System and method for dual conditioned catalyst for polymerization process

Abstract

The present disclosure relates to a process comprising providing a catalyst slurry comprising a supported catalyst comprising a support material, at least a first catalyst compound, and at least one activator. The process comprises contacting the catalyst slurry with one or more catalyst solutions to obtain a modified catalyst slurry. The one or more catalyst solutions comprises a first catalyst solution comprising a second catalyst compound and a third catalyst compound. The modified catalyst slurry comprises a modified supported catalyst comprising the first catalyst compound, the second catalyst compound, and the third catalyst compound. The process comprises feeding the modified catalyst slurry to a fluidized bed gas phase reactor. The process comprises polymerizing an alpha-olefin in the fluidized bed gas phase reactor under polymerization conditions to obtain a polyolefin.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 635030, filed April 17, 2024, entitled "System and method for dual-trimmed catalysts for polymerization processes," the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to catalyst slurry mixtures. More specifically, this disclosure relates to conditioning catalyst slurry mixtures with one or more conditioning catalyst solutions in polymerization processes (e.g., gas-phase polyethylene (GPPE) polymerization processes and slurry-phase polymerization processes). Background Technology

[0004] Supported multicomponent catalysts are widely used in commercial-scale polymer production because they enable the production of multi-modal polymer resins. For example, supported bicomponent catalysts comprise a support on which two types of active sites are disposed. The relative contribution of the first and second active sites to polymerization determines the composition of the resulting multi-modal polymer resin, where the relative contribution of each active site depends on the ratio of active sites on the supported bicomponent catalyst.

[0005] In some cases, additional catalysts are added to the polymerization process to adjust the catalyst concentration (e.g., trimming) (regarding multi-component supported catalysts), thereby "in situ" modulating one or more properties of the polymer formed in the reactor. However, the degree of freedom associated with this method is limited because the adjustment of the catalyst concentration is determined by the composition of the trimming solution.

[0006] Therefore, it is desirable to develop a trimming process that allows two or more different trimming solutions to be added independently to the polymerization process, thereby providing a greater degree of control over the polymerization process and the properties of the resulting polymer. A trimming process that allows the independent addition of two or more different trimming solutions to the polymerization process would be advantageous in continuous reactor processes because the properties and composition of the resulting polymer can be adjusted in real time to maintain them within the desired specifications.

[0007] References of potential interest in this regard include: U.S. Patent Publications US2022 / 0033537, US2020 / 0071437 and US2022 / 0033535, and U.S. Patents 8,429,100; 6,546,379; 7,505,949; 6,243,696; 11,288,577; 11,203,653; 10,494,462; 9,963,528; and 10,865,259; and U.S. Provisional Patent Application Serials 63 / 503,915; 63 / 503,810; and 63 / 503,851. Summary of the Invention

[0008] This disclosure relates to gas-phase polymerization and methods thereof.

[0009] In at least one embodiment, the method includes providing a catalyst slurry comprising a supported catalyst, the supported catalyst comprising a support material, at least a first catalyst compound, and at least one activator. The method includes contacting the catalyst slurry with one or more catalyst solutions to obtain a modified catalyst slurry. The one or more catalyst solutions comprise a first catalyst solution comprising a second catalyst compound and a third catalyst compound. The modified catalyst slurry comprises a modified supported catalyst comprising a first catalyst compound, a second catalyst compound, and a third catalyst compound. The method includes feeding the modified catalyst slurry into a fluidized bed gas-phase reactor. The method includes polymerizing α-olefins in the fluidized bed gas-phase reactor under polymerization conditions to obtain polyolefins.

[0010] In at least one embodiment, the method includes providing a catalyst slurry comprising a supported catalyst, the supported catalyst comprising a support material, at least a first catalyst compound, and at least one activator. The method includes contacting the catalyst slurry with two or more catalyst solutions to obtain a modified catalyst slurry. The two or more catalyst solutions comprise a first catalyst solution comprising a second catalyst compound and a second catalyst solution, the second catalyst solution comprising a third catalyst compound. The modified catalyst slurry comprises a modified supported catalyst comprising a first catalyst compound, a second catalyst compound, and a third catalyst compound. The method includes feeding the modified catalyst slurry into a fluidized bed gas-phase reactor. The method includes polymerizing α-olefins in a fluidized bed gas-phase reactor under polymerization conditions to obtain polyolefins.

[0011] These and other features and properties of the disclosed methods and systems, and their advantageous applications and / or uses, will become apparent from the following detailed description. Attached Figure Description

[0012] To assist those skilled in the art in creating and using this topic, please refer to the accompanying diagrams, in which:

[0013] Figure 1 This is a schematic diagram of a gas phase reactor system according to certain embodiments of this disclosure. Detailed Implementation

[0014] This document discloses a method for gas-phase polymerization in a fluidized bed to polymerize ethylene and ethylene comonomers to produce polyethylene polymers and copolymer compositions. The properties and performance of the polyethylene compositions can be controlled by a combination of: (1) altering one or more reactor conditions, such as reactor temperature, hydrogen concentration, and / or comonomer concentration; and (2) selecting a multi-trimmed catalyst feed system, wherein a first catalyst slurry is trimmed with one or more trimming solutions having one or more different catalyst compositions to achieve the desired polyethylene composition by a continuous production process. For example, a supported catalyst can be trimmed (e.g., online) with a separate trimming solution having catalysts that are different from each other and different from the supported catalyst to provide a multi-catalyst system that can be fed into the polymerization reactor. Alternatively, a supported catalyst can be trimmed (e.g., online) with two trimming solutions, wherein the first trimming solution has a catalyst different from the catalyst of the supported catalyst, and wherein the second trimming solution has a catalyst different from the catalyst of the supported catalyst and different from the catalyst of the first trimming solution. Such catalyst trimming methods can provide controllable adjustment of the properties of polyethylene by allowing the adjustment of the ratio of catalyst slurry and one or more trimming solutions provided in a multi-catalyst system fed into the reactor.

[0015] In this case, a supported catalyst is added to a diluent to form a catalyst slurry, which is then pumped to the polymerization reactor. Alternatively, one or more catalyst solutions having one or more different trimming catalyst compounds can be added (i.e., "trimmed") to the catalyst slurry to "in situ" adjust one or more properties of the polymer formed in the reactor. The feed rate and concentration of one or more catalyst solutions can be customized, allowing adjustment of the relative ratios of the individual catalysts to achieve the desired polymer properties.

[0016] The polyolefins disclosed herein can possess long-chain branching (LCB), a traditionally recognized characteristic in low-density polyethylene (LDPE) that results in good processability and optical properties. However, such LCB can hinder the mechanical properties of films containing such polyolefins. Compared to films containing other LDPE polymers, the polyolefins of this disclosure provide films that maintain or improve mechanical properties (i.e., tear resistance and dart impact strength) while maintaining or improving desired optical properties and improving the processability of such materials.

[0017] As used herein, the indefinite article “a” or “an” shall mean “at least one” unless otherwise stated or the context clearly indicates otherwise. Thus, embodiments using “α-olefin” include embodiments using one, two or more α-olefins, unless otherwise stated or the context clearly indicates that only one α-olefin is used.

[0018] As used herein, “wt%” means weight percentage, “volume%” means volume percentage, “molar%” means molar percentage, “ppm” means parts per million, and “ppm wt” and “wppm” are used interchangeably and mean parts per million based on weight. All concentrations herein, unless otherwise stated, are based on the total amount of the compositions discussed. Unless otherwise stated, temperatures are provided in degrees Celsius (°C).

[0019] "Olefin" is a linear, branched, or cyclic compound having at least one double bond between carbon and hydrogen. For the purposes of this specification and its appended claims, when referring to a polymer or copolymer containing an olefin, such as ethylene and at least one C3-C... 20 In the case of α-olefins, the olefin present in such polymers or copolymers is a polymeric form of olefin. For example, when the "ethylene" content of the copolymer is claimed to be 35%-55% by weight, it is understood that the repeating units / monomer units in the copolymer, or simply the units in the copolymer, are derived from ethylene in the polymerization reaction, and the derived units are present at 35%-55% by weight, based on the weight of the copolymer. For the purposes of this disclosure, ethylene should be considered as an α-olefin.

[0020] A “polymer” has two or more identical or different repeating units / monomer units, or simply units. A “homopolymer” is a polymer having identical units. A “copolymer” is a polymer having two or more different types of units. A “terpolymer” is a polymer having three different types of units. The term “different” used to refer to units means that the units are different from each other at at least one atom or are isomerically different. The definition of copolymer used herein includes terpolymers, etc. Similarly, the definition of polymer used herein includes homopolymers, copolymers, etc. Furthermore, the terms “polyethylene copolymer,” “ethylene copolymer,” and “vinyl polymer” are used interchangeably to refer to copolymers containing at least 50 mol% units derived from ethylene.

