US20010007848A1 - Single-site catalysts for olefin polymerization - Google Patents
Single-site catalysts for olefin polymerization Download PDFInfo
- Publication number
- US20010007848A1 US20010007848A1 US09/772,159 US77215901A US2001007848A1 US 20010007848 A1 US20010007848 A1 US 20010007848A1 US 77215901 A US77215901 A US 77215901A US 2001007848 A1 US2001007848 A1 US 2001007848A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- group
- ligand
- aryl
- transition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC1=CC2=C(C=C1)N(C)c1c3c(cc=12)=CC=CC=3.CC1=CC2=C(C=C1)N(C)c1c3c(cc=12)=CC=CC=3.C[Zr](C)(Cl)Cl Chemical compound CC1=CC2=C(C=C1)N(C)c1c3c(cc=12)=CC=CC=3.CC1=CC2=C(C=C1)N(C)c1c3c(cc=12)=CC=CC=3.C[Zr](C)(Cl)Cl 0.000 description 2
- CKGXYRUIGHKWPJ-UHFFFAOYSA-N CC1=CC2=C(C=C1)N(C)C1=C2CC2=CC=CC=C21.CC1=CC=C(NN)C=C1.O=C1CCC2=CC=CC=C12.[H]N1C2=C(C=C(C)C=C2)C2=C1C1=CC=CC=C1C2 Chemical compound CC1=CC2=C(C=C1)N(C)C1=C2CC2=CC=CC=C21.CC1=CC=C(NN)C=C1.O=C1CCC2=CC=CC=C12.[H]N1C2=C(C=C(C)C=C2)C2=C1C1=CC=CC=C1C2 CKGXYRUIGHKWPJ-UHFFFAOYSA-N 0.000 description 1
- YWOQUYASJOJVPR-UHFFFAOYSA-N CN1C2=C(C=CC=C2)C2=C1C1=CC=CC=C1C2 Chemical compound CN1C2=C(C=CC=C2)C2=C1C1=CC=CC=C1C2 YWOQUYASJOJVPR-UHFFFAOYSA-N 0.000 description 1
- YGRCIFRFDDKIRR-UHFFFAOYSA-N Cc(cc1)cc2c1[nH]c-1c2Cc2c-1cccc2 Chemical compound Cc(cc1)cc2c1[nH]c-1c2Cc2c-1cccc2 YGRCIFRFDDKIRR-UHFFFAOYSA-N 0.000 description 1
- UERDRKZGACRLPC-UHFFFAOYSA-N Cc(cc1)cc2c1[n](C)c-1c2Cc2c-1cccc2 Chemical compound Cc(cc1)cc2c1[n](C)c-1c2Cc2c-1cccc2 UERDRKZGACRLPC-UHFFFAOYSA-N 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N O=C(CC1)c2c1cccc2 Chemical compound O=C(CC1)c2c1cccc2 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- HRBKLORGSGUHSB-UHFFFAOYSA-N [H]N1C2=C(C=CC=C2)C2=C1C1=CC3=CC=CC=C3C=C1C2 Chemical compound [H]N1C2=C(C=CC=C2)C2=C1C1=CC3=CC=CC=C3C=C1C2 HRBKLORGSGUHSB-UHFFFAOYSA-N 0.000 description 1
- BMGLVVNENOOPFC-UHFFFAOYSA-N [H]N1C2=C(C=CC=C2)C2=C1C1=CC=CC=C1C2 Chemical compound [H]N1C2=C(C=CC=C2)C2=C1C1=CC=CC=C1C2 BMGLVVNENOOPFC-UHFFFAOYSA-N 0.000 description 1
- JDTRVJYDVHSJKB-UHFFFAOYSA-N [H]N1C2=C(C=CC=C2)C2=C1CC1=CC=CC=C12 Chemical compound [H]N1C2=C(C=CC=C2)C2=C1CC1=CC=CC=C12 JDTRVJYDVHSJKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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 catalysts useful for olefin polymerization.
- the invention relates to “single-site” catalysts that incorporate at least one indenoindolyl ligand.
- bridged complexes are stereospecific catalysts for a-olefin polymerizations, providing a route to isotactic or syndiotactic polypropylene (see, for example, Herzog et al., J. Am. Chem. Soc. 118 (1996) 11988 and Mansel et al., J. Organometal. Chem. 512 (1996) 225).
- the invention is a single-site olefin polymerization catalyst.
- the catalyst comprises an activator and an organometallic complex.
- the organometallic complex comprises a Group 3 to 10 transition or lanthanide metal, M, and at least one indenoindolyl ligand that is -bonded to M.
- the invention includes a three-step method for making the organometallic complex.
- an indanone reacts with an aryl hydrazine in the presence of a basic or acidic catalyst to produce an aryl hydrazone.
- the aryl hydrazone is cyclized in the presence of an acidic catalyst to produce an indenoindole ligand precursor.
- the precursor is deprotonated, and the resulting anion reacts with a Group 3 to 10 transition or lanthanide metal source to produce the desired organometallic complex.
- the invention provides a remarkably simple synthetic route to single-site olefin polymerization catalysts. Because many indanones and aryl hydrazines are commerically available or easily made, a wide variety of organometallic complexes that contain -bonded indenoindolyl ligands can be expeditiously prepared. The ease and inherent flexibility of the synthesis puts polyolefin makers in charge of a new family of single-site catalysts.
- Catalysts of the invention comprise an activator and an organometallic complex.
- the catalysts are “single site” in nature, i.e., they are distinct chemical species rather than mixtures of different species. They typically give polyolefins with characteristically narrow molecular weight distributions (Mw/Mn ⁇ 3) and good, uniform comonomer incorporation.
- the organometallic complex includes a Group 3 to 10 transition or lanthanide metal, M. More preferred complexes include a Group 4 to 6 transition metal; most preferably, the complex contains a Group 4 metal such as titanium or zirconium.
- the organometallic complex also comprises at least one indenoindolyl ligand that is -bonded to M.
- indenoindole 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 or more 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.
- an indeno[3,2-b]indole ring system such as:
- the indene ring is numbered beginning with the —CH 2 - group.
- the “b” side of the indole ring matches the “3,2” side of the indene.
- the order of the numbers (3,2) conforms to the direction of the base (indolyl) component (i.e., from a to b).
- Suitable ring systems 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. This is an indeno[2,3-b]indole ring system:
- any of 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.
- a benzo ring can be fused in the “e,” “f,” or “g” positions of either or both of the indene and indole rings, as in a benzo[f]indeno[3,2-b]indole system:
- Suitable indenoindole ligand precursors include, for example, 5,10-dihydroindeno[3,2-b]indole, 4,8,10-trimethyl-5H-indeno[3,2-b]indole, 4-tert-butyl-8-methyl-5,10-dihydroindeno[3,2-b]indole, 4,8-dichloro-5,10-dihydroindeno[3,2-b]indole, 10-methylbenzo[f]-5H-indeno[3,2-b]indole, benzo[g]-5,10-dihydroindeno[3,2-b]indole, 5,10-dihydroindeno[3,2-b]benzo[e]indole, benzo[g]-5,10-dihydroindeno[3,2-b]benzo[e]indole, and the like.
