not_active IP Right Cessation
- 1998-12-18 US US09/216,163 patent/US6265513B1/en not_active Expired - Lifetime
- 1998-12-18 US US09/213,627 patent/US6320002B1/en not_active Expired - Fee Related
-
1999
- 1999-12-08 US US09/456,853 patent/US6320005B1/en not_active Expired - Lifetime
-
2001
- 2001-10-24 US US10/001,381 patent/US6610627B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996033202A2 (en) * | 1995-04-17 | 1996-10-24 | Lyondell Petrochemical Company | Transition metal catalyst based on bidentate ligands containing pyridine or quinoline moiety |
EP0803520A1 (en) * | 1996-04-25 | 1997-10-29 | Basf Aktiengesellschaft | Polymerization catalysts containing beta-diketiminate-ligands |
Non-Patent Citations (2)
Title |
---|
GIBSON V C ET AL: "Synthesis and structural characterisation of aluminium imino-amide and pyridyl-amide complexes: bulky monoanionic N,N chelate ligands via methyl group transfer", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 550, no. 1-2, 15 January 1998 (1998-01-15), pages 453-456, XP004109893 * |
ORRELL K G ET AL: "Stereochemically non-rigid transition metal complexes of 2,6-bis[1 -(phenylimino)ethyl]pyridine (BIP). Part 3. Dynamic NMR studies of fac-[PtXMe3(BIP)] (X=C1, Br, or I). Crystal structure of fac -[PtIMe3(BIP)]", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 555, no. 1, 25 March 1998 (1998-03-25), pages 35-47, XP004112400 * |
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US6713577B2 (en) | 2000-11-07 | 2004-03-30 | Symyx Technologies, Inc. | Substituted pyridyl amine catalysts and processes for polymerizing and polymers |
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US8383730B2 (en) | 2004-08-19 | 2013-02-26 | Univation Technologies, Llc | Bimodal polyethylene compositions for blow molding applications |
US8202940B2 (en) | 2004-08-19 | 2012-06-19 | Univation Technologies, Llc | Bimodal polyethylene compositions for blow molding applications |
WO2006036748A2 (en) * | 2004-09-22 | 2006-04-06 | Symyx Technologies, Inc. | Heterocycle-amine ligands, compositions, complexes, and catalysts, and methods of making and using the same |
WO2006036748A3 (en) * | 2004-09-22 | 2006-07-27 | Symyx Technologies Inc | Heterocycle-amine ligands, compositions, complexes, and catalysts, and methods of making and using the same |
US7387980B2 (en) | 2004-09-22 | 2008-06-17 | Symyx Technologies, Inc. | Methods of using heterocycle-amine ligands, compositions, complexes, and catalysts |
US7642324B2 (en) | 2004-09-22 | 2010-01-05 | Symyx Solutions, Inc. | Methods of using heterocycle-amine ligands, compositions, complexes, and catalysts |
US7642216B2 (en) | 2004-09-22 | 2010-01-05 | Symyx Solutions, Inc. | Methods of using heterocycle-amine ligands, compositions, complexes, and catalysts |
US7256296B2 (en) | 2004-09-22 | 2007-08-14 | Symyx Technologies, Inc. | Heterocycle-amine ligands, compositions, complexes, and catalysts |
US6987152B1 (en) | 2005-01-11 | 2006-01-17 | Univation Technologies, Llc | Feed purification at ambient temperature |
US7504055B2 (en) | 2005-02-07 | 2009-03-17 | Univation Technologies, Llc | Polyethylene blend compositions |
US7312279B2 (en) | 2005-02-07 | 2007-12-25 | Univation Technologies, Llc | Polyethylene blend compositions |
US7432328B2 (en) | 2005-06-14 | 2008-10-07 | Univation Technologies, Llc | Enhanced ESCR bimodal HDPE for blow molding applications |
US7868092B2 (en) | 2005-06-14 | 2011-01-11 | Univation Technologies, Llc | Bimodal polyethylene compositions for blow molding applications |
US7858702B2 (en) | 2005-06-14 | 2010-12-28 | Univation Technologies, Llc | Enhanced ESCR bimodal HDPE for blow molding applications |
EP2103633A1 (en) | 2005-09-14 | 2009-09-23 | Univation Technologies, LLC | Method for operating a gas-phase reactor while controlling polymer stickiness |
US8066423B2 (en) | 2005-11-16 | 2011-11-29 | Univation Technologies, Llc | High speed and direct driven rotating equipment for polyolefin manufacturing |
EP3467077A1 (en) | 2006-10-03 | 2019-04-10 | Univation Technologies, LLC | System for olefin polymerization |
US9133081B2 (en) | 2007-11-15 | 2015-09-15 | Univation Technologies, Llc | Methods for the removal of impurities from polymerization feed streams |
EP3309182A2 (en) | 2007-11-15 | 2018-04-18 | Univation Technologies, LLC | Polymerization catalysts, methods of making; methods of using, and polyolefinproducts made therefrom |
EP2112175A1 (en) | 2008-04-16 | 2009-10-28 | ExxonMobil Chemical Patents Inc. | Activator for metallocenes comprising one or more halogen substituted heterocyclic heteroatom containing ligand coordinated to an alumoxane |
WO2010071798A1 (en) | 2008-12-18 | 2010-06-24 | Univation Technologies, Llc | Method for seed bed treatment for a polymerization reaction |
WO2011103280A1 (en) | 2010-02-18 | 2011-08-25 | Univation Technologies, Llc | Methods for operating a polymerization reactor |
