WO2004050718A1 - Bimetallic indenoindolyl catalysts - Google Patents
Bimetallic indenoindolyl catalysts Download PDFInfo
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- WO2004050718A1 WO2004050718A1 PCT/US2003/028209 US0328209W WO2004050718A1 WO 2004050718 A1 WO2004050718 A1 WO 2004050718A1 US 0328209 W US0328209 W US 0328209W WO 2004050718 A1 WO2004050718 A1 WO 2004050718A1
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- indenoindolyl
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- 0 Cl*(C1C=CC=C1)(*1CCCCCCC1)Cl Chemical compound Cl*(C1C=CC=C1)(*1CCCCCCC1)Cl 0.000 description 3
- BMGLVVNENOOPFC-UHFFFAOYSA-N C(c1c-2cccc1)c1c-2[nH]c2ccccc12 Chemical compound C(c1c-2cccc1)c1c-2[nH]c2ccccc12 BMGLVVNENOOPFC-UHFFFAOYSA-N 0.000 description 1
- JDTRVJYDVHSJKB-UHFFFAOYSA-N C(c1ccccc1-1)c2c-1c1ccccc1[nH]2 Chemical compound C(c1ccccc1-1)c2c-1c1ccccc1[nH]2 JDTRVJYDVHSJKB-UHFFFAOYSA-N 0.000 description 1
- QOTHVYKPVUKABU-UHFFFAOYSA-N CC(C12)c3ccccc3C1N(C)c1c2cc(C)cc1 Chemical compound CC(C12)c3ccccc3C1N(C)c1c2cc(C)cc1 QOTHVYKPVUKABU-UHFFFAOYSA-N 0.000 description 1
- WMEMQYIMQRZARJ-UHFFFAOYSA-N CC1c2ccccc2C2N(C)C(C=CC(C)=C3)C3=C12 Chemical compound CC1c2ccccc2C2N(C)C(C=CC(C)=C3)C3=C12 WMEMQYIMQRZARJ-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/00—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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
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- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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- C08F2420/00—Metallocene catalysts
- C08F2420/05—Cp or analog where at least one of the carbon atoms of the coordinating ring is replaced by a heteroatom
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- C08F2420/00—Metallocene catalysts
- C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
Definitions
- the invention relates to catalyst systems that include bimetallic complexes having covalently linked indenoindolyl ligands.
- the catalysts are useful for olefin polymerization.
- Ziegler-Natta catalysts are a mainstay for polyolefin manufacture
- single-site (metallocene and non-metallocene) catalysts represent the industry's future. These catalysts are often more reactive than Ziegler-Natta catalysts, and they often produce polymers with improved physical properties.
- Organometallic complexes that incorporate "indenoindolyl" ligands are known (see U.S. Pat. Nos. 6,232,260 and 6,451 ,724). in many of the known complexes, an indenoindolyl group is bridged to another group, which may be a second indenoindolyl group.
- the ligands are versatile because a wide variety of indanone and aryihydrazine precursors can be used to produce indenoindoles. Thus, substituent effects can be exploited and catalyst structure can be altered to produce polyolefins having a desirable balance of physical and mechanical properties.
- the complexes disclosed in the '260 and 724 patents are monometallic.
- indenoindolyl complexes One drawback of at least some of the indenoindolyl complexes is their relatively limited ability to produce polyolefins having a desirably low melt index.
- our gas-phase ethylene polymerizations with an indenoindolyl(cyclopentadienyl)zirconium dichloride complex performed in the absence of hydrogen, often failed to give linear low density polyethylene (LLDPE) having a melt index less than about 1.
- LLDPE linear low density polyethylene
- a catalyst will give polymers with fractional melt indices (preferably 0.1-0.8) when the polymerization is performed in the absence of hydrogen.
- conventional indenoindolyl complexes often provide limited opportunities for controlling molecular weight distribution (MWD).
- the complexes typically give polyethylenes having melt index ratios (MIR) in a narrow window in the range of about 17-19, and this value is independent of the amount of comonomer or aluminum activator used. Because of their relatively low MIR values, the resulting polyolefins have a limited degree of processability. Ideally, the MIR value could be increased in a controlled way to enhance processability.