[0021] The nomenclature of elements and their families used in this article follows the NEWNOTATION published in Hawley's Condensed Chemical Dictionary, 13th Edition, John Wiley & Sons, Inc. (1997) (reproduced with permission from IUPAC), unless a previous IUPAC form in Roman numerals (also appearing in the same document) is mentioned, or unless otherwise indicated. IUPAC refers to the International Union of Pure and Applied Chemistry.

[0022] As used herein, the term "slurry catalyst mixture" refers to a contact product comprising at least one catalyst compound and a support fluid (e.g., mineral oil), and optionally one or more of an activator, co-activator, and support. In a preferred embodiment, the slurry catalyst mixture comprises a contact product comprising at least two catalyst compounds and a support fluid (e.g., mineral oil), and optionally one or more of an activator, co-activator, and support.

[0023] As used herein, the term "catalyst system" refers to a combination of at least one catalyst compound, optional activator, optional co-activator, and optional support material, wherein if only a catalyst compound is present, two or more different catalyst compounds are present to provide the catalyst system. Therefore, in some embodiments, when the optional activator, optional co-activator, and optional support material are not present, the catalyst system may contain only a single catalyst compound. In other embodiments, when the optional activator, optional co-activator, and optional support material are not present, the catalyst system may contain only two or more catalyst compounds. For the purposes of this disclosure, when a catalyst system is described as comprising a neutral, stable form of a component, as is well known to those skilled in the art, the ionic form of the component is the form in which it reacts with the monomer to produce a polymer. The catalyst systems, catalysts, and activators of this disclosure are intended to cover ionic forms in addition to the neutral forms of the compounds / components.

[0024] Metallocene catalysts are organometallic compounds having at least one π-bonded cyclopentadienyl structural moiety (or a substituted cyclopentadienyl structural moiety), and more frequently having two π-bonded cyclopentadienyl structural moieties or a substituted cyclopentadienyl structural moiety bonded to a transition metal. In this specification, metallocene catalysts may be described as catalyst precursors, precatalyst compounds, metallocene catalyst compounds, or transition metal compounds, and these terms are used interchangeably. An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. For the purposes of this disclosure, with respect to metallocene catalyst compounds, the term "substituted" means that a hydrogen group has been replaced by a hydrocarbon group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group.

[0025] The term "melt index" ("MI") is the number of grams extruded in 10 minutes under a standard load (2.16 kg) and is an inverse measure of viscosity. A high MI indicates low viscosity, and a low MI indicates high viscosity. Furthermore, polymers can exhibit shear-thinning behavior, meaning their flow resistance decreases with increasing shear rate. This is due, for example, to molecular alignment and deentanglement in the flow direction. As provided herein, MI (I2) is determined according to ASTM D1238-E (190°C / 2.16 kg) and is sometimes also referred to as I2 or I... 2.16 .

[0026] The term "High Load Melt Index" ("HLMI") refers to the number of grams extruded in 10 minutes under a standard load (21.6 kg) and is an inverse measure of viscosity. As provided herein, HLMI (I 21 ) Measured according to ASTM D1238 (190℃ / 21.6kg), and sometimes also referred to as I 21 Or I 21.6 .

[0027] The melt index ratio (“MIR”) provides a quantitative indication of the shear-thinning behavior of a polymer and is a parameter that can be correlated with the molecular weight distribution data of the overall polymer mixture obtained alone using gel permeation chromatography (“GPC”) and possibly in combination with other polymer analyses, including TREF. MIR is I 21 The ratio of / I2 (also known as HLMI / MI).

[0028] The properties and performance of polyethylene compositions can be improved by a combination of: (1) altering one or more reactor conditions, such as reactor temperature, hydrogen concentration, comonomer concentration, etc.; and (2) selecting a dual-conditioning catalyst feed system, wherein a first catalyst slurry is conditioned with one or more conditioning solutions having one or more different catalyst compositions to achieve the desired polyethylene composition by a continuous production process. For example, a supported catalyst can be conditioned (e.g., online) with separate conditioning solutions having two or more catalysts that are different from each other and different from the catalyst of the supported catalyst to provide a multi-catalyst system that can be fed to the polymerization reactor. Alternatively, the supported catalyst can be conditioned (e.g., online) with two conditioning solutions, wherein the first conditioning solution has a catalyst different from the catalyst of the supported catalyst, and wherein the second conditioning solution has a catalyst different from the catalyst of the supported catalyst and different from the catalyst of the first conditioning solution. Such a catalyst conditioning process provides easy tuning of the properties of polyethylene by allowing adjustment of the ratio of catalyst compounds provided by the catalyst slurry and one or more conditioning solutions in the multi-catalyst system fed to the reactor.

[0029] In various embodiments according to this disclosure, the slurry catalyst mixture may comprise a first catalyst compound that can provide a polymer having a first molecular weight range. Consistent with the foregoing description regarding trimming solutions, one or more catalyst compounds may be added to the polymerization process in the form of online addition of one or more trimming solutions. In some embodiments, two or more trimming catalysts may be added to the polymerization process via trimming using two or more trimming solutions. In one or more embodiments, the first trimming catalyst may be provided to the polymerization process via a first trimming pot. In one or more embodiments, the second trimming catalyst may be provided to the polymerization process via a second trimming pot. In at least one embodiment, the ratio of trimming solution to catalyst slurry is from about 1.5 g / hr / cc / hr to about 3.2 g / hr / cc / hr, for example from about 2 g / hr / cc / hr to about 3 g / hr / cc / hr. In at least one embodiment, the first catalyst compound of the catalyst slurry and any one or more trimming catalysts of the one or more trimming solutions are independently metallocene catalyst compounds.

[0030] gas phase reactor

[0031] Figure 1This is a schematic diagram of a gas-phase reactor system 100, illustrating the addition of at least two catalysts, at least one of which is added as a trimming catalyst. The catalyst slurry mixture from catalyst tank 102 and the solution catalyst mixture from trimming tank 104A can be mixed online. For example, the solution catalyst mixture and the catalyst slurry mixture can be mixed using a mixer (e.g., a static mixer 108 and / or a stirred vessel). Alternatively, any suitable mixer can be used, including, for example, mixing in a pipe, mixing using a mixing device, or mixing in a continuously stirred tank. Any mixer capable of contacting the solution catalyst mixture and the catalyst slurry mixture can be used.

[0032] Catalyst tank 102 contains a first catalyst slurry mixture. The first catalyst slurry mixture can be prepared by any suitable method, including, for example, by mixing particles of one or more catalyst compounds with mineral oil. Catalyst tank 102 can be a stirred storage tank configured to maintain a uniform solids concentration. In at least one embodiment, catalyst tank 102 can be maintained at an elevated temperature (relative to room temperature), for example, 30°C to 80°C. Alternatively, catalyst tank 102 can be maintained at any range between 30°C and 40°C, 40°C and 50°C, 50°C and 60°C, 60°C and 80°C. The elevated temperature can be obtained by electrically heating catalyst tank 102, for example, using a heating blanket. Maintaining catalyst tank 102 at the elevated temperature can further reduce or eliminate the formation of solid residues on the container walls, which would otherwise slide off the walls and cause blockages in downstream delivery lines. In at least one embodiment, the volume of catalyst tank 102 can be 0.5 cubic meters (m³). 3 ) to 8.0m 3 Alternatively, the catalyst tank 106 may have a volume of 0.5 m³. 3 Up to 1.0m 3 1.0m 3 Up to 2.0m 3 2.0m 3 Up to 3.0m 3 3.0m 3 Up to 4.0m 3 4.0m 3 up to 5.0m 3 5.0m 3 Up to 6.0m 3 6.0m 3 Up to 7.0m 3 7.0m 3 up to 8.0m 3 or any range thereof.

[0033] The catalyst tank 102 can be maintained at a pressure of 1.0 bar to 4.0 bar. Alternatively, the pressure of the catalyst tank 106 can be any range between 1.0 bar and 1.5 bar, 1.5 bar and 2.0 bar, 2.0 bar and 2.5 bar, 2.5 bar and 3.0 bar, 3.0 bar and 3.5 bar, 3.5 bar and 4.0 bar. In at least one embodiment, the conduits 130 and 140 of the gas phase reactor system 100 can be maintained at an elevated temperature (relative to room temperature), for example, 30°C to 80°C. Alternatively, the temperature of conduits 130 and 140 can be any range between 30°C and 40°C, 40°C and 50°C, 50°C and 60°C, 60°C and 80°C. The elevated temperature can be obtained by electrically heating conduits 130 and / or 140, for example, using a heating blanket. Maintaining pipes 130 and / or 140 at elevated temperatures can provide the same or similar benefits as described for the elevated temperature of catalyst tank 102.