WO2011103402A1 (en) | 2010-02-22 | 2011-08-25 | Univation Technologies, Llc | Catalyst systems and methods for using same to produce polyolefin products |
WO2011129956A1 (en) | 2010-04-13 | 2011-10-20 | Univation Technologies, Llc | Polymer blends and films made therefrom |
WO2012009215A1 (en) | 2010-07-16 | 2012-01-19 | Univation Technologies, Llc | Systems and methods for measuring static charge on particulates |
WO2012009216A1 (en) | 2010-07-16 | 2012-01-19 | Univation Technologies, Llc | Systems and methods for measuring particle accumulation on reactor surfaces |
WO2012015898A1 (en) | 2010-07-28 | 2012-02-02 | Univation Technologies, Llc | Systems and methods for measuring velocity of a particle/fluid mixture |
WO2012074710A1 (en) | 2010-11-30 | 2012-06-07 | Univation Technologies, Llc. | Catalyst composition having improved flow characteristics and methods of making and using the same |
WO2012074709A1 (en) | 2010-11-30 | 2012-06-07 | Univation Technologies, Llc | Processes for the polymerization of olefins with extracted metal carboxylate salts |
WO2012082674A1 (en) | 2010-12-17 | 2012-06-21 | Univation Technologies, Llc | Systems and methods for recovering hydrocarbons from a polyolefin purge gas product |
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WO2013028283A1 (en) | 2011-08-19 | 2013-02-28 | Univation Technologies, Llc | Catalyst systems and methods for using same to produce polyolefin products |
US9234060B2 (en) | 2011-11-08 | 2016-01-12 | Univation Technologies, Llc | Methods of preparing a catalyst system |
WO2013070601A2 (en) | 2011-11-08 | 2013-05-16 | Univation Technologies, Llc | Methods of preparing a catalyst system |
WO2013070602A1 (en) | 2011-11-08 | 2013-05-16 | Univation Technologies, Llc | Methods for producing polyolefins with catalyst systems |
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WO2014149361A1 (en) | 2013-03-15 | 2014-09-25 | Univation Technologies, Llc | Ligands for catalysts |
EP3287473A1 (en) | 2013-06-05 | 2018-02-28 | Univation Technologies, LLC | Protecting phenol groups |
WO2014197169A1 (en) | 2013-06-05 | 2014-12-11 | Univation Technologies, Llc | Protecting phenol groups |
EP3747913A1 (en) | 2014-04-02 | 2020-12-09 | Univation Technologies, LLC | Continuity compositions and olefin polymerisation method using the same |
WO2015153082A1 (en) | 2014-04-02 | 2015-10-08 | Univation Technologies, Llc | Continuity compositions and methods of making and using the same |
CN106795181B (en) * | 2014-09-17 | 2019-10-08 | 维尔萨利斯股份公司 | The pyridine complex of zirconium, the catalyst system of pyridine complex comprising the zirconium and the technique that makes conjugated diene (co) polymerization |
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KR20170057277A (en) * | 2014-09-17 | 2017-05-24 | 베르살리스 에스.피.에이. | Pyridine complex of zirconium, catalytic system comprising said pyridine complex of zirconium and process of (co)polymerization of conjugated dienes |
KR102418429B1 (en) * | 2014-09-17 | 2022-07-06 | 베르살리스 에스.피.에이. | Pyridine complex of zirconium, catalytic system comprising said pyridine complex of zirconium and process of (co)polymerization of conjugated dienes |
WO2016145179A1 (en) | 2015-03-10 | 2016-09-15 | Univation Technologies, Llc | Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes |
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WO2018048472A1 (en) | 2016-09-09 | 2018-03-15 | Exxonmobil Chemical Patents Inc. | Pilot plant scale semi-condensing operation |
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WO2019217173A1 (en) | 2018-05-02 | 2019-11-14 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
WO2019213227A1 (en) | 2018-05-02 | 2019-11-07 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
WO2023069407A1 (en) | 2021-10-21 | 2023-04-27 | Univation Technologies, Llc | Bimodal poly(ethylene-co-1-alkene) copolymer and blow-molded intermediate bulk containers made therefrom |
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WO2024081272A1 (en) | 2022-10-11 | 2024-04-18 | Dow Global Technologies Llc | Bimodal hdpe and polyethylene blend containing virgin and recycled hdpe materials |
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US6103657A (en) | 2000-08-15 |
CA2295215A1 (en) | 1999-01-14 |
CA2295215C (en) | 2005-05-17 |
US20020065379A1 (en) | 2002-05-30 |
JP3491761B2 (en) | 2004-01-26 |
DE69813556D1 (en) | 2003-05-22 |
EP0993464B1 (en) | 2003-04-16 |
BR9810213A (en) | 2001-10-02 |
AR016297A1 (en) | 2001-07-04 |
ZA985782B (en) | 1999-01-21 |
EP0993464A1 (en) | 2000-04-19 |
US6610627B2 (en) | 2003-08-26 |
AU8380698A (en) | 1999-01-25 |
DE69813556T2 (en) | 2004-01-29 |
AU735915B2 (en) | 2001-07-19 |
US6265513B1 (en) | 2001-07-24 |
JP2001524162A (en) | 2001-11-27 |
US6320002B1 (en) | 2001-11-20 |
US6320005B1 (en) | 2001-11-20 |
TW467921B (en) | 2001-12-11 |
ES2191946T3 (en) | 2003-09-16 |
BR9810213B1 (en) | 2010-05-04 |
ATE237622T1 (en) | 2003-05-15 |
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