- the indenoindolyl ligand i s generated by deprotonating a ligand precursor with a base to give an anionic ring system with a high degree of aromaticity ( highly delocalized). Reaction of the anion with, e.g., a transition metal halide gives the desired organometallic complex.
- the indenoindolyl ligand is -bonded to M in the complex.
- the organometallic complex optionally includes one or more additional polymerization-stable, anionic ligands.
- additional polymerization-stable, anionic ligands include substituted and unsubstituted cyclopentadienyl, fluorenyl, and indenyl, or the like, such as those described in U.S. Pat. Nos. 4,791,180 and 4,752,597, the teachings of which are incorporated herein by reference.
- a preferred group of polymerization-stable ligands are heteroatomic ligands such as boraaryl, pyrrolyl, indolyl, quinolinyl, pyridinyl, and azaborolinyl as described in U.S. Pat. Nos.
- the organometallic complex also usually includes one or more labile ligands such as halides, alkyls, alkaryls, aryls, dialkylaminos, or the like. Particularly preferred are halides, alkyls, and alkaryis (e.g., chloride, methyl, benzyl).
- the indenoindolyl and/or polymerization-stable ligands can be bridged.
- a —CH 2 —, —CH 2 CH 2 —, or (CH 3 ) 2 Si bridge can be used to link two indenoindolyl groups through the indolyl nitrogens.
- Groups that can be used to bridge the ligands include, for example, methylene, ethylene, 1,2-phenylene, and dialkyl silyls. Normally, only a single bridge is included. Bridging changes the geometry around the transition or lanthanide metal and can improve catalyst activity and other properties such as comonomer incorporation.
- Exemplary organometallic complexes 10H-indeno[3,2-b]indolyl titanium trichloride, 10H-indeno[3,2-b]indolyl zirconium trichloride, bis(3,7-dimethyl-10H-indeno[3,2-b]indolyl)titanium dimethyl, (3-tert-butyl-8,10-dimethylindeno[3,2-b]indolyl)zirconium trichloride, bis(10H-indeno[3,2-b]indolyl)zirconium dichloride, (10-phenyl-benzo[g]-indeno[3,2-b]indolyl)zirconium trichloride, (cyclopentadienyl)(10H-indeno[3,2-b]indolyl)zirconium dichloride, (8-quinolinoxy)(10H-indeno[3,2-b]indolyl)zi
- the catalysts include an activator.
- Suitable activators ionize the organometallic complex to produce an active olefin polymerization 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.
- 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. These and other suitable boron-containing activators are described in U.S. Pat. Nos. 5,153,157, 5,198,401, and 5,241,025, the teachings of which are incorporated herein by reference.
- the amount of activator needed relative to the amount of organometallic 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 0.1 to about 500 moles, of aluminum per mole of 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 500 moles, of activator per mole of M.
- a catalyst support such as silica or alumina can be used.
- a support is generally not necessary for practicing the process of the invention.
- the invention includes a three-step method for making the organometallic complex.
- a first step an indanone reacts with an aryl hydrazine in the presence of a basic or acidic catalyst to produce an aryl hydrazone by a known synthetic procedure.
- Indanones are bicyclic compounds that have a cyclopentanone ring fused to a benzene ring. Both rings can be unsubstituted or substituted with alkyl, aryl, aralkyl, nitro, halide, thioether, or other groups. Additional fused rings can be present as long as an indanone moiety is present.
- Suitable indanones include, for example, 1-indanone, 2-indanone, 6-methylindan-1-one, 5-chloroindan-1-one, 6-nitroindan-2-one, benzo[f]indan-1-one, and the like, and mixtures thereof.
- Aryl hydrazines are aromatic compounds that have a hydrazine (—NHNH 2 ) group attached to an aromatic ring. They are often used and commercially available in the form of the acid salt, as in phenyl hydrazine hydrochloride.
- the aromatic ring of the aryl hydrazine can be substituted with the groups described above, and it can be fused to other rings.
- Suitable aryl hydrazines include, for example, phenyl hydrazine, p-tolyl hydrazine, m-tolyl hydrazine, p-chlorophenyl hydrazine, 1-naphthyl hydrazine, 2-naphthyl hydrazine, and the like, and mixtures thereof.
- a wide variety of well-known acidic and basic compounds catalyze the reaction between the aryl hydrazine and the indanone. Examples include hydrochloric acid, acetic acid, sulfuric acid, p-toluenesulfonic acid, ammonia, triethylamine, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium acetate, and the like.
- the aryl hydrazine and the indanone are simply heated together with the catalyst, often with a reaction solvent, for a time needed to give the aryl hydrazone.
- the reaction product can be isolated and purified by conventional means (e.g., filtration, recrystallization), but more often, the aryl hydrazone is used in the next step without purification.
- a typical procedure is shown in J. Chem. Soc. (1952) 2225.
- step two the aryl hydrazone cyclizes in the presence of an acidic catalyst in a Fischer indole reaction with elimination of ammonia to give an indenoindole ligand precursor.
- the reaction apparently involves an interesting [3,3]sigmatropic rearrangement (see J. March, Advanced Organic Chemistry, 2 nd ed. (1977) 1054).
- a variety of acidic catalysts are suitable, including, for example, Lewis acids (zinc chloride, boron trifluoride), and protic acids (hydrochloric acid, acetic acid, p-toluenesulfonic acid).
- Lewis acids zinc chloride, boron trifluoride
- protic acids hydrochloric acid, acetic acid, p-toluenesulfonic acid.
- the crude aryl hydrazone is simply heated with the acidic catalyst for a brief period to cause the cyclization reaction.
- the reaction product is isolated and purified by any suitable method.
- the cyclization reaction mixture is poured into ice water and extracted into an organic solvent.
- the solution is dried, filtered, and evaporated to give the crude indenoindole ligand precursor, which can be further purified by recrystallization.
- the ligand precursor is deprotonated by reacting it with at least one equivalent of a potent base such as lithium diisopropylamide, n-butyllithium, sodium hydride, a Grignard reagent, or the like.
- a potent base such as lithium diisopropylamide, n-butyllithium, sodium hydride, a Grignard reagent, or the like.
- the resulting anion is reacted with a Group 3 to 10 transition or lanthanide metal source to produce an organometallic complex.
- the complex comprises the metal, M, and at least one indenoindolyl ligand that is -bonded to the metal. Any convenient source of the Group 3 to 10 transition or lanthanide metal can be used.
- the source is a complex that contains one or more labile ligands that are easily displaced by the indenoindolyl anion. Examples are halides (e.g., TICl 4 , ZrCl 4 ), alkoxides, amides, and the like.
- the metal source can incorporate one or more of the polymerization-stable anionic ligands described earlier.