[0034] The solution catalyst mixture prepared by mixing a solvent and at least one second catalyst and / or activator can be placed in a separate container, such as trimming tank 104A. Trimming tank 104A may have a 0.5m... 3 Up to 1.0m 3 1.0m 3 Up to 2.0m 3 2.0m 3 Up to 3.0m 3 3.0m 3 Up to 4.0m 3 4.0m 3 up to 5.0m 3 5.0m 3 Up to 6.0m 3 6.0m 3 Up to 7.0m 3 7.0m 3 up to 8.0m 3 Volumes within or between these ranges. Dressing tank 104A can be maintained at elevated temperatures (relative to room temperature), for example, 30°C to 80°C. Alternatively, the temperature of dressing tank 108 can be 30°C to 40°C, 40°C to 50°C, 50°C to 60°C, 60°C to 80°C, or any range between these ranges. Dressing tank 104A can be heated, for example, by electrically tracing it via a heating blanket. Maintaining dressing tank 104A at elevated temperatures can provide reduced or eliminated foaming in conduits 130 and / or 140 when the catalyst slurry mixture from catalyst tank 102 is combined online (also referred to herein as "on-line") with the solution catalyst mixture from dressing tank 104A.

[0035] The catalyst slurry mixture can then be combined online with the solution catalyst mixture in trimming tank 104A and / or the second trimming tank (trimming tank 104B) to form a slurry / solution catalyst mixture or a final catalyst composition. Trimming tank 104A may have one or more trimming catalysts. Trimming tank 104B may have one or more trimming catalysts different from the trimming catalyst in trimming tank 104A.

[0036] In some implementations, one or more additional trimming tanks (by...) Figure 1 The dressing tank (represented by 104B) can have a capacity of 0.5m. 3 Up to 1.0m 3 1.0m 3 Up to 2.0m 3 2.0m 3 Up to 3.0m 3 3.0m 3 Up to 4.0m 3 4.0m 3 up to 5.0m 3 5.0m 3 Up to 6.0m 3 6.0m 3 Up to 7.0m 3 7.0m 3 up to 8.0m 3 The trimming tank 104B can be any volume within or between these ranges. The trimming tank 104B can be maintained at an elevated temperature (relative to room temperature), for example, 30°C to 80°C. Alternatively, the temperature of the trimming tank 108 can be any range between 30°C and 40°C, 40°C and 50°C, 50°C and 60°C, 60°C and 80°C. The trimming tank 104B can be heated, for example, by electrically heating it via a heating blanket.

[0037] Optionally, nucleating agent 106, such as silica, alumina, fumed silica, or any other suitable particulate matter, can be added online to the slurry and / or solution, and / or to catalyst tank 102 or trimming tank 104A. Similarly, additional activators or catalyst compounds can be added online. For example, a second solution catalyst mixture can be introduced from a second trimming tank 104B. In some embodiments, the second solution catalyst mixture comprises at least one catalyst compound different from the first solution catalyst mixture. Additionally, any one or more solution catalyst mixtures may contain a combination of two or more catalyst compounds. In other words, the solution catalyst mixture may contain at least a first catalyst compound and a second catalyst compound, wherein the second catalyst compound is different from the first catalyst compound. The second solution catalyst mixture can be introduced via line 181 (via line 182) together with the first solution catalyst mixture to form a slurry / solution catalyst mixture or a final catalyst composition, wherein the second solution catalyst mixture is supplied by and / or stored within one or more secondary trimming tanks 104B. Additionally or alternatively, the second solution catalyst mixture is supplied via line 183 to main line 130 (downstream of line 130 where the first solution catalyst mixture is added) (shown) or line 140 (downstream of static mixer 108) (not shown). If the second solution catalyst mixture is supplied to line 140 downstream of static mixer 108, the second static mixer (not shown) can be used to mix the second solution catalyst mixture with the already loaded catalyst supplied by static mixer 108. Generally, such sequential addition of trimmed catalysts can provide a suitable trimming process where the order in which the catalyst is added to the support material is required. Those skilled in the art will recognize that implementing multiple trimming tanks having one or more different solution catalyst mixture compositions allows the reaction conditions and the properties of the resulting polymer to be adjusted to the desired specifications (the optional addition in...). Figure 1 (See 104B in the examples). Furthermore, the online addition of each of one or more solution catalyst mixtures can be individually metered to independently adjust and control the relative catalyst composition and concentration within the gas-phase reaction vessel. The benefit of such independent control is that the process can be adjusted in real time in response to monitoring polymer properties and reactor conditions and parameters.

[0038] Catalyst slurry mixtures and solution catalyst mixtures (one or more) can be mixed online. For example, the solution catalyst mixtures (one or more) and catalyst slurry mixtures can be mixed using a mixer 108 (e.g., a static mixer and / or a stirred mixer). In some embodiments, the mixer may include a static mixer 108 followed by a stirred mixer. The mixing of the catalyst slurry mixture and the solution catalyst mixtures (one or more) is sufficient to disperse the catalyst compounds in the solution catalyst mixture in the catalyst slurry mixture, causing the catalyst components (initially in solution) to migrate to the supported activator (initially present in the slurry). The combination can form a homogeneous dispersion of the catalyst compounds on the supported activator, thereby forming a catalyst composition. The contact time between the slurry and the solution can range from 1 minute to 4 hours. Alternatively, this time length can be 1 minute to 10 minutes, 10 minutes to 30 minutes, 30 minutes to 1 hour, 1 hour to 1.5 hours, 1.5 hours to 2 hours, 2 hours to 2.5 hours, 2.5 hours to 3 hours, 3 hours to 3.5 hours, 3.5 hours to 4 hours, or any range therebetween.

[0039] The static mixer 108 of the gas-phase reactor system 100 can be maintained at an elevated temperature (relative to room temperature), for example, 30°C to 80°C. Alternatively, the temperature of the static mixer 109 can be 30°C to 40°C, 40°C to 50°C, 50°C to 60°C, 60°C to 80°C, or any range therebetween. The elevated temperature of the static mixer 108 can be achieved by electrically heating the static mixer 108, for example, using a heating blanket. Maintaining the static mixer 108 at the elevated temperature can provide reduced or eliminated foaming in the static mixer 108 and can promote the mixing of the catalyst slurry mixture and catalyst solution (one or more) (compared to a lower temperature), which reduces the run time in the static mixer and the run time in the overall polymerization process.

[0040] Optionally, an antistatic agent (e.g., alkylaluminum, ethoxylated alkylaluminum and / or aluminoxane) or a borate ester activator, such as C1-C, can be used. 15 Alkyl aluminum (e.g., triisobutylaluminum, trimethylaluminum, etc.), C1-C 15Ethoxylated alkyl aluminum or methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, modified aluminoxane, etc., are added online to the slurry / solution catalyst mixture and / or directly to the reactor. Antistatic agents, borate ester activators, and / or aluminoxanes can be added directly from container 110 to the combination of the solution catalyst mixture and the catalyst slurry mixture, or they can be added via an additional alkane (e.g., hexane, heptane, and / or octane) support stream, for example, from support container 112. The additional alkyl compounds, antistatic agents, borate ester activators, and / or aluminoxanes can be present at up to 500 ppm, 1-300 ppm, 10-300 ppm, or 10-100 ppm. Support gases 114, such as nitrogen, argon, ethane, propane, etc., can be added online to the slurry and solution mixture. In embodiments, the support gas can be added at a rate of 1 kg / hr to 100 kg / hr. Alternatively, the carrier gas addition rate can be 1 kg / hr-50 kg / hr, 1 kg / hr-25 kg / hr, 2 kg / hr-20 kg / hr, 2.5 kg / hr-15 kg / hr, or any range therebetween.

[0041] A liquid support stream can be introduced into a combination of a solution catalyst mixture and a catalyst slurry mixture. The mixture of solution, slurry, and liquid support stream can be mixed using a mixer or a pipe of a certain length, and then contacted with the gaseous support stream. Similarly, comonomers such as hexene, other α-olefins, or dienes can be added online to the mixture of slurry and solution.

[0042] A gaseous stream 126, such as recirculated or recycled gas 124, monomer, nitrogen, or other materials, can be introduced into the injection nozzle 300, which may include a support tube 128 at least partially surrounded by the injection tube 120. A slurry / solution catalyst mixture can be introduced into the fluidized bed reactor 122 through the injection tube 120. In at least one embodiment, the injection tube 120 can atomize the slurry / solution mixture. Any number of suitable tube sizes and configurations can be used to atomize and / or inject the slurry / solution mixture.