- MIR melt index ratios
- U.S. Pat. No. 6,414,162 describes bimetallic complexes that derive from dianionic indenoindolyl ligands. These complexes can include two metals, each of which is bonded to two indenoindolyl groups, and the indenoindolyl groups are not otherwise linked together.
- bimetallic complexes In sum, there is considerable current interest in bimetallic complexes and their potential value as catalysts for the manufacture of polyolefins because bimetallic complexes can have electronically coupled active sites.
- Known indenoindolyl complexes which are mostly monometallic, have limited ability to give polyolefins with desirably low melt indices and broadenable MWDs.
- the industry would benefit from the availability of new bimetallic catalysts, especially ones that can provide polymers with desirable attributes. Particularly valuable catalysts would capitalize on the inherent flexibility of the indenoindolyl framework.
- the invention is a catalyst system which comprises an activator and a bimetallic complex.
- the complex includes two Group 3-10 transition metals and two monoanionic indenoindolyl groups, each of which is pi-bonded through its cyclopentadienyl ring to one of the metals.
- a divalent linking group joins the indenoindolyl groups through an indenyl carbon or an indolyl nitrogen of each indenoindolyl group.
- the complex includes two or more ancillary ligands bonded to each metal that satisfy the valence of the metals.
- Catalyst systems of the invention are inherently versatile because of the ability to control polymer properties by exploiting substituent effects on the indenoindolyl framework.
- the bimetallic complexes of the invention also have enhanced ability to give polyolefins with desirably low melt indices.
- certain bimetallic indenoindolyl complexes also provide an opportunity to broaden polymer molecular weight distribution and thereby improve processability simply by regulating the amounts of comonomer and activator used in the polymerization.
- Catalyst systems of the invention comprise an activator and a bimetallic indenoindolyl complex.
- the complex includes two metal atoms, which may be the same or different, from Groups 3- 0.
- the complexes include two Group 4-6 transition metals.
- Most preferred are complexes that include two Group 4 transition metal atoms, such as titanium or zirconium.
- indenoindole compound we mean an organic compound that has both indole and indene rings.
- the five-membered rings from each are fused, i.e., they share two carbon atoms.
- the rings are fused such that the indole nitrogen and the only sp 3 -hybridized carbon on the indenyl ring are "trans" to each other.
- indeno[1 ,2- b] ring system such as:
- Suitable ring systems also include those in which the indole nitrogen and the sp 3 -hybridized carbon of the indene are beta to each other, i.e., they are on the same side of the molecule.
- the ring atoms can be unsubstituted or substituted with one or more groups such as alkyl, aryl, aralkyl, halogen, silyl, nitro, dialkylamino, diarylamino, alkoxy, aryloxy, thioether, or the like. Additional fused rings can be present, as long as an indenoindole moiety is present.
- indenoindole compounds are well known. Suitable methods and compounds are disclosed, for example, in U.S. Pat. No. 6,232,260 and references cited therein, including the method of Buu-Hoi and Xuong, , Chem. Soc. (1952) 2225. Suitable procedures also appear in PCT Int. Appls. WO 99/24446 and WO 01/53360.
- the bimetallic complex incorporates two indenoindolyl groups. Each of these groups is "monoanionic," i.e., the cyclopentadienyl ring of each indenoindolyl group has a -1 charge and donates pi electrons to one of the metals.
- the indolyl nitrogen of each indenoindolyl group is typically substituted with an alkyl, aryl, or trialkylsilyl group. Alternatively, the nitrogen is attached to the divalent linking group as described below.
- bimetallic complexes in which the indenoindolyl groups are "dianionic" (see, e.g., U.S. Pat. No. 6,414,162).
- each indenoindole compound is deprotonated at both the indolyl nitrogen and the cyclopentadienyl group.
- the indenoindolyl groups are joined by a divalent linking group.
- the linking group joins the indenoindolyls through an indenyl carbon or an indolyl nitrogen.
- the indenoindolyl groups can be joined through C-G-C, C-G-N, or N- G-N linkages, where G is the linking group, C is an indenyl methylene carbon, and N is an indolyl nitrogen.
- a wide variety of linking groups are suitable for use and are described in the art.