- the organometallic complex can be used “as is.” Often, however, the complex is converted to an alkyl derivative by treating it with an alkylating agent such as methyl lithium.
- the alkylated complexes are more suitable for use with certain activators (e.g., ionic borates).
- Step three is normally performed by first generating the indenoindolyl anion at low temperature (0° C. to ⁇ 100° C.), preferably in an inert solvent (e.g., a hydrocarbon). The anion is then usually added to a solution of the transition or lanthanide metal source at low to room temperature. After the reaction is complete, by-products and solvents are removed to give the desired transition metal complex. Examples A and B below illustrate typical catalyst syntheses.
- the catalysts 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 C 3 -C 10 ⁇ -olefins are especially preferred.
- the process is practiced in the liquid phase, which can include slurry, solution, suspension, or bulk processes, or a combination of these.
- High-pressure fluid phase or gas phase techniques can also be used.
- the process of the invention is particularly valuable for solution and slurry processes.
- the olefin 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 50,000 psia. More preferred is the range from about 15 psia to about 1000 psia.
- Catalyst concentrations used for the olefin polymerization depend to 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.
- Examples 1-9 below illustrate typical olefin polymerizations using catalysts of the invention. As the examples show, the catalysts have good activity and give polymers with favorable melt-flow properties.
- Slurry polymerizations are performed in a 1.7-L, stainless-steel stirred reactor. Dry, oxygen-free toluene (850 mL) is charged to the clean, dry, oxygen-free reactor at room temperature.
- the activator used in each polymerization is a solution of 10 wt. % methalumoxane (MAO) in toluene (from Ethyl Corporation). The specified amounts (from Table 1 below) of MAO, 1-butene (comonomer), and hydrogen are then added, in that order, to the reactor. The reactor is heated to the desired reaction temperature and allowed to equilibrate.
- MAO methalumoxane
- Ethylene is introduced to give a total pressure in the reactor of 150 psig, and the reactor is again allowed to equilibrate.
- the desired quantity of catalyst, dissolved in toluene, is then injected into the reactor to start the polymerization.
- Ethylene is fed on demand to keep the reactor pressure at 150 psig.
- the ethylene flow is stopped, and the reaction mixture cools to room temperature.
- the polymer is isolated by vacuum filtration, is dried overnight in a vacuum oven, and is weighed and characterized. Table 1 gives polymerization conditions; Table 2 gives polymer properties.
- Example 3 uses a slightly modified procedure: Half of the MAO is added as described above, while the other half is mixed with the organometallic complex and allowed to react for 15 min. prior to injecting the catalyst mixture into the reactor.
- the melt index of the polymer is measured using ASTM D ⁇ 1238, Conditions E and F.
- MI2 is the melt index measured with a 2.16 kg weight (Condition E).
- MI20 is the melt index measured with a 21.6 kg weight (Condition F).
- MFR is the ratio of MI20 to MI2. Densities are measured in using ASTM D-1505.
- Table 1 summarizes process conditions and Table 2 gives polymer properties for the examples.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
- The invention relates to catalysts useful for olefin polymerization. In particular, the invention relates to “single-site” catalysts that incorporate at least one indenoindolyl ligand.
- Interest in single-site (metallocene and non-metallocene) catalysts continues to grow rapidly in the polyolefin industry. These catalysts are more reactive than Ziegler-Natta catalysts, and they produce polymers with improved physical properties. The improved properties include narrow molecular weight distribution, reduced low molecular weight extractables, enhanced incorporation of a-olefin comonomers, lower polymer density, controlled content and distribution of long-chain branching, and modified melt rheology and relaxation characteristics.
- While traditional metallocenes commonly include one or more cyclopentadienyl groups, many other ligands have been used. Putting substituents on the cyclopentadienyl ring, for example, changes the geometry and electronic character of the active site. Thus, a catalyst structure can be fine-tuned to give polymers with desirable properties. “Constrained geometry” or “open architecture” catalysts have been described (see, e.g., U.S. Pat. No. 5,624,878). Bridging ligands in these catalysts lock in a single, well-defined active site for olefin complexation and chain growth. Other bridged complexes are stereospecific catalysts for a-olefin polymerizations, providing a route to isotactic or syndiotactic polypropylene (see, for example, Herzog et al.,J. Am. Chem. Soc. 118 (1996) 11988 and Mansel et al., J. Organometal. Chem. 512 (1996) 225).
- Other known single-site catalysts replace cyclopentadienyl groups with one or more heteroatomic ring ligands such as boraaryl (see, e.g., U.S. Pat. No. 5,554,775), pyrrolyl, indolyl, (U.S. Pat. No. 5,539,124), or azaborolinyl groups (U.S. Pat. No. 5,902,866).
- Substituted metallocenes, constrained-geometry catalysts, bridged complexes, and many heterometallocenes offer interesting advantages, including higher activity, control over polyolefin properties, and stereoregular polymers. Variety, however, comes at a price: ligands used to make many of these catalysts require costly multi-step syntheses from expensive and often hard-to-handle starting materials and reagents.
- In sum, there is a continuing need for single-site catalysts that can be prepared inexpensively and in short order. In particular, there is a need for catalysts that can be tailored to have good activities and to give polyolefins with desirable physical properties.
-
- The invention includes a three-step method for making the organometallic complex. First, an indanone reacts with an aryl hydrazine in the presence of a basic or acidic catalyst to produce an aryl hydrazone. Next, the aryl hydrazone is cyclized in the presence of an acidic catalyst to produce an indenoindole ligand precursor. Finally, the precursor is deprotonated, and the resulting anion reacts with a Group 3 to 10 transition or lanthanide metal source to produce the desired organometallic complex.
- The invention provides a remarkably simple synthetic route to single-site olefin polymerization catalysts. Because many indanones and aryl hydrazines are commerically available or easily made, a wide variety of organometallic complexes that contain -bonded indenoindolyl ligands can be expeditiously prepared. The ease and inherent flexibility of the synthesis puts polyolefin makers in charge of a new family of single-site catalysts.
- Catalysts of the invention comprise an activator and an organometallic complex. The catalysts are “single site” in nature, i.e., they are distinct chemical species rather than mixtures of different species. They typically give polyolefins with characteristically narrow molecular weight distributions (Mw/Mn<3) and good, uniform comonomer incorporation.
- The organometallic complex includes a Group 3 to 10 transition or lanthanide metal, M. More preferred complexes include a Group 4 to 6 transition metal; most preferably, the complex contains a Group 4 metal such as titanium or zirconium.