[0043] The fluidized bed reactor 122 may include a reaction zone 132 and a deceleration zone 134. The reaction zone 132 may include a bed 136, which may include grown polymer particles, formed polymer particles, a small amount of catalyst particles fluidized by a continuous flow of gaseous monomers, and a diluent to remove the heat of polymerization passing through the reaction zone. Optionally, a portion of the recirculated gas 124 may be cooled and compressed to form a liquid, which can increase the heat removal capacity of the recirculated gas stream when the liquid is reintroduced into the reaction zone. A suitable gas flow rate can be readily determined experimentally. The rate at which gaseous monomers are supplied to the recirculated gas stream can be equal to the rate at which particulate polymer product and associated monomers are extracted from the reactor, and the composition of the gas passing through the reactor can be adjusted to maintain a substantially steady-state gaseous composition within the reaction zone. Gas leaving the reaction zone 132 may proceed to the deceleration zone 134, where, as entrained particles decelerate and fall back into the reaction zone 132, the entrained particles can be removed, for example, by gravity separation. The recirculated gas 124 can then be compressed in compressor 142 and passed through heat exchanger 144, where at least a portion of the heat of polymerization can be removed. The gas can then be returned to reaction zone 132. To promote particle formation in fluidized bed reactor 122, nucleating agent 118 (e.g., fumed silica) can be added directly to fluidized bed reactor 122. Conventional trimmed polymerization processes involve introducing nucleating agents into the polymerization reactor. Furthermore, when using metallocene catalysts or other similar catalysts in the gas-phase reactor, oxygen or fluorobenzene can be added directly to fluidized bed reactor 122 or gas stream 126 to control the polymerization rate.

[0044] Figure 1 This is not limiting, as additional solution catalyst mixtures and / or catalyst slurry mixtures can be used. For example, a catalyst slurry mixture can be combined with two or more solution catalyst mixtures having the same or different catalyst compounds and / or activators. Similarly, a solution catalyst mixture can be combined with two or more catalyst slurry mixtures, each having the same or different supports and the same or different catalyst compounds and / or activators. Likewise, two or more catalyst slurry mixtures can be combined with one or more solution catalyst mixtures, for example, in-line combination, wherein each catalyst slurry mixture contains the same or different supports and may contain the same or different catalyst compounds and / or activators, and the solution catalyst mixture may contain the same or different catalyst compounds and / or activators. For example, a catalyst slurry mixture may contain a supported activator and two different catalyst compounds, and two solution catalyst mixtures, each containing one catalyst from the slurry, wherein each can be independently combined in-line with the slurry.

[0045] The reactor temperature for fluidized bed processes can range from 30°C to 200°C. Alternatively, the reactor temperature can be 30°C to 40°C, 40°C to 50°C, 50°C to 80°C, 80°C to 100°C, 100°C to 150°C, 150°C to 200°C, or any range therebetween. Typically, the reactor can be operated at a suitable temperature taking into account the sintering temperature of the polymer product within the reactor. Therefore, in various embodiments, the upper limit temperature can be the melting temperature of the polyethylene copolymer produced in the reactor. However, higher temperatures can produce a narrower molecular weight distribution, which can be improved by adding a catalyst or other co-catalyst.

[0046] Hydrogen can be used in polymerization processes to help control or otherwise modulate the final properties of polyolefins. Using certain catalyst systems, increased hydrogen concentration (partial pressure) can increase the flow index, such as the melt index, of polyethylene polymers. Therefore, the melt index can be influenced by hydrogen concentration. The amount of hydrogen in polymerization can be expressed as a molar ratio relative to the total polymerizable monomers, such as ethylene, or a blend of ethylene and hexene or propylene. The amount of hydrogen used in the polymerization process can be the amount needed to achieve the desired melt index of the final polyolefin polymer. For example, the molar ratio of hydrogen to total monomers (H2:monomer) can be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater. Furthermore, the molar ratio of hydrogen to total monomers (H2:monomer) can be 10 or less, 5 or less, 3 or less, or 0.10 or less. The range of hydrogen to monomer molar ratios can include any combination of any upper molar ratio and any lower molar ratio described herein. In various embodiments, the amount of hydrogen in the reactor at any given time can be up to 5,000 ppm, up to 4,000 ppm, up to 3,000 ppm, or 50 ppm to 5,000 ppm, or 50 ppm to 2,000 ppm. The amount of hydrogen in the reactor can be 1 ppm, 50 ppm, or 100 ppm to 400 ppm, 800 ppm, 1,000 ppm, 1,500 ppm, or 2,000 ppm, based on weight. Furthermore, the ratio of hydrogen to total monomers (H2:monomers) can be 0.00001:1 to 2:1, 0.005:1 to 1.5:1, or 0.0001:1 to 1:1. The pressure of one or more reactors in a gas-phase process (single-stage, two-stage, or more stages) can be from 690 kPa to 1,379 kPa, or from 1,724 kPa to 2,414 kPa, or from 2,759 kPa to 3,448 kPa.

[0047] In the embodiments, the melt index ratio (MIR) of the polymer product can be from 10 to less than 300, or in many embodiments, from 20 to 66, for example, from 25 to 55. The melt index (MI, I2) can be measured according to ASTM D-1238-20, in which a 2.1 kg load is used to determine the melt index, and the melt index ratio is determined by the ratio of a 21.6 kg load to a 2.1 kg load (both at 190°C).

[0048] Polymer products can have a concentration of 0.89 g / cm³. 3 ), 0.90 g / cm 3 0.91g / cm 3 Or 0.92g / cm 3 Up to 0.93 g / cm 3 0.95g / cm 3 0.96 g / cm 3 Or 0.97g / cm 3 The density can be determined according to ASTM D-792-20. The polymer can have a density of 0.25 g / cm³ as measured according to ASTM D-1895-17 Method B. 3 up to 0.5 g / cm 3 The bulk density. For example, the bulk density of a polymer can be 0.30 g / cm³. 3 0.32g / cm 3 Or 0.33g / cm 3 Up to 0.40 g / cm 3 0.44 g / cm 3 Or 0.48g / cm 3 .

[0049] The polymerization process, according to various embodiments, may include contacting one or more olefin monomers with a catalyst slurry mixture that may contain mineral oil and catalyst particles. The one or more olefin monomers may be ethylene and / or propylene, and the polymerization process may include heating the one or more olefin monomers and the catalyst system to 70°C or higher to form an ethylene polymer or a propylene polymer.

[0050] The monomers useful in this article include substituted or unsubstituted C2 to C3. 40 α-olefins, such as C2 to C 20 α-olefins, such as C2 to C 12 α-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and their isomers. For example, the monomer may include ethylene and one or more optional comonomers selected from propylene or C4 to C5. 40 Alkenes, such as C4 to C5 20Alkenes, such as C6 to C6 12 Alkenes. C4 to C 40 Olefin monomers can be linear, branched, or cyclic. (C4 to C5) 40 Cyclic alkenes can be tensioned or non-tensioned, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups.

[0051] In some implementations, C2 to C 40 α-olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives and isomers, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene and their respective homologues and derivatives, such as norbornene, norbornadiene and dicyclopentadiene.

[0052] In various embodiments, one or more dienes may be present in the polymer product at a maximum of 10% by weight, for example, from 0.00001 to 1.0% by weight, or from 0.002 to 0.5% by weight, or from 0.003 to 0.2% by weight, based on the total weight of the composition. 500 ppm or less of dienes may be added to the polymer, for example, 400 ppm or less, or for example, 300 ppm or less; additionally or alternatively, at least 50 ppm of dienes may be added to the polymer, or 100 ppm or more, or 150 ppm or more.

[0053] Diene monomers include any hydrocarbon structure having at least two unsaturated bonds, such as C4 to C5. 30At least two of the unsaturated bonds are readily incorporated into the polymer via stereospecific or non-stereospecific catalysts (one or more). The diene monomer may be selected from α,ω-diene monomers (i.e., divinyl monomers). The diene monomer is a linear divinyl monomer, for example, those containing 4 to 30 carbon atoms. Examples of dienes include, but not limited to, butadiene, pentadiene, hexadiene, heptadecadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, heptadecanadiene, octadecadiene, nonadecanadiene, eicosadiene, icosadiene, icosadiene, icosadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecanadiene, octadecadiene, nonadecanadiene, triadecadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tetadecanadiene, 1,13-tetradecadiene, and low molecular weight polybutadiene (e.g., weight-average molecular weight (Mw) less than 1000 g / mol). Cyclic dienes include cyclopentadiene, vinyl norbornene, norbornene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, or higher rings containing dienes, with or without substituents at each ring position.

[0054] The catalyst compositions (catalysts and / or catalyst systems) disclosed herein are capable of producing ethylene polymers with a melt index (MI) of 40,000 g / mol, 70,000 g / mol, 90,000 g / mol, or 100,000 g / mol up to 200,000 g / mol, 300,000 g / mol, 600,000 g / mol, 1,000,000 g / mol, or 1,500,000 g / mol. The ethylene polymers may have a melt index (MI) of 0.6 g / 10 min or greater, for example, 0.7 g / 10 min or greater, for example, 0.8 g / 10 min or greater, for example, 0.9 g / 10 min or greater, for example, 1.0 g / 10 min or greater, for example, 1.1 g / 10 min or greater, for example, 1.2 g / 10 min or greater.

[0055] "Catalyst productivity" is the percentage of catalysts that can be produced using ... W The polymerization catalyst of cat catalyst in T How many grams of polymer are produced within an hour? P The measure of ); and can be expressed by the following formula: P / ( T x W ), and with gPgcat -1 hr -1The units are expressed as follows. The productivity of the catalyst compositions disclosed herein can be at least 50 g(polymer) / g(cat) / hour, for example 500 g(polymer) / g(catalyst) / hour or higher, for example 800 g(polymer) / g(cat) / hour or higher, for example 5,000 g(polymer) / g(cat) / hour or higher, for example 6,000 g(polymer) / g(cat) / hour or higher, for example 7,000 g(polymer) / g(cat) / hour or higher.