- the linking group can be a conjugated pi-electron system, but it need not be conjugated.
- Suitable divalent linking groups include dialkylsilyl, diarylsilyl, alkylboranyl, arylboranyl, siloxy, polysiloxy, and hydrocarby.l groups.
- Preferred hydrocarbyl groups are alkylene, dialkylene, polyalkylene, arylene, diarylene, polyarylene, cycloalkyl, adamantyl, aralkylene, alkenyl, and alkynyl.
- divalent linking groups are methylene, 1 ,2-dimethylene, polymethylene, 1 ,2-ethenyl, 1 ,2-ethynyl, isopropylidene, 1 ,4-phenylene, ⁇ , ⁇ '-xylyl, 4,4'-biphenylene, 1 ,3-adamantyl, 1 ,4- adamantyl, phenylboranyl, methylboranyl, dimethylsilyl, diphenylsilyl, bis(dimethylsilyl), oxybis(dimethylsilyl), and the like.
- divalent linking groups are described in the background references. (For some examples, see J. Organometal. Chem. 460 (1993) 191 ; 518 (1996) 1 ; 580 (1999) 90.)
- the bimetallic complex includes ancillary ligands that are bonded to each metal.
- Each metal has two or more neutral or anionic ancillary ligands that satisfy the valence of the metals.
- the ancillary ligands can be labile or polymerization-stable, but usually at least one labile ligand (such as halides, alkoxys, aryloxys, alkyls, alkaryls, aryls, dialkylaminos, ' or the like) is present.
- Particularly preferred labile ligands are halides, alkyls, and alkaryls (e.g., chloride, methyl, benzyl).
- Suitable polymerization-stable ligands include cyclopentadienyl, indenyl, fluorenyl, boraaryl, indenoindolyl, and the like.
- the bimetallic complex has the general structure: X n M-J-G-J-MXn in which G is the divalent linking group, each J. is independently an indenoindolyl group, each M is independently a Group 3-10 transition metal, each X is independently an ancillary ligand, and each n satisfies the valence of the metal.
- G is the divalent linking group
- each J. is independently an indenoindolyl group
- each M is independently a Group 3-10 transition metal
- each X is independently an ancillary ligand
- each n satisfies the valence of the metal.
- Particularly preferred complexes have one of the following general structures:
- L is a polymerization-stable ancillary ligand selected from the group consisting of cyclopentadienyl, indenyl, fluorenyl, boraaryl, and indenoindolyl, and R is hydrogen or hydrocarbyl.
- the complexes can be made by any suitable method; those skilled in the art will recognize a variety of acceptable synthetic strategies. Often, the synthesis begins with preparation of the desired indenoindole compound from particular indanone and arylhydrazine precursors. Next, the indenoindoles are usually linked together to give the ligand precursor. The final step normally involves reaction of the ligand precursor with a transition metal source to give the bimetallic complex.
- indenoindole compound is first prepared by reacting 6-methyl-1 -indanone and p- tolylhydrazine. Deprotonation of the indenoindole at nitrogen, followed by reaction with 0.5 eq. of dichlorodimethylsilane gives a bis(indeno[1 ,2- b]indolyl)dimethylsilane (5). This neutral compound is doubly deprotonated and then reacted with 2 eq. of cyclopentadienyl-zirconium trichloride to give the desired bimetallic complex, 6. A similar approach is used to generate phenylboranyl complex 8.
- the ligand precursor is usually deprotonated with at least about 2 equivalents of a strong base. Two equivalents of transition metal source are then added to give the bimetallic complex.
- the ligand precursor is not deprotonated. Instead, the precursor is simply combined (and optionally heated) with a bis(dialkylamino)-substituted transition metal compound. This approach, known as "amine elimination,” gives the complex without a discrete deprotonation step. See, e.g., U.S. Pat. No. 6,440,889.
- transition metal source conveniently has labile ligands such as halide or dialkylamino groups that are easily displaced by indenoindolyl anions. Examples are halides (e.g., TiCI 4 , ZrCI ), alkoxides, amides, and the like.
- Catalyst systems of the invention include, in addition to the bimetallic indenoindolyl complex, an activator.
- the activator helps to ionize the bimetallic complex and activate the catalyst.