- The organometallic complex also comprises at least one indenoindolyl ligand that is -bonded to M. By “indenoindole,” 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 or more carbon atoms. Preferably, the rings are fused such that the indole nitrogen and the only sp3-hybridized carbon on the indenyl ring are “trans” to each other. Such is the case in an indeno[3,2-b]indole ring system such as:
-
- Any of 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. For example, a benzo ring can be fused in the “e,” “f,” or “g” positions of either or both of the indene and indole rings, as in a benzo[f]indeno[3,2-b]indole system:
-
- Suitable indenoindole ligand precursors include, for example, 5,10-dihydroindeno[3,2-b]indole, 4,8,10-trimethyl-5H-indeno[3,2-b]indole, 4-tert-butyl-8-methyl-5,10-dihydroindeno[3,2-b]indole, 4,8-dichloro-5,10-dihydroindeno[3,2-b]indole, 10-methylbenzo[f]-5H-indeno[3,2-b]indole, benzo[g]-5,10-dihydroindeno[3,2-b]indole, 5,10-dihydroindeno[3,2-b]benzo[e]indole, benzo[g]-5,10-dihydroindeno[3,2-b]benzo[e]indole, and the like.
- The indenoindolyl ligand i s generated by deprotonating a ligand precursor with a base to give an anionic ring system with a high degree of aromaticity ( highly delocalized). Reaction of the anion with, e.g., a transition metal halide gives the desired organometallic complex. The indenoindolyl ligand is -bonded to M in the complex.
- The organometallic complex optionally includes one or more additional polymerization-stable, anionic ligands. Examples include substituted and unsubstituted cyclopentadienyl, fluorenyl, and indenyl, or the like, such as those described in U.S. Pat. Nos. 4,791,180 and 4,752,597, the teachings of which are incorporated herein by reference. A preferred group of polymerization-stable ligands are heteroatomic ligands such as boraaryl, pyrrolyl, indolyl, quinolinyl, pyridinyl, and azaborolinyl as described in U.S. Pat. Nos. 5,554,775, 5,539,124, 5,637,660, and 5,902,866, the teachings of which are incorporated herein by reference. The organometallic complex also usually includes one or more labile ligands such as halides, alkyls, alkaryls, aryls, dialkylaminos, or the like. Particularly preferred are halides, alkyls, and alkaryis (e.g., chloride, methyl, benzyl).
- The indenoindolyl and/or polymerization-stable ligands can be bridged. For instance, a —CH2—, —CH2CH2—, or (CH3)2Si bridge can be used to link two indenoindolyl groups through the indolyl nitrogens. Groups that can be used to bridge the ligands include, for example, methylene, ethylene, 1,2-phenylene, and dialkyl silyls. Normally, only a single bridge is included. Bridging changes the geometry around the transition or lanthanide metal and can improve catalyst activity and other properties such as comonomer incorporation.
- Exemplary organometallic complexes: 10H-indeno[3,2-b]indolyl titanium trichloride, 10H-indeno[3,2-b]indolyl zirconium trichloride, bis(3,7-dimethyl-10H-indeno[3,2-b]indolyl)titanium dimethyl, (3-tert-butyl-8,10-dimethylindeno[3,2-b]indolyl)zirconium trichloride, bis(10H-indeno[3,2-b]indolyl)zirconium dichloride, (10-phenyl-benzo[g]-indeno[3,2-b]indolyl)zirconium trichloride, (cyclopentadienyl)(10H-indeno[3,2-b]indolyl)zirconium dichloride, (8-quinolinoxy)(10H-indeno[3,2-b]indolyl) titanium dichloride, (1 -methylborabenzene)(10H-indeno[3,2-b]indolyl)zirconium dimethyl, ansa-methylene-N,N′-bis(10H-indeno[3,2-b]indolyl)zirconium dichloride, and the like.
- The catalysts include an activator. Suitable activators ionize the organometallic complex to produce an active olefin polymerization 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. These and other suitable boron-containing activators are described in U.S. Pat. Nos. 5,153,157, 5,198,401, and 5,241,025, the teachings of which are incorporated herein by reference.
- The amount of activator needed relative to the amount of organometallic 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 0.1 to about 500 moles, of aluminum per mole of 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 500 moles, of activator per mole of M.
- If desired, a catalyst support such as silica or alumina can be used. However, the use of a support is generally not necessary for practicing the process of the invention.
- The invention includes a three-step method for making the organometallic complex. In a first step, an indanone reacts with an aryl hydrazine in the presence of a basic or acidic catalyst to produce an aryl hydrazone by a known synthetic procedure.
- Indanones are bicyclic compounds that have a cyclopentanone ring fused to a benzene ring. Both rings can be unsubstituted or substituted with alkyl, aryl, aralkyl, nitro, halide, thioether, or other groups. Additional fused rings can be present as long as an indanone moiety is present. Suitable indanones include, for example, 1-indanone, 2-indanone, 6-methylindan-1-one, 5-chloroindan-1-one, 6-nitroindan-2-one, benzo[f]indan-1-one, and the like, and mixtures thereof.
- Aryl hydrazines are aromatic compounds that have a hydrazine (—NHNH2) group attached to an aromatic ring. They are often used and commercially available in the form of the acid salt, as in phenyl hydrazine hydrochloride. The aromatic ring of the aryl hydrazine can be substituted with the groups described above, and it can be fused to other rings. Suitable aryl hydrazines include, for example, phenyl hydrazine, p-tolyl hydrazine, m-tolyl hydrazine, p-chlorophenyl hydrazine, 1-naphthyl hydrazine, 2-naphthyl hydrazine, and the like, and mixtures thereof.
- The ability to vary the substituents on the indanone and aryl hydrazine provides catalyst makers access to a diverse array of indenoindolyl ligands. This allows them to “fine tune” the activity of the corresponding organometallic complexes and, ultimately, the physical properties of the polyolefins. Because of the unique geometries of their active sites, some of the complexes should be valuable for making stereoregular polyolefins such as isotactic or syndiotactic polypropylene.
- A wide variety of well-known acidic and basic compounds catalyze the reaction between the aryl hydrazine and the indanone. Examples include hydrochloric acid, acetic acid, sulfuric acid, p-toluenesulfonic acid, ammonia, triethylamine, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium acetate, and the like.
- Usually, the aryl hydrazine and the indanone are simply heated together with the catalyst, often with a reaction solvent, for a time needed to give the aryl hydrazone. The reaction product can be isolated and purified by conventional means (e.g., filtration, recrystallization), but more often, the aryl hydrazone is used in the next step without purification. A typical procedure is shown inJ. Chem. Soc. (1952) 2225.
- In step two, the aryl hydrazone cyclizes in the presence of an acidic catalyst in a Fischer indole reaction with elimination of ammonia to give an indenoindole ligand precursor. The reaction apparently involves an interesting [3,3]sigmatropic rearrangement (see J. March,Advanced Organic Chemistry, 2nd ed. (1977) 1054). A variety of acidic catalysts are suitable, including, for example, Lewis acids (zinc chloride, boron trifluoride), and protic acids (hydrochloric acid, acetic acid, p-toluenesulfonic acid). Usually, the crude aryl hydrazone is simply heated with the acidic catalyst for a brief period to cause the cyclization reaction. The reaction product is isolated and purified by any suitable method. In one method, the cyclization reaction mixture is poured into ice water and extracted into an organic solvent. The solution is dried, filtered, and evaporated to give the crude indenoindole ligand precursor, which can be further purified by recrystallization. In contrast to the previous step, it is preferred to purify this reaction product prior to using it in the next step.