[0056] Method for preparing slurry catalyst mixture

[0057] A storage container or vessel can be used to generate or otherwise prepare a slurry catalyst mixture. One or more mineral oils can be introduced into the vessel. The mineral oil can be heated within the vessel to a temperature of 30°C to 100°C. Alternatively, the mineral oil can be heated to temperatures of 30°C to 40°C, 40°C to 50°C, 50°C to 60°C, 60°C to 80°C, 80°C to 100°C, or any range thereof, to produce heated mineral oil. The water concentration of the heated mineral oil can be reduced to produce dry mineral oil. For example, the water concentration of the heated mineral oil can be reduced by at least one of the following: (i) passing a first inert gas through the heated mineral oil, (ii) passing a second inert gas through the headspace of the vessel, (iii) subjecting the heated mineral oil to a vacuum, and (iv) adding an aluminum-containing compound to the heated mineral oil. In various implementations, two or more, three or more, or four or more of the above may be used in combination; for example, according to some implementations, a combination of (i) and (ii) may be used; and / or in particular implementations, a combination of (iii) and (iv) may be used.

[0058] Regarding (i) and (ii), the first and / or second inert gas may be, independently, or comprise, but not limited to, nitrogen, carbon dioxide, argon, or any mixture thereof. The amount of the first and / or second inert gas (via mineral oil or headspace into the container) may be measured in volumetric turnovers (where each turnover equals the volume of the container) and is a low value of 5, 10, 15, or 20 volumetric turnovers to a high value of 30, 40, 45, 50, 55, or 60 volumetric turnovers (considering any range from low to high). The container volume is not limited but may be, for example, 0.75, 1.15, 1.5, 1.9, or 2.3 cubic meters (m³). 3 The lowest value of any of the following is 3, 3.8, 5.7 or 7.6m. 3The high value. Regarding (iii), the heated mineral oil can be subjected to a vacuum (e.g., a pressure less than 101 kPa-absolute, less than 75 kPa-absolute, less than 60 kPa-absolute, or less than 55 kPa-absolute). In various embodiments, the vacuum pressure can be from the low of any of 0.67, 1, 10, 15, or 20 kPa-absolute to the high of any of 30, 40, 55, 60, 65, or 80 kPa-absolute, with any of the aforementioned low to any of the aforementioned high ranges considered herein. The heated mineral oil can be subjected to a vacuum for a duration of 1 hour (hr), 2 hours, 3 hours, 4 hours, or 5 hours to 6 hours, 8 hours, 10 hours, 12 hours, 24 hours, or longer. Regarding (iv), the aluminum-containing compound can be or may contain, but is not limited to, compounds of the formula AlR. (3-a) X a The compound is indicated by R being a branched or linear alkyl, cycloalkyl, heterocycloalkyl, aryl, or hydride group having 1 to 30 carbon atoms, X being a halogen, and a being 0, 1, or 2. For example, aluminum-containing compounds may be or may contain trihexylaluminum, triethylaluminum, trimethylaluminum, triisobutylaluminum, diisobutylaluminum bromide, diisobutylaluminum hydride, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or any mixture thereof. Modified methylaluminoxanes can be produced by the hydrolysis of trimethylaluminum and higher trialkylaluminums such as triisobutylaluminum. Modified methylaluminoxanes generally have higher solubility in aliphatic solvents and higher stability during storage. Various known methods exist for the preparation of aluminoxanes and modified aluminoxanes.

[0059] According to ASTM D1533-12, the water concentration of dried mineral oil can be less than or equal to 100 parts per million (ppmw), less than or equal to 85 ppmw, less than or equal to 70 ppmw, less than or equal to 60 ppmw, less than or equal to 55 ppmw, less than or equal to 50 ppmw, less than or equal to 45 ppmw, less than or equal to 40 ppmw, less than or equal to 35 ppmw, less than or equal to 30 ppmw, less than or equal to 25 ppmw, or less than or equal to 20 ppmw. According to ASTM D4052-18a, dried mineral oil can have a water concentration of 0.85 g / cm³ at 25°C. 3 0.86 g / cm 3 Or 0.87g / cm 3 Up to 0.88 g / cm 3 0.89 g / cm 3 or 0.9g / cm 3The density; and / or, according to ASTM D341-20e1, the dried mineral oil may have a kinematic viscosity of 50 centistokes (cSt), 75 cSt, or 100 cSt to 150 cSt, 200 cSt, 250 cSt, or 300 cSt at 40°C. Optionally, according to ASTM D2502-14(2019)e1, the dried mineral oil may additionally or alternatively have an average molecular weight of 250 g / mol, 300 g / mol, 350 g / mol, 400 g / mol, 450 g / mol, or 500 g / mol to 550 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, or 750 g / mol.

[0060] Once dried mineral oil is produced, catalyst particles can be introduced into the dried mineral oil to produce a mixture. The mixture may be mixed, blended, stirred, or otherwise agitated for at least 2 hours to remove at least a portion of any gas that may be present within the pores of the catalyst particles, thereby producing a slurry catalyst mixture. In some embodiments, the mixture may be agitated for 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or longer to produce a slurry catalyst mixture; and / or during agitation, the temperature of the mixture may be maintained at 50°C, 55°C, 60°C, or 65°C to 75°C, 80°C, 85°C, or 90°C. In other embodiments, the mixture may be cooled. For example, during agitation, the mixture may be cooled to 45°C, 40°C, 35°C, or 30°C.

[0061] The container may include one or more mixing devices configured to mix, blend, stir, or otherwise agitate the mixture within the container. For example, the mixing device may be a rotatable mixing device. Suitable rotatable mixing devices may include one or more blades or impellers configured to agitate one or more components of the slurry catalyst mixture within the container when rotated. The rotatable mixing device may rotate at 40 rpm, 50 rpm, 75 rpm, or 100 rpm to 150 rpm, 175 rpm, 200 rpm, 225 rpm, or 250 rpm. As another example, the mixture may be agitated via ultrasound; and / or by moving the container, such as by rolling the container or by rotating the container back and forth along its axis.

[0062] Mineral oil may also be agitated during introduction into the container; during heating of the mineral oil; during reduction of the water concentration in the mineral oil; and / or during introduction of catalyst particles into the mineral oil.

[0063] Mineral oil in the slurry catalyst mixture can also be referred to as a diluent. In addition to mineral oil, the slurry catalyst mixture may optionally contain one or more additional diluents. These additional diluents may be, or can be included in, but are not limited to, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof.

[0064] The slurry catalyst mixture can have a solids content of 1% to 40% by weight. For example, the slurry catalyst mixture can have a solids content of 1% to 5% by weight, 5% to 10% by weight, 10% to 15% by weight, 15% to 20% by weight, 20% to 25% by weight, 25% to 30% by weight, 35% to 40% by weight, or any range thereof.

[0065] Although wax has previously been considered necessary for many slurry catalyst mixtures, for example, for stability (especially for storage and transport), it should be noted that wax can advantageously be omitted from the slurry catalyst mixtures of the various embodiments described herein. Thus, according to such embodiments, the slurry catalyst mixture may be free of any wax having a melting point greater than or equal to 25°C at atmospheric pressure, based on the total weight of the slurry catalyst mixture. More generally, the slurry catalyst mixture may contain less than or equal to 3% by weight, less than or equal to 2.5% by weight, less than or equal to 2% by weight, less than or equal to 1.5% by weight, less than or equal to 1% by weight, less than or equal to 0.9% by weight, less than or equal to 0.8% by weight, less than or equal to 0.7% by weight, less than or equal to 0.6% by weight, less than or equal to 0.5% by weight, less than or equal to 0.4% by weight, less than or equal to 0.3% by weight, less than or equal to 0.2% by weight, or less than or equal to 0.1% by weight of any wax having a melting point greater than or equal to 25°C at atmospheric pressure, based on the total weight of the slurry catalyst mixture. As used herein, the term "wax" includes wax pastes also known as petroleum jelly or petroleum wax. Petroleum waxes include paraffin wax and microcrystalline wax, which include porous paraffin wax and deoiled wax. If present, the wax may have a concentration of 0.7 g / cm³. 3 0.73g / cm 3 Or 0.75g / cm 3 Up to 0.87 g / cm 3 0.9g / cm 3 or 0.95g / cm 3The density (at 100°C). If present, the wax may have a kinematic viscosity at 100°C of 5 cSt, 10 cSt, or 15 cSt to 25 cSt, 30 cSt, or 35 cSt. If present, the wax may have a melting point at atmospheric pressure of 25°C, 35°C, or 50°C to 80°C, 90°C, or 100°C. If present, the wax may have a boiling point of 200°C or higher, 225°C or higher, or 250°C or higher.