- Suitable activators are well known in the art. Examples include alumoxanes (methyl alumoxane (MAO), PMAO, ethyl alumoxane, diisobutyl alumoxane), alkylaluminum compounds (triethylaluminum, diethyl aluminum chloride, trimethylaluminum, triisobutyl aluminum), and the like.
- Suitable activators include acid salts that contain non-nucleophilic anions. These compounds generally consist of bulky ligands attached to boron or aluminum.
- Examples include lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)aluminate, anilinium tetrakis(pentafluorophenyl)- borate, and the like.
- Suitable activators also include organoboranes, which include boron and one or more alkyl, aryl, or aralkyl groups.
- Suitable activators include substituted and unsubstituted trialkyl and triarylboranes such as tris(pentafluorophenyl)borane, triphenylborane, tri-n-octylborane, and the like.
- boron-containing activators are described in U.S. Pat. Nos. 5,153,157, 5,198,401 , and 5,241,025. Suitable activators also include aluminoboronates-reaction products of alkyl aluminum compounds and organoboronic acids-as described in U.S. Pat. Nos. 5,414,180 and 5,648,440. Alumoxane activators, such as MAO, are preferred.
- the optimum amount of activator needed relative to the amount of bimetallic complex depends on many factors, including the nature of the complex and activator, the desired reaction rate, the kind of polyolefin product, the reaction conditions, and other factors. Generally, however, when the activator is an alumoxane or an alkyl aluminum compound, the amount used will be within the range of about 0.01 to about 5000 moles, preferably from about 10 to about 500 moles, and more preferably from about 10 to about 200 moles, of aluminum per mole of transition metal, M. When the activator is an organoborane or an ionic borate or aluminate, the amount used will be within the range of about 0.01 to about 5000 moles, preferably from about 0.1 to about
- the activator can be combined with the complex and added to the reactor as a mixture, or the components can be added to the reactor separately.
- the catalyst systems can be used with a support such as silica, alumina, titania, or the like. Silica is preferred.
- the support is preferably treated
- Thermal treatment consists of heating (or "calcining") the support in a dry atmosphere at elevated temperature, preferably greater than about 100°C, and more preferably from about 150 to about 600°C, prior to use.
- elevated temperature preferably greater than about 100°C, and more preferably from about 150 to about 600°C, prior to use.
- a variety of different chemical treatments can be used, including reaction with
- organo-aluminum, -magnesium, -silicon, or -boron compounds See, for example, the techniques described in U.S. Pat. No. 6,211 ,311.
- the catalyst systems are particularly valuable for polymerizing olefins.
- Preferred olefins are ethylene and C 3 -C 20 ⁇ -olefins such as propylene, 1-butene, 1-hexene, 1-octene, and the like. Mixtures of olefins can be used. Ethylene and
- mixtures of ethylene with C3-C 1 0 ⁇ -olefins are especially preferred.
- olefin polymerization processes can be used. Preferred processes are slurry, bulk, solution, and gas-phase proceses. A slurry or gas- phase process is preferably used. Suitable methods for polymerizing olefins using the catalysts of the invention are described, for example, in U.S. Pat. Nos.
- the polymerizations can be performed over a wide temperature range, such as about -30°C to about 280°C. A more preferred range is from about 30°C to about 180°C; most preferred is the range from about 60°C to about 100°C. Olefin partial pressures normally range from about 15 psia to about
- Catalyst concentrations used for the olefin polymerization depend on many factors. Preferably, however, the concentration ranges from about 0.01 micromoles per liter to about 100 micromoles per liter. Polymerization times depend on the type of process, the catalyst concentration, and other factors. Generally, polymerizations are complete within several seconds to several hours.
- the organometallic complexes are generally prepared in a dry-box under a nitrogen atmosphere. Air-sensitive reagents are transferred by syringe or cannula using standard techniques.
- Butyllithium (1.5 mL of 2.5 M solution in hexane, 3.75 mmol, 2.1 eq.) is added by syringe at room temperature, and the mixture turns bright yellow. The dianion mixture is stirred overnight at room temperature.