- In step three of the method, the ligand precursor is deprotonated by reacting it with at least one equivalent of a potent base such as lithium diisopropylamide, n-butyllithium, sodium hydride, a Grignard reagent, or the like. The resulting anion is reacted with a Group 3 to 10 transition or lanthanide metal source to produce an organometallic complex. The complex comprises the metal, M, and at least one indenoindolyl ligand that is -bonded to the metal. Any convenient source of the Group 3 to 10 transition or lanthanide metal can be used. Usually, the source is a complex that contains one or more labile ligands that are easily displaced by the indenoindolyl anion. Examples are halides (e.g., TICl4, ZrCl4), alkoxides, amides, and the like. The metal source can incorporate one or more of the polymerization-stable anionic ligands described earlier. The organometallic complex can be used “as is.” Often, however, the complex is converted to an alkyl derivative by treating it with an alkylating agent such as methyl lithium. The alkylated complexes are more suitable for use with certain activators (e.g., ionic borates).
- Step three is normally performed by first generating the indenoindolyl anion at low temperature (0° C. to −100° C.), preferably in an inert solvent (e.g., a hydrocarbon). The anion is then usually added to a solution of the transition or lanthanide metal source at low to room temperature. After the reaction is complete, by-products and solvents are removed to give the desired transition metal complex. Examples A and B below illustrate typical catalyst syntheses.
- The catalysts are particularly valuable for polymerizing olefins. Preferred olefins are ethylene and C3-C20 α-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-C10 α-olefins are especially preferred.
- Many types of olefin polymerization processes can be used. Preferably, the process is practiced in the liquid phase, which can include slurry, solution, suspension, or bulk processes, or a combination of these. High-pressure fluid phase or gas phase techniques can also be used. The process of the invention is particularly valuable for solution and slurry processes.
- The olefin 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 50,000 psia. More preferred is the range from about 15 psia to about 1000 psia.
- Catalyst concentrations used for the olefin polymerization depend to 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.
- Examples 1-9 below illustrate typical olefin polymerizations using catalysts of the invention. As the examples show, the catalysts have good activity and give polymers with favorable melt-flow properties.
- The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.
-
- Preparation of Catalyst A
- 3,10-Dimethyl-5H-indeno[3,2-b]indole is deprotonated with n-butyllithium in toluene. A solution of the resulting anion (1.18 g, 0.0049 mol) in tetrahydrofuran (20 mL) is added to a solution of zirconium tetrachloride (0.60 g, 0.0026 mol) in THF (40 mL) at −78° C. After stirring for 15 h at room temperature, a bright red precipitate is isolated and and vacuum dried. The resulting material (0.71 g) is used without further purification. The principal catalyst component is bis(3,10-dimethylindeno[3,2-b]indolyl)zirconium dichloride:
- Preparation of Catalyst B
- 3,10-Dimethyl-5H-indeno[3,2-b]indole is deprotonated with n-butyllithium in diethyl ether. The resulting anionic complex (2.2 g, 0.0703 mol) is dissolved in diethyl ether (50 mL). Zirconium tetrachloride (0.819 g, 0.00352 mol) is added to the anion at −78° C. The reaction mixture is stirred for 15 h at room temperature, and solvent is removed under vacuum to obtain a red catalyst sample that is used without further purification. The principal catalyst component is bis(3,10-dimethylindeno[3,2-b]indolyl)zirconium dichloride.
- Slurry polymerizations are performed in a 1.7-L, stainless-steel stirred reactor. Dry, oxygen-free toluene (850 mL) is charged to the clean, dry, oxygen-free reactor at room temperature. The activator used in each polymerization is a solution of 10 wt. % methalumoxane (MAO) in toluene (from Ethyl Corporation). The specified amounts (from Table 1 below) of MAO, 1-butene (comonomer), and hydrogen are then added, in that order, to the reactor. The reactor is heated to the desired reaction temperature and allowed to equilibrate. Ethylene is introduced to give a total pressure in the reactor of 150 psig, and the reactor is again allowed to equilibrate. The desired quantity of catalyst, dissolved in toluene, is then injected into the reactor to start the polymerization. Ethylene is fed on demand to keep the reactor pressure at 150 psig. At the end of 1 h, the ethylene flow is stopped, and the reaction mixture cools to room temperature. The polymer is isolated by vacuum filtration, is dried overnight in a vacuum oven, and is weighed and characterized. Table 1 gives polymerization conditions; Table 2 gives polymer properties.
- Example 3 uses a slightly modified procedure: Half of the MAO is added as described above, while the other half is mixed with the organometallic complex and allowed to react for 15 min. prior to injecting the catalyst mixture into the reactor.
- The melt index of the polymer is measured using ASTM D−1238, Conditions E and F. MI2 is the melt index measured with a 2.16 kg weight (Condition E). MI20 is the melt index measured with a 21.6 kg weight (Condition F). MFR is the ratio of MI20 to MI2. Densities are measured in using ASTM D-1505.
- Table 1 summarizes process conditions and Table 2 gives polymer properties for the examples.
- The preceding examples are meant only as illustrations. The following claims define the invention.