[0066] The term "wax" also refers to or otherwise includes any wax not considered petroleum wax, including animal waxes, plant waxes, fossil or earth waxes, vinyl polymers and polyol ether-esters, chlorinated naphthalene, and hydrocarbon waxes. Animal waxes can include beeswax, lanolin, shellac wax, and Chinese insect wax. Plant waxes can include carnauba wax, candelilla wax, laurel wax, and sugarcane wax. Fossil or earth waxes can include ozocerite, purified ozocerite, and montan wax. Vinyl polymers and polyol ether-esters include polyethylene glycol and methoxy polyethylene glycol. Hydrocarbon waxes include waxes produced via Fischer-Tropsch synthesis.

[0067] Once the slurry catalyst mixture has been produced, it can be transferred from the vessel to a reactor configured to introduce the slurry catalyst mixture into a gas-phase polymerization reactor (e.g., Figure 1 The catalyst tank or catalyst (CAT) in the gas-phase polymerization reactor described herein. Therefore, in various embodiments, the container can be located at the manufacturing facility site, including the gas-phase polymerization reactor. By preparing the slurry catalyst mixture at the manufacturing facility site, the use of a slurry catalyst tank for transporting the slurry catalyst mixture can be avoided, as the slurry catalyst mixture can be introduced into the catalyst tank or "catalyst (CAT) tank" after preparation, from which the slurry catalyst mixture can be introduced into the gas-phase polymerization reactor. By preparing the slurry catalyst mixture on-site at the manufacturing facility, the slurry catalyst mixture can be introduced into the gas-phase polymerization reactor within a time period of less than or equal to 180 minutes, less than or equal to 150 minutes, less than or equal to 125 minutes, less than or equal to 100 minutes, less than or equal to 80 minutes, less than or equal to 60 minutes, less than or equal to 50 minutes, or less than or equal to 40 minutes after the start of mixing. On the other hand, by preparing the slurry catalyst mixture on-site at the manufacturing facility, the slurry catalyst mixture can be introduced into the gas-phase polymerization reactor within a time period of less than or equal to 180 minutes, less than or equal to 150 minutes, less than or equal to 125 minutes, less than or equal to 100 minutes, less than or equal to 80 minutes, less than or equal to 60 minutes, less than or equal to 50 minutes, or less than or equal to 40 minutes after the agitation of the mixture is terminated or stopped.

[0068] Although, as stated above, wax can be advantageously omitted in cases where storage and / or transport stability is not required for certain catalyst mixtures, it has surprisingly been found that, in some cases, wax and / or additional diluents in certain catalyst mixtures can aid the polymerization process, for example, depending on the identity of the catalyst compound(s) in the slurry catalyst mixture. Therefore, it is surprising that even when it would be considered necessary to omit wax or other diluents (e.g., because improved storage / transport stability is not required), certain catalyst slurries have been found to contain wax or other diluents. Thus, methods according to various embodiments may include identifying slurry catalyst mixtures(s) that require wax and / or additional diluents, and including wax in such slurry catalyst mixtures(s) (preferably not including wax and / or additional diluents in the slurry catalyst mixture where the presence of wax and / or diluents does not provide processing advantages).

[0069] Therefore, the polymerization method according to some embodiments may include, in a first instance, introducing a support gas, one or more olefins, and a first slurry catalyst mixture into a polymerization reactor. The first slurry catalyst mixture may comprise one or more catalysts selected from a first catalyst group, a first support, a first activator, a first mineral oil, and a contact product of a wax having a melting point greater than or equal to 25°C at atmospheric pressure. The first slurry catalyst mixture may contain more than 1% by weight of wax, based on the total weight of the first slurry catalyst mixture. One or more olefins may be polymerized within the polymerization reactor in the presence of the first catalyst to produce a first polymer product.

[0070] catalyst

[0071] The catalyst or catalyst compound may be, or may contain, but is not limited to, one or more metallocene catalyst compounds. In some embodiments, the catalyst may contain at least a first metallocene catalyst compound and a second metallocene catalyst compound, wherein the first and second metallocene catalyst compounds have different chemical structures from each other. The metallocene catalyst compound may include a catalyst compound having one or more Cp ligands (cyclopentadienyl and ligands similar to cyclopentadienyl isovalve ligands) that are bound to at least one Group 3-12 metal atom, and one or more leaving groups bound to the at least one metal atom. In other embodiments, the catalyst further includes a third and / or a fourth metallocene catalyst compound, wherein the third and fourth metallocene catalyst compounds have different chemical structures from each other and different chemical structures from the first and second metallocene catalyst compounds.

[0072] It is also suitable to use a catalyst system of a mixture of three metallocene catalysts, and specifically, a catalyst system of the following mixtures: (1) dicyclopentadienyl hafnium (preferably bridged dicyclopentadienyl hafnium), (2) non-bridged zirconium, such as non-bridged indyl-cyclopentadienyl zirconium (preferably non-bridged indyl-cyclopentadienyl zirconium) and (3) bridged zirconium, such as bridged indyl-cyclopentadienyl zirconium.

[0073] In some embodiments, the metallocene catalyst compound includes hafnium. Suitable hafnium can include bridged or non-bridged hafnium, preferably bridged hafnium. Bridged hafnium compounds can include dimethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)dimethylhafnium, dimethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)diethylhafnium, diethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)dimethylhafnium, diethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)diethylhafnium, dimethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)diethylhafnium, dimethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)diethylhafnium, dimethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)diethylhafnium, and dimethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)diethylhafnium. Hafnium, dimethylsilyl(tetrahydroindyl)(triethylsilylmethylcyclopentadienyl)dimethylhafnium, dimethylsilyl(tetrahydroindyl)(triethylsilylmethylcyclopentadienyl)diethylhafnium, diethylsilyl(tetrahydroindyl)(triethylsilylmethylcyclopentadienyl)diethylhafnium, dimethylsilyl(tetrahydroindyl)(triethylsilylmethylcyclopentadienyl)hafnium dichloride, dimethylsilyl(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)hafnium dichloride, and combinations thereof.

[0074] As described above, suitable catalyst compounds may additionally or alternatively include one or more zirconium cascades, such as non-bridged zirconium cascades, including bis(5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)dimethylzirconium, bis(5,5,8,8-pentaethyl ... Bis(5,5,8,8-pentabutyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)dimethylzirconium, bis(5,5,8,8-pentabutyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)dimethylzirconium, bis(5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium, bis(5,5,8,8-pentaethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium, bis(5,5,8,8-pentaethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium, bis(5,5,8,8-pentaethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium, bis(5,5,8,8-pentaethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)dimethyl ... bis(5,5,8,8-pentapropyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium, bis(5,5,8,8-pentapropyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium, bis(5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium, bis(5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)diethylzirconium Zirconium dichloride, bis(5,5,8,8-pentaethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium dichloride, bis(5,5,8,8-pentapropyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium dichloride, bis(5,5,8,8-pentabutyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium dichloride, and combinations thereof.

[0075] In some embodiments, a suitable catalyst compound may additionally or alternatively comprise one or more zirconium cyclopentadienyl chlorides, such as bridged zirconium cyclopentadienyl chlorides, including dimethylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindyl)]zirconium chloride, diethylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindyl)]zirconium chloride, dipropylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindyl)]zirconium chloride, diisopropylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindyl)]zirconium chloride, dimethylsilyl[tetraethyl ...methylcyclopentadienyl(3-methyltetrahydroindyl)]zirconium chloride, dimethylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindyl)]zirconium chloride, dimethylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindyl)]zirconium chloride, dimethylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindyl)]zir Zirconium chloride, dimethylsilyl[tetrapropylcyclopentadienyl(3-methyltetrahydroindene)]zirconium chloride, dimethylsilyl[tetramethylcyclopentadienyl(3-ethyltetrahydroindene)]zirconium chloride, diethylsilyl[tetramethylcyclopentadienyl(3-ethyltetrahydroindene)]zirconium chloride, diethylsilyl[tetramethylcyclopentadienyl(3-ethyltetrahydroindene)]zirconium chloride, dimethylsilyl[tetramethylcyclopentadienyl(3-propyltetrahydroindene)]zirconium chloride, dimethylsilyl[tetramethylcyclopentadienyl(3-isopropyltetrahydroindene)]zirconium chloride, and combinations thereof.