- cyclopentadienylzirconium trichloride (1.00 g, 3.55 mmol, 2.0 eq.) is combined with toluene (70 mL) and diethyl ether (10 mL). The dianion is added at room temperature by pipette, and the mixture turns orange.
- a two-liter, stainless-steel reactor is charged with isobutane (900 mL), 1- hexene (100 mL), triisobutylaluminum (0.8 mL of 1.0 M solution in hexane) and optionally hydrogen (measured as a pressure drop from a 7-mL vessel, Table 1).
- the reactor is pressurized with ethylene to 350 psig, and the contents are heated to 70°C.
- a sample of silica-supported catalyst (0.1 to 0.5 g) is injected into the reactor to start the polymerization. Ethylene is supplied on demand to keep the reactor pressure at 350 psig. After 30 min., the reactor is vented to recover polyethylene (10 to 50 g, calculated activities and polymer properties are presented in Table 1).
- complex 10 p-xylyl- coupled bis(indenoindoiyl)zirconium complex
- the bimetallic catalyst also makes it possible to broaden molecular weight distribution in a predictable way by varying the amount of comonomer or aluminum activator.
- An important trade-off is the reduced activity of bimetallic complex 10 versus monometallic complex 3. As Examples 3 and 6 show, the activity of the bimetallic complex can be boosted by including some F15 activator.
- Low Ml material can also be made with complex 8, the phenylboranyl- linked bimetallic complex (see Examples 8-14).
- the molecular weight distribution is broadenable, but to a lesser degree compared with complex 10. Again, the activity of this bimetallic complex is boosted by including F15 activator.
- EXAMPLE B Supported Catalyst from Bimetallic Complex 10
- bimetallic complex 10 (74 mg, 0.13 mmol Zr) is used instead of monometallic complex 3.
- Component loadings: MAO: 9.6 mmol/g silica; Complex 10: 0.022 mmol/g silica (0.044 mmol Zr/g silica. Al/Zr 215.
- results from the gas-phase experiments confirm the results obtained using the slurry process.
- the results show that bimetallic complexes can be used to prepare linear low density polyethylenes having reduced melt index and broadened molecular weight distribution.
- these benefits come at the expense of reduced catalyst activity and slightly less efficient comonomer incorporation (as indicated by higher density).
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60327802T DE60327802D1 (en) | 2002-12-03 | 2003-09-10 | BIMETALIC INDENOINDOLYL CATALYSTS |
EP03754472A EP1567561B1 (en) | 2002-12-03 | 2003-09-10 | Bimetallic indenoindolyl catalysts |
BR0316966-9A BR0316966A (en) | 2002-12-03 | 2003-09-10 | Indenoindolyl bimetallic catalysts |
CA002505685A CA2505685A1 (en) | 2002-12-03 | 2003-09-10 | Bimetallic indenoindolyl catalysts |
AU2003272296A AU2003272296A1 (en) | 2002-12-03 | 2003-09-10 | Bimetallic indenoindolyl catalysts |
MXPA05005910A MXPA05005910A (en) | 2002-12-03 | 2003-09-10 | Bimetallic indenoindolyl catalysts. |
AT03754472T ATE432296T1 (en) | 2002-12-03 | 2003-09-10 | BIMETALLIC INDENOINDOLYL CATALYSTS |
JP2004557119A JP2006509071A (en) | 2002-12-03 | 2003-09-10 | Two metal-containing indenoindolyl catalysts |
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US10/308,842 | 2002-12-03 | ||
US10/308,842 US6841500B2 (en) | 2002-12-03 | 2002-12-03 | Bimetallic indenoindolyl catalysts |
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WO2004050718A1 true WO2004050718A1 (en) | 2004-06-17 |
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PCT/US2003/028209 WO2004050718A1 (en) | 2002-12-03 | 2003-09-10 | Bimetallic indenoindolyl catalysts |
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US (1) | US6841500B2 (en) |
EP (1) | EP1567561B1 (en) |
JP (1) | JP2006509071A (en) |
KR (1) | KR20050085300A (en) |
CN (1) | CN1308354C (en) |
AT (1) | ATE432296T1 (en) |