TABLE 1 Polymerization Conditions Catalyst Amt. MAO Temp. 1-butene Hydrogen Ex. # ID (mmoles) (mmoles) (° C.) (mL) (mmoles) 1 A 8.0 × 10−4 9.0 80 0 0 2 A 3.2 × 10−3 9.0 80 0 0 3 A 3.2 × 10−3 9.0 80 0 0 4 A 3.2 × 10−3 9.0 110 0 0 5 A 8.0 × 10−3 9.0 80 0 0 6 A 8.0 × 10−3 9.0 110 0 60 7 A 8.0 × 10−3 9.0 110 20 60 8 A 3.2 × 10−3 6.0 80 0 0 9 B 8.0 × 10−3 9.0 80 0 0 -
TABLE 2 Polymerization Results Catalyst Polymer Productivity MI2 MI20 Density Ex. # ID wt. (g) (kg/g Zr) (dg/min) (dg/min) (g/mL) 1 A 4.8 65.8 — — — 2 A 29.0 99.4 0.048 1.41 0.963 3 A 21.6 74.0 0.028 0.63 — 4 A 9.4 32.3 1.32 7.98 — 5 A 49.9 68.4 0.62 16.6 0.967 6 A 36.6 50.2 1092 — >0.970 7 A 33.5 45.9 2075 — 0.973 8 A 19.0 65.1 0.023 0.30 — 9 B 31.8 43.6 0.034 1.27 —
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/772,159 US6376629B2 (en) | 1999-10-14 | 2001-01-29 | Single-site catalysts for olefin polymerization |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/417,510 US6232260B1 (en) | 1999-10-14 | 1999-10-14 | Single-site catalysts for olefin polymerization |
US09/772,159 US6376629B2 (en) | 1999-10-14 | 2001-01-29 | Single-site catalysts for olefin polymerization |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/417,510 Division US6232260B1 (en) | 1999-10-14 | 1999-10-14 | Single-site catalysts for olefin polymerization |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010007848A1 true US20010007848A1 (en) | 2001-07-12 |
US6376629B2 US6376629B2 (en) | 2002-04-23 |
Family
ID=23654299
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/417,510 Expired - Lifetime US6232260B1 (en) | 1999-10-14 | 1999-10-14 | Single-site catalysts for olefin polymerization |
US09/772,159 Expired - Fee Related US6376629B2 (en) | 1999-10-14 | 2001-01-29 | Single-site catalysts for olefin polymerization |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/417,510 Expired - Lifetime US6232260B1 (en) | 1999-10-14 | 1999-10-14 | Single-site catalysts for olefin polymerization |
Country Status (3)
Country | Link |
---|---|
US (2) | US6232260B1 (en) |
AU (1) | AU6642300A (en) |
WO (1) | WO2001027125A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6583242B2 (en) * | 2001-08-02 | 2003-06-24 | Equistar Chemicals, Lp | Supported olefin polymerization catalysts |
US20040176241A1 (en) * | 2003-03-04 | 2004-09-09 | Sandor Nagy | Benzoindenoindolyl metal catalysts for olefin polymerization |
Families Citing this family (81)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6451938B1 (en) * | 1997-02-25 | 2002-09-17 | Exxon Mobil Chemical Patents Inc. | Polymerization catalyst system comprising heterocyclic fused cyclopentadienide ligands |
AU1870999A (en) * | 1997-11-12 | 1999-05-31 | Montell Technology Company B.V. | Metallocenes and catalysts for olefin-polymerisation |
US6730754B2 (en) * | 2000-01-18 | 2004-05-04 | Basell Polyolefine Gmbh | Process for producing substantially amorphous propylene-based polymers |
ES2220725T3 (en) * | 2000-02-24 | 2004-12-16 | Basell Polyolefine Gmbh | ORGANOMETAL COMPOSITE USED AS C-CATALYST TO POLYMERIZE OLEFINS. |
US6255415B1 (en) * | 2000-02-29 | 2001-07-03 | Equistar Chemicals, L.P. | Ethylene polymerization process |
US6414162B1 (en) | 2001-04-05 | 2002-07-02 | Equistar Chemicals, Lp | Bimetallic catalysts for olefin polymerization |
US6579957B2 (en) | 2001-04-11 | 2003-06-17 | Equistar Chemicals, Lp | Single-site catalysts based on anionic thiopyran dioxide ligands |
US6541583B2 (en) * | 2001-05-17 | 2003-04-01 | Equistar Chemicals, Lp | Polypropylene preparation |
US6759361B2 (en) * | 2001-06-04 | 2004-07-06 | Equistar Chemicals, Lp | Aluminoboronate activators for single-site olefin polymerization catalysts |
US6489414B1 (en) * | 2001-06-06 | 2002-12-03 | Equistar Chemicals, Lp | Chelating pyrimidines as ligands for single-site olefin polymerization catalysts |
US6440889B1 (en) * | 2001-08-15 | 2002-08-27 | Equistar Chemicals, Lp | Amine elimination process for making single-site catalysts |
US6950725B2 (en) | 2001-12-07 | 2005-09-27 | General Electric Company | Home latch-key web based automation system |
US6586545B1 (en) | 2001-12-20 | 2003-07-01 | Equistar Chemicals, Lp | Complexes based on four-membered cyclic anionic six-electron-donor ligands |
US6596826B1 (en) | 2001-12-20 | 2003-07-22 | Equistar Chemicals, Lp | Olefin polymerization catalysts containing 1,3-diboretanyl ligands |
US6989341B2 (en) | 2002-01-28 | 2006-01-24 | Univation Technologies, Llc | Halogen substituted catalyst system for olefin polymerization |
US6908972B2 (en) * | 2002-04-16 | 2005-06-21 | Equistar Chemicals, Lp | Method for making polyolefins |
US6642326B1 (en) | 2002-05-03 | 2003-11-04 | Equistar Chemicals, Lp | Use of silanes to enhance activity in single-site polymerizations |
US6756455B2 (en) * | 2002-05-31 | 2004-06-29 | Equistar Chemicals, Lp | High-temperature solution process for polyolefin manufacture |
US6762255B2 (en) | 2002-06-06 | 2004-07-13 | Equistar Chemicals L.P. | Prealkylated olefin polymerization catalysts and olefin polymerization employing such catalysts |
US6630547B1 (en) * | 2002-06-11 | 2003-10-07 | Equistar Chemicals, Lp | Use of silanes to control molecular weight in olefin polymerizations |
US6737487B2 (en) * | 2002-07-30 | 2004-05-18 | Equistar Chemicals, Lp | Polyolefin block copolymers |
MXPA05001075A (en) | 2002-08-02 | 2005-06-06 | Equistar Chem Lp | Catalysts and process for making polyolefins. |
US6559251B1 (en) * | 2002-08-02 | 2003-05-06 | Equistar Chemicals, Lp | Process for making low-density polyolefins |
US6765074B2 (en) * | 2002-09-27 | 2004-07-20 | Equistar Chemicals, Lp | Olefin polymerization process |
US6884749B2 (en) | 2002-10-17 | 2005-04-26 | Equistar Chemicals L.P. | Supported catalysts which reduce sheeting in olefin polymerization, process for the preparation and the use thereof |
US6630548B1 (en) | 2002-11-01 | 2003-10-07 | Equistar Chemicals, Lp | Static reduction |
US6841500B2 (en) | 2002-12-03 | 2005-01-11 | Equistar Chemicals, Lp | Bimetallic indenoindolyl catalysts |
US6716936B1 (en) | 2002-12-16 | 2004-04-06 | Equistar Chemicals L.P. | Cascaded boiling pool slurry reactors for producing bimodal low to medium density polyethylene polymers |
US6683150B1 (en) | 2002-12-19 | 2004-01-27 | Equistar Chemicals, Lp | High molecular weight polypropylene process |
US6713576B1 (en) | 2003-02-25 | 2004-03-30 | Equistar Chemicals, Lp | Olefin polymerization catalysts based on convex, polcyclic ligands |
US6693155B1 (en) | 2003-03-05 | 2004-02-17 | Equistar Chemicals, Lp | Propylene polymerization process |
US6984599B2 (en) * | 2003-04-23 | 2006-01-10 | Equistar Chemicals, Lp | Olefin polymerization catalysts based on hydroxyl-depleted calixarene ligands |
US6774078B1 (en) | 2003-04-23 | 2004-08-10 | Equistar Chemicals, Lp | Olefin polymerization catalysts based on annulated cyclopentadienyl ligands |