[0076] In some implementations, the catalyst is represented by formula (I):

[0077] (I)

[0078] in:

[0079] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0080] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' Each is independently hydrogen, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, R 5 and R 6 R 7 and R 8 R 8 and R 9 and R 9 and R 10 One or more pairs of rings in R are coupled to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, or R 7' and R 8' R 8' and R 9' and R 9' and R 10' One or more pairs of the present form are absent, such that there are carbon-carbon double bonds between the corresponding carbon atoms of the indenyl hydride ring shown in formula (I);

[0081] T represents R a 2J、(R a )4J2 or (R a )6J3, where each J is independently C, Si, or Ge, and each R a Independently hydrogen, halide, substituted or unsubstituted C1 to C2 groups 40 Hydrocarbon group, or two Rs a It can form substituted or unsubstituted cyclic structures, including substituted or unsubstituted fully saturated rings, substituted or unsubstituted partially saturated rings, or substituted or unsubstituted aromatic rings; and

[0082] X 1 and X 2 Each can be independently a monovalent anionic ligand, diene ligand, alkylidene ligand, or X 1 and X 2 Joined to form a metallic ring. X 1 and X 2 Each can be independently a halogenated, hydride-based, alkyl-based, alkenyl-based, or arylalkyl group. In at least one embodiment, X 1 and X 2 Each independently is C1 to C 20 Hydrocarbon groups, including functional groups of elements in groups 13 to 17 of the periodic table, or X 1 and X 2 Joined together to form C4 to C 62 Ring-shaped or multi-ring-shaped structure. In at least one embodiment, X 1 and X 2 Each group is independently selected from hydrocarbon groups, aryl, hydrogen, amino (amide), alkoxy, thio, phosphorus, halogen, diene, amine, phosphine, ether, and combinations thereof having 1 to 20 carbon atoms. (X) 1 and X 2 Each can form a fused ring or part of a ring system, for example, X 1 and X 2 Independently selected from halogenated, aryl, and C1 to C5 alkyl groups, such as phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloro. In at least one embodiment, X 1 and X 2 Each of them is a chlorine group.

[0083] The catalyst of formula (I) may be the catalyst of catalyst tank 102 or the trimmed catalyst of trimmed tank 104A or 104B. The catalyst of formula (I) may be synthesized according to the procedure described in U.S. Patent Application Serial No. 63 / 503,869, which is incorporated herein by reference.

[0084] In at least one implementation, R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' Independently selected from hydrogen, halogens, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, functional groups of elements in groups 13 to 17 of the periodic table (e.g., -NR'2, -SR', -OR', -OSiR'3 or -PR'2, where each R' is independently hydrogen, halogen, C1-C...). 10Alkyl or C6-C 10 aryl), or R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' The two bonds in the ring combine to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring, such as substituted or unsubstituted C4 to C6 rings. 62 Annular or multi-annular rings. In at least one embodiment, R 7 R 8 R 9 R 10 R 11 R 12 and R 13 Each is hydrogen.

[0085] In at least one implementation, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' Independently hydrogen, halogen, alkoxy, or C1 to C2 40 Substituted or unsubstituted hydrocarbon groups (e.g., C1 to C2) 12 (substituted or unsubstituted hydrocarbon group), or -R''-SiR'3 or -R''-CR'3, wherein R'' is a C1 to C4 hydrocarbon group (e.g., -CH2-, -CH2CH2-, -(Me)CHCH2- or -(Me)CH-, and each R' is independently C1 to C4). 20 Substituted or unsubstituted hydrocarbon groups and at least one R' is C1 to C2. 20 Substituted or unsubstituted hydrocarbon group. In at least one embodiment, each R' is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or isomers thereof, and R' is C1 to C2. 20 Alkyl or aryl, such as methyl, methylphenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl or di-tert-butylphenyl, provided that at least one R' is not H, alternatively two R's are not H, or alternatively three R's are not H.

[0086] In at least one embodiment, C1-C 40Hydrocarbon group, C1-C 20 Hydrocarbon group or C1-C 12 The hydrocarbon group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isonyl, sec-nonyl, n-decyl, isodel, or sec-decyl.

[0087] In at least one implementation, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' Independently, it is hydrogen, -CH2-SiMe3, -CH2-SiEt3, -CH2-SiPr3, -CH2-SiBu3, -CH2-SiCy3, -CH2-C(CH3)3, -CH2-CH(CH3)2, -CH2CPh3, -CH2(C6Me5), -CH2-C(CH3)2Ph, -CH2-C(Cy)Ph2, -CH2-SiPh3, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)2Ph, -CH2-Si(Et)2Ph, -CH2-Si(Et)Ph2, -CH2-Si(Cy)Ph2, or -CH2-Si(Cy)2Ph.

[0088] In at least one implementation, R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' It is hydrogen, and R 1 R 2 R 3 R 4 R 5 and R 6Each of these can be independently hydrogen, -CH2-SiMe3, -CH2-SiEt3, -CH2-SiPr3, -CH2-SiBu3, -CH2-SiCy3, -CH2-C(CH3)3, -CH2-CH(CH3)2, -CH2CPh3, -CH2(C6Me5), -CH2-C(CH3)2Ph, -CH2-C(Cy)Ph2, -CH2SiPh3, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)Ph2, -CH2-Si(Et)2Ph, -CH2-Si(Et)Ph2, -CH2-Si(Cy)Ph2, or -CH2-Si(Cy)2Ph, where R 1 R 2 R 3 R 4 R 5 Or R 6 At least one of them is not hydrogen.

[0089] In at least one embodiment, the catalyst can be represented by formula (I), where M is hafnium (Hf), R 1 R 2 R 4 R 5 R 6 R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' Each is independently hydrogen or C1-C5 alkyl, R 3 -CH2-SiMe3, X 1 and X 2 Each is either methyl or halogen, and T is derived from formula R. a 2J represents, where J is Si and each R a It is a C1-C5 alkyl group. In at least one embodiment, the catalyst may be represented by the following formula.

[0090]

[0091] In at least one embodiment, the catalyst can be represented by formula (I), where M is zirconium (Zr) and R... 5 R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10'Each is independently hydrogen or C1-C5 alkyl, R 1 R 2 R 3 R 4 and R 6 Each is a C1-C5 alkyl group, X 1 and X 2 Each is either methyl or halogen, and T is derived from formula R. a 2J represents, where J is Si and each R a It is a C1-C5 alkyl group. In at least one embodiment, the catalyst may be represented by the following formula.

[0092]

[0093] In some implementations, the catalyst is represented by formula (II): (II)

[0094] in:

[0095] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0096] R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 21' R 22 R 22' R 23 R 23' R 24 R 24' R 25 R 25' R 26 R 26' R 27 R 27' R 28 and R 28' Each is independently hydrogen, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; and

[0097] Each X is independently a halogen, substituted or unsubstituted hydrocarbon, hydrogen, amino, substituted or unsubstituted alkoxy, thio, phosphorus, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metal ring, or two Xs are joined together to form a chelate ligand, diene ligand, or alkylidene group.

[0098] In some implementations, R of formula (II) 14 R 15 R 19 R 20 R 21 R 21' R 22 R 22' R 23 R 23' R 24 R 24' R 25 R 25' R 26 R 26' R 27 R 27' R 28 and R 28' Each is independently hydrogen or C1-C 10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R 21 R 21' R 24 R 24' R 25 R 25' R 28 and R 28' Each is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, R 21 R 21' R 24 R 24' R 25 R 25' R 28 and R 28' Each is hydrogen. In some implementations, R 21 R 21' R 24 R 24' R 25 R 25' R 28 and R 28' Each is C1-C 10 Alkyl (e.g., methyl). In some embodiments, R 14 R 15 R 19 R20 R 22 R 22' R 23 R 23' R 26 R 26' R 27 and R 27' Each is hydrogen.

[0099] In some implementations, R of formula (II) 11 R 12 R 13 R 16 R 17 and R 18 Each is independently hydrogen or C1-C 10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R 11 R 12 R 13 R 16 R 17 and R 18 Each is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, R 11 R 12 R 13 R 16 R 17 and R 18 Each is hydrogen. In some implementations, R 11 R 12 R 13 R 16 R 17 and R 18 Each is a methyl group. In some embodiments, R 13 and R 18 At least one of them is C1-C 10 Alkyl group. In some embodiments, R 13 and R 18 Each independently is C1-C 10 Alkyl group. In some embodiments, R 13 and R 18 For C1-C 10 Alkyl (e.g., methyl), and R 11 R 12 R 16 and R 17 It is hydrogen.

[0100] In some embodiments of formula (II), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf), such as Zr or Hf. In some embodiments, each X is independently a halogen group, such as chlorine. In still other embodiments, each X is independently a C1-C4 alkyl group, such as methyl. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbon groups, heteroatoms, or substituted or unsubstituted heteroatom-containing groups, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrogen, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino. In some embodiments of formula (II), (1) M is Zr or Hf, (2) X is chlorine, (3) R 11 R 12 R 13 R 14 R 15 R 21 R 21' R 22 R 22' R 23 R 23' R 24 and R 24' Independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl, (4)R 16 R 17 R 18 R 19 R 20 R 25 R 25' R 26 R 26' R 27 R 27' R 28 and R 28' Independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl groups, and (5)R 13 and R 18 At least one of them is C1-C 10 alkyl.