AU (1) | AU2003272296A1 (en) |
BR (1) | BR0316966A (en) |
CA (1) | CA2505685A1 (en) |
DE (1) | DE60327802D1 (en) |
MX (1) | MXPA05005910A (en) |
WO (1) | WO2004050718A1 (en) |
Cited By (1)
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US8524846B1 (en) | 2009-07-02 | 2013-09-03 | The University Of Toledo | Trianionic ligand precursor compounds and uses thereof in constrained geometry catalysts |
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US7473745B2 (en) * | 2005-09-02 | 2009-01-06 | Equistar Chemicals, Lp | Preparation of multimodal polyethylene |
JP4825648B2 (en) * | 2006-11-28 | 2011-11-30 | 三菱電機株式会社 | Switch control device |
US7863210B2 (en) * | 2007-12-28 | 2011-01-04 | Chevron Phillips Chemical Company Lp | Nano-linked metallocene catalyst compositions and their polymer products |
US8012900B2 (en) * | 2007-12-28 | 2011-09-06 | Chevron Phillips Chemical Company, L.P. | Nano-linked metallocene catalyst compositions and their polymer products |
US8080681B2 (en) | 2007-12-28 | 2011-12-20 | Chevron Phillips Chemical Company Lp | Nano-linked metallocene catalyst compositions and their polymer products |
US7919639B2 (en) * | 2009-06-23 | 2011-04-05 | Chevron Phillips Chemical Company Lp | Nano-linked heteronuclear metallocene catalyst compositions and their polymer products |
KR101894023B1 (en) * | 2011-05-11 | 2018-10-05 | 삼성디스플레이 주식회사 | Condensed-cyclic compound, organic light-emitting diode comprising the same, and flat display device |
US9233996B2 (en) | 2011-09-13 | 2016-01-12 | California Institute Of Technology | Multi-metallic organometallic complexes, and related polymers, compositions, methods and systems |
KR20140075589A (en) | 2012-12-11 | 2014-06-19 | 주식회사 엘지화학 | Novel ligand compound, method for preparing the same, transition metal compound and method for preparing the same |
WO2014092327A1 (en) | 2012-12-11 | 2014-06-19 | 주식회사 엘지화학 | Novel ligand compound and production method for same, and transition metal compound comprising the novel ligand compound and production method for same |
KR101703274B1 (en) * | 2014-08-12 | 2017-02-22 | 주식회사 엘지화학 | Metallocene compounds, catalyst compositions comprising the same, and method for preparing olefin polymers using the same |
EP3510060A1 (en) * | 2016-09-08 | 2019-07-17 | Total Research & Technology Feluy | Process for preparing polypropylene |
WO2018046567A1 (en) * | 2016-09-08 | 2018-03-15 | Total Research & Technology Feluy | Process for preparing polyethylene |
CN110799551B (en) * | 2017-06-20 | 2022-12-13 | 陶氏环球技术有限责任公司 | Biarylphenoxy group IV transition metal catalysts for olefin polymerization |
CN108341903B (en) * | 2018-02-08 | 2020-07-14 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst |
WO2019160710A1 (en) * | 2018-02-19 | 2019-08-22 | Exxonmobil Chemical Patents Inc. | Catalysts, catalyst systems, and methods for using the same |
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- 2003-09-10 EP EP03754472A patent/EP1567561B1/en not_active Expired - Lifetime
- 2003-09-10 WO PCT/US2003/028209 patent/WO2004050718A1/en active Application Filing
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- 2003-09-10 CA CA002505685A patent/CA2505685A1/en not_active Abandoned
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KR20050085300A (en) | 2005-08-29 |
CN1308354C (en) | 2007-04-04 |
US20040106514A1 (en) | 2004-06-03 |
MXPA05005910A (en) | 2005-08-26 |
EP1567561A1 (en) | 2005-08-31 |
US6841500B2 (en) | 2005-01-11 |
JP2006509071A (en) | 2006-03-16 |
CN1708517A (en) | 2005-12-14 |
BR0316966A (en) | 2005-10-25 |
EP1567561B1 (en) | 2009-05-27 |
ATE432296T1 (en) | 2009-06-15 |
AU2003272296A1 (en) | 2004-06-23 |
DE60327802D1 (en) | 2009-07-09 |
CA2505685A1 (en) | 2004-06-17 |
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