US6794468B1 (en) | 2003-05-12 | 2004-09-21 | Equistar Chemicals, Lp | Olefin polymerization process |
US6927264B2 (en) * | 2003-05-28 | 2005-08-09 | Dow Global Technologies Inc. | Metal complexes and polymerization process using same |
US6995216B2 (en) * | 2003-06-16 | 2006-02-07 | Equistar Chemicals, Lp | Process for manufacturing single-site polyolefins |
US6998451B2 (en) * | 2003-07-01 | 2006-02-14 | Equistar Chemicals, Lp | Olefin polymerization process |
US6933353B2 (en) * | 2003-07-07 | 2005-08-23 | Equistar Chemicals, Lp | Olefin polymerization process |
US6818713B1 (en) | 2003-08-11 | 2004-11-16 | Equistar Chemicals, Lp | Process for making polyethylene |
US6939930B2 (en) | 2003-09-09 | 2005-09-06 | Equistar Chemicals, Lp | Hydrosilane additives for increased polyolefin molecular weight |
US6958377B2 (en) * | 2003-10-15 | 2005-10-25 | Equistar Chemicals, Lp | Olefin polymerization process |
US7220695B2 (en) * | 2004-01-07 | 2007-05-22 | Exxonmobil Chemical Patents Inc. | Supported activator |
US7741417B2 (en) * | 2004-01-07 | 2010-06-22 | Exxonmobil Chemical Patents Inc. | Preparation of polymerization catalyst activators utilizing indole-modified silica supports |
US20050228156A1 (en) | 2004-04-07 | 2005-10-13 | Holland Charles S | Preparation of polyethylene films |
US6995220B2 (en) * | 2004-04-29 | 2006-02-07 | Equistar Chemicals, Lp | Ethylene polymerization process |
US7402546B2 (en) * | 2004-09-23 | 2008-07-22 | Equistar Chemicals, Lp | Magnesium chloride support |
US6967231B1 (en) | 2004-09-23 | 2005-11-22 | Equistar Chemicals, Lp | Olefin polymerization process |
US7230056B2 (en) * | 2005-07-01 | 2007-06-12 | Equistar Chemicals, Lp | Catalyst preparation method |
US7196147B2 (en) * | 2005-07-01 | 2007-03-27 | Equistar Chemicals, Lp | Olefin polymerization process with improved operability and polymer properties |
US20070010626A1 (en) * | 2005-07-11 | 2007-01-11 | Shankernarayanan Manivakkam J | Polyethylene compositions |
US7273914B2 (en) * | 2005-08-03 | 2007-09-25 | Equistar Chemicals, Lp | Olefin polymerization methods |
US7473745B2 (en) * | 2005-09-02 | 2009-01-06 | Equistar Chemicals, Lp | Preparation of multimodal polyethylene |
US7538173B2 (en) * | 2005-11-21 | 2009-05-26 | Equistar Chemicals Lp | Polyolefin compositions |
US7608327B2 (en) * | 2005-12-20 | 2009-10-27 | Equistar Chemicals, Lp | High tear strength film |
US7423098B2 (en) * | 2006-01-17 | 2008-09-09 | Equistar Chemicals, Lp | Polyethylene process |
US7638584B2 (en) * | 2006-06-20 | 2009-12-29 | Equistar Chemicals, Lp | Olefin polymerization process |
US7638586B2 (en) | 2006-09-26 | 2009-12-29 | Equistar Chemicals, Lp | Olefin polymerization process |
US7429635B2 (en) * | 2006-09-28 | 2008-09-30 | Equistar Chemicals, Lp | Preparation of ultra high molecular weight linear low density polyethylene |
US8475898B2 (en) * | 2007-08-29 | 2013-07-02 | Equistar Chemicals, Lp | Polyolefin resin blends for crack-resistant pipe |
US7666961B2 (en) * | 2007-09-04 | 2010-02-23 | Equistar Chemicals, Lp | Olefin polymerization process |
US7655740B2 (en) * | 2007-09-04 | 2010-02-02 | Equistar Chemicals, Lp | Olefin polymerization process |
US7781549B2 (en) * | 2007-09-04 | 2010-08-24 | Equistar Chemicals, Lp | Olefin polymerization process |
US7723451B2 (en) * | 2007-09-04 | 2010-05-25 | Equistar Chemicals, Lp | Olefin polymerization process |
US8022005B2 (en) | 2007-11-08 | 2011-09-20 | Exxonmobil Chemical Patents Inc. | Halogen substituted heterocyclic heteroatom containing ligands-alumoxane activation of metallocenes |
US7776974B2 (en) * | 2008-04-30 | 2010-08-17 | Equistar Chemicals, Lp | Olefin polymerization process |
US7671151B2 (en) * | 2008-05-21 | 2010-03-02 | Equistar Chemicals, Lp | Olefin polymerization process |
US7829641B2 (en) * | 2008-07-16 | 2010-11-09 | Equistar Chemicals, Lp | Process for the preparation of multimodal polyethylene resins |
US7816478B2 (en) * | 2008-09-03 | 2010-10-19 | Equistar Chemicals, Lp | Polyethylene thick film and process for preparing polyethylene |
US20100129924A1 (en) * | 2008-11-21 | 2010-05-27 | Sandor Nagy | Quality assurance method for olefin polymerization catalysts |
US8524846B1 (en) | 2009-07-02 | 2013-09-03 | The University Of Toledo | Trianionic ligand precursor compounds and uses thereof in constrained geometry catalysts |
KR101650092B1 (en) | 2013-08-01 | 2016-08-22 | 주식회사 엘지화학 | Metallocene compound, catalyst composition comprising the same, and method for preparation of olefin-based polymer using the same |
US9321854B2 (en) | 2013-10-29 | 2016-04-26 | Exxonmobil Chemical Patents Inc. | Aluminum alkyl with C5 cyclic and pendent olefin polymerization catalyst |
WO2016195824A1 (en) | 2015-05-29 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Polymerization process using bridged metallocene compounds supported on organoaluminum treated layered silicate supports |
WO2017039994A1 (en) | 2015-08-31 | 2017-03-09 | Exxonmobil Chemical Patents Inc. | Aluminum alkyls with pendant olefins on clays |
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 |
US11041029B2 (en) | 2015-08-31 | 2021-06-22 | Exxonmobil Chemical Patents Inc. | Aluminum alkyls with pendant olefins for polyolefin reactions |
US10059788B2 (en) | 2016-04-29 | 2018-08-28 | Exxonmobil Chemical Patents Inc. | Organoaluminum activators on clays |
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 |
US20180174147A1 (en) * | 2016-12-15 | 2018-06-21 | Mastercard International Incorporated | Systems and methods for blocking ineligible fraud-related chargebacks |
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 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US5153157A (en) | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US5241025A (en) | 1987-01-30 | 1993-08-31 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US5198401A (en) | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
NZ268270A (en) | 1993-06-24 | 1997-10-24 | Dow Chemical Co | Titanium (ii)- or zirconium (ii)- containing complexes and addition polymerisation catalysts therefrom (m is ti or zr) |
US5466810A (en) | 1994-06-10 | 1995-11-14 | Eli Lilly And Company | 2-amino-3-aroyl-benzo[β]thiophenes and methods for preparing and using same to produce 6-hydroxy-2-(4-hydroxyphenyl)-3-[4-(2-aminoethoxy)-benzoyl]benzo[β]thiophenes |
US5539124A (en) | 1994-12-19 | 1996-07-23 | Occidental Chemical Corporation | Polymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring |
US5554775A (en) | 1995-01-17 | 1996-09-10 | Occidental Chemical Corporation | Borabenzene based olefin polymerization catalysts |
US5637660A (en) | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
WO1996034021A1 (en) | 1995-04-25 | 1996-10-31 | Lyondell Petrochemical Company | Azaborolinyl metal complexes as olefin polymerization catalysts |
AU1870999A (en) | 1997-11-12 | 1999-05-31 | Montell Technology Company B.V. | Metallocenes and catalysts for olefin-polymerisation |
-
1999
- 1999-10-14 US US09/417,510 patent/US6232260B1/en not_active Expired - Lifetime
-
2000
- 2000-08-16 AU AU66423/00A patent/AU6642300A/en not_active Abandoned
- 2000-08-16 WO PCT/US2000/022331 patent/WO2001027125A1/en active Application Filing
-
2001
- 2001-01-29 US US09/772,159 patent/US6376629B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6583242B2 (en) * | 2001-08-02 | 2003-06-24 | Equistar Chemicals, Lp | Supported olefin polymerization catalysts |
US20040176241A1 (en) * | 2003-03-04 | 2004-09-09 | Sandor Nagy | Benzoindenoindolyl metal catalysts for olefin polymerization |
Also Published As
Publication number | Publication date |
---|---|
US6232260B1 (en) | 2001-05-15 |
AU6642300A (en) | 2001-04-23 |
US6376629B2 (en) | 2002-04-23 |
WO2001027125A1 (en) | 2001-04-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6232260B1 (en) | Single-site catalysts for olefin polymerization | |
US6838410B2 (en) | Catalysts for making polyolefins | |
US6908972B2 (en) | Method for making polyolefins | |
US5637660A (en) | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety | |
KR101066969B1 (en) | Method for preparing olefin polymer using transition metal catalyst having better copolymerization | |
EP1456217B1 (en) | Metallocenes and catalyst compositions derived therefrom | |
EP0720627B1 (en) | Catalysts and processes for the polymerization of olefins | |
EP1421090B1 (en) | Metallocenes and catalyst compositions derived therefrom | |
US6111046A (en) | Atactic copolymers of propylene with ethylene | |
EP1664131A1 (en) | Hydrosilane additives for increased polyolefin molecular weight | |
AU653029B2 (en) | Catalyst and process for the preparation of high-molecular-weight polyolefins | |
CA2494611C (en) | Catalyst comprising bridged indeno[1,2-b]indolyl metal complex | |
US6818713B1 (en) | Process for making polyethylene | |
CA2516516C (en) | Propylene polymerization process | |
US5670436A (en) | Metallocene compound | |
US7157591B2 (en) | Metallocenes and catalyst compositions derived therefrom | |
WO2005111094A1 (en) | Ethylene polymerization process | |
EP3783004A1 (en) | Transition metal compound, catalyst composition comprising same, and polymer preparation method using same | |
US6228959B1 (en) | Single-site catalysts containing homoaromatic ligands |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK Free format text: GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AND PATENT APPLICATIONS;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:020704/0562 Effective date: 20071220 Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK Free format text: GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AND PATENT APPLICATIONS;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:020704/0562 Effective date: 20071220 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:021354/0708 Effective date: 20071220 Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNORS:BASELL POLYOLEFINE GMBH;ARCO CHEMICAL TECHNOLOGY L.P.;ARCO CHEMICAL TECHNOLOGY, INC.;AND OTHERS;REEL/FRAME:021354/0708 Effective date: 20071220 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS ADMINISTRATIVE AGENT AND COLLAT Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS, LP;REEL/FRAME:022678/0860 Effective date: 20090303 |
|
XAS | Not any more in us assignment database |
Free format text: SECURITY AGREEMENT;ASSIGNOR:CITIBANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT;REEL/FRAME:022529/0087 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
AS | Assignment |
Owner name: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT, CONN Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS, LP;REEL/FRAME:023449/0687 Effective date: 20090303 Owner name: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT,CONNE Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS, LP;REEL/FRAME:023449/0687 Effective date: 20090303 |
|
AS | Assignment |
Owner name: EQUISTAR CHEMICALS, LP,TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024329/0535 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024329/0535 Effective date: 20100430 |
|
AS | Assignment |
Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P.,DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP,TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P.,DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP,TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP,TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT;REEL/FRAME:024337/0186 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT;REEL/FRAME:024337/0186 Effective date: 20100430 Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P., DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0705 Effective date: 20100430 Owner name: LYONDELL CHEMICAL TECHNOLOGY, L.P., DELAWARE Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A., AS COLLATERAL AGENT;REEL/FRAME:024337/0856 Effective date: 20100430 |
|
AS | Assignment |
Owner name: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS COLLATERA Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS, LP;REEL/FRAME:024342/0443 Effective date: 20100430 |
|
AS | Assignment |
Owner name: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT,CONNE Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS. LP;REEL/FRAME:024351/0001 Effective date: 20100430 Owner name: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT, CONN Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS. LP;REEL/FRAME:024351/0001 Effective date: 20100430 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS ADMINISTRATIVE AGENT,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS, LP;REEL/FRAME:024397/0861 Effective date: 20100430 Owner name: CITIBANK, N.A., AS ADMINISTRATIVE AGENT, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS, LP;REEL/FRAME:024397/0861 Effective date: 20100430 |
|
AS | Assignment |
Owner name: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATE Free format text: SECURITY AGREEMENT;ASSIGNOR:EQUISTAR CHEMICALS, LP;REEL/FRAME:024402/0655 Effective date: 20100430 |
|
REMI | Maintenance fee reminder mailed | ||
AS | Assignment |
Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:DEUTSCHE BANK TRUST COMPANY AMERICAS;REEL/FRAME:032113/0684 Effective date: 20131017 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:BANK OF AMERICA, N.A.;REEL/FRAME:032113/0730 Effective date: 20131016 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:032113/0644 Effective date: 20131018 Owner name: EQUISTAR CHEMICALS, LP, TEXAS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:WELLS FARGO BANK, NATIONAL ASSOCIATION;REEL/FRAME:032112/0786 Effective date: 20131022 Owner name: BANK OF AMERICA, N.A., TEXAS Free format text: APPOINTMENT OF SUCCESSOR ADMINISTRATIVE AGENT;ASSIGNOR:UBS AG, STAMFORD BRANCH;REEL/FRAME:032112/0863 Effective date: 20110304 |
|
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20140423 |