[0101] In at least one embodiment, the catalyst can be represented by formula (II), where M is zirconium (Zr) and R... 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R21 R 21' R 22 R 22' R 23 R 23' R 26 R 26' R 27 and R 27' Each is independently hydrogen or C1-C5 alkyl, R 21 R 21' R 24 R 24' R 24 R 24' R 25 R 25' and R 28' X2 is methyl, and each X2 is methyl. In at least one embodiment, the catalyst can be represented by the following formula.

[0102]

[0103] The catalyst of formula (II) may be the catalyst of catalyst tank 102 or the trimmed catalyst of trimmed tank 104A or 104B. The catalyst of formula (II) may be synthesized according to the procedure described in U.S. Patent Application Serial No. 63 / 503,893 (which is incorporated herein by reference).

[0104] Slurry catalyst mixture containing activator and support

[0105] As described above, slurry catalyst mixtures may contain one or more activators and / or supports in addition to one or more catalysts. The term "activator" refers to any supported or unsupported compound or combination of compounds that can, for example, activate a unit site catalyst compound or component by forming a cationic substance of the catalyst component. For example, this may include abstracting at least one leaving group (the "X" group in the unit site catalyst compound described herein) from the metal center of the unit site catalyst compound / component. Activators may also be referred to as "co-catalysts." For example, a slurry catalyst mixture may contain two or more activators (e.g., aluminoxanes and modified aluminoxanes) and catalyst compounds, or a slurry catalyst mixture may contain a supported activator and more than one catalyst compound. In a particular embodiment, a slurry catalyst mixture may contain at least one support, at least one activator, and at least two catalyst compounds. For example, a slurry may contain at least one support, at least one activator, and two different catalyst compounds, which may be added separately or in combination to produce a slurry catalyst mixture. For example, a mixture of a support (e.g., silica) and an activator (e.g., aluminoxane) can be contacted with a first catalyst compound to cause a reaction, and the mixture can then be contacted with a second, different catalyst compound, for example, in a trimming system. Furthermore, additional catalyst compounds (third, fourth, etc.) can be contacted sequentially or together with the first and / or second catalyst compounds in a similar manner.

[0106] The molar ratio of the metal in the activator to the metal in the catalyst compound in the slurry catalyst mixture can be from 1000:1 to 0.5:1, 300:1 to 1:1, 100:1 to 1:1, or 150:1 to 1:1. The slurry catalyst mixture may contain a support material, which can be any inert particulate support material known in the art, including but not limited to silica, fumed silica, alumina, clay, talc, or other support materials, such as those disclosed above. In one embodiment, the slurry may contain silica and an activator, such as methylaluminoxane (“MAO”) or modified methylaluminoxane (“MMAO”), as discussed further below. In embodiments, the activator includes aluminoxane compounds, modified aluminoxane compounds, and ionized anionic precursor compounds that abstract reactive σ-bonded metal ligands, giving the metal compound a positive charge and providing a charge-balanced uncoordinated or weakly coordinated anion.

[0107] As described above, one or more organoaluminum compounds, such as one or more alkylaluminum compounds, can be used with aluminum oxanes. For example, usable alkylaluminum substances include diethylethoxyaluminum, diethylaluminum chloride, and / or dibutylaluminum hydride. Examples of trialkylaluminum compounds include, but are not limited to, trimethylaluminum, triethylaluminum (“TEAL”), triisobutylaluminum (“TiBA1”), tri-n-hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, etc.

[0108] Suitable supports include, but are not limited to, active and inactive materials, synthetic or naturally occurring zeolites, and inorganic materials such as clay and / or oxides, such as silica, alumina, zirconium oxide, titanium oxide, silica-alumina, cerium oxide, magnesium oxide, or combinations thereof. In particular, the support can be silica-alumina, alumina, and / or zeolites, especially alumina. Silica-alumina can be naturally occurring or in the form of a gel-like precipitate or gel (containing a mixture of silica and metal oxides).

[0109] In some embodiments, at least a portion of the slurry catalyst mixture may be contacted with the solution catalyst mixture to produce or otherwise form a slurry / solution catalyst mixture.

[0110] In some embodiments, the slurry catalyst mixture may comprise one or more supported metallocenes. For example, the metallocene catalyst may be contacted with and reacted with a co-catalyst such as MAO. A support structure may then be added to produce a supported metallocene catalyst. The supported catalyst may be added to a sufficient amount of the slurry mixture to produce the slurry catalyst mixture. In at least one embodiment, the metallocene catalyst may be any one or more catalysts previously described in Formulas I and II. In some embodiments, the supported metallocene may comprise one or more metallocene catalysts on a support structure. In at least one embodiment, the metallocene catalyst of the supported metallocene catalyst is any one or more of the following: dimethylsilyl(tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl)dimethylhafnium, dimethylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindenyl)]zirconium dichloride, (5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthyl-1-yl)dimethylzirconium, and combinations thereof. In at least one embodiment, the metallocene catalyst of the supported metallocene catalyst is dimethylsilyl(tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl)dimethylhafnium.

[0111] Solution catalyst mixture – trimmed solution

[0112] The solution catalyst mixture may contain a solvent and only catalyst compounds (one or more) (e.g., without a support material), such as one or more metallocene catalyst compounds as previously described in formulas (I) and (II), or may also contain an activator. In some embodiments, the solution catalyst mixture may be, or may contain, but is not limited to, the contact product of a solvent / diluent with a first catalyst and / or a second catalyst compound. In some embodiments, the solution catalyst mixture may contain the contact product of a solvent / diluent with any one or more of the first, second, third, etc., catalyst compounds. The catalyst compounds (one or more) in the solution catalyst mixture are unsupported. Furthermore, the slurry / solution catalyst mixture may be introduced into the gas-phase polymerization reactor. The solution catalyst mixture may be a single solution catalyst mixture (e.g., provided by trimming tank 104A or trimming tank 104B) or may be a sum of two or more solution catalyst mixtures (e.g., provided by trimming tank 104A and trimming tank 104B respectively to line 130). The catalyst mixture in trimming tank 104A or trimming tank 104B may contain one catalyst compound, two catalyst compounds, three catalyst compounds, or more.

[0113] Solution catalyst mixtures are prepared by dissolving one or more metallocene catalyst compounds as described in the previous formulas (I) and (II) and an optional activator in a liquid solvent. The liquid solvent may be an alkane, such as a C5-C... 30 Alkanes or C5-C 10 Alkanes. Cycloalkanes (e.g., cyclohexane) and aromatic compounds (e.g., toluene) can also be used. Mineral oils can be used as a substitute for other alkanes (e.g., one or more C5-C6 hydrocarbons). 30 The solvent may be an alkane or other solvent used in addition to other alkanes. If mineral oil is used in the solution catalyst mixture, it may have the same properties as the mineral oil used to prepare the slurry catalyst mixture described above. The solvent should be liquid and relatively inert under polymerization conditions. Optionally, the solvent used in the solution catalyst mixture may be different from the diluent used in the slurry catalyst mixture. Alternatively, on the other hand, the solvent used in the solution catalyst mixture may be the same as the diluent (i.e., one or more mineral oils and any additional diluent used in the slurry catalyst mixture).

[0114] If the solution catalyst mixture comprises both one or more metallocene catalyst compounds and an activator, the ratio of the metal in the activator to the metal in all catalyst compounds (one or more) in the solution catalyst mixture can be from 1000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. In various embodiments, the activator and catalyst compounds (one or more) can be present together in the solution catalyst mixture at a maximum of 90% by weight, a maximum of 50% by weight, a maximum of 20% by weight, for example, a maximum of 10% by weight, a maximum of 5% by weight, or less than 1% by weight or from 100 ppm to 1% by weight, based on the weight of the solvent, activator, and catalyst. If one or more activators from the solution catalyst mixture are used, they can be the same as or different from one or more activators used in the slurry catalyst mixture.

[0115] The solution catalyst mixture may contain any one or more of the catalyst compounds disclosed herein. Since the catalyst is dissolved in solution, higher solubility is desirable. Therefore, the catalyst in the solution catalyst mixture may often include metallocenes, which may have higher solubility than other catalysts. In the polymerization process, any of the above-described solution catalyst mixtures may be combined with any of the above-described slurry catalyst mixtures. Furthermore, more than one solution catalyst mixture may be used (e.g., a first trimming solution and a second trimming solution, which may have the same or different catalysts and may be supplied at the same or different flow rates).

[0116] Continuous additives - static control agents

[0117] In the production process of fumed polyethylene, it is desirable to use one or more electrostatic control agents to help regulate the electrostatic level within the reactor. Continuous additives are chemical compositions that, when introduced into a fluidized bed within the reactor, can influence or drive the electrostatic charge (negative, positive, or to zero) within the fluidized bed. The continuous additive used can depend at least in part on the nature of the electrostatic charge, and the choice of electrostatic control agent can vary at least in part based on the polymer being produced and / or the unit point catalyst compound used. In some embodiments, the continuous additive or electrostatic control agent can be introduced into the reactor in amounts from 0.05 ppm to 200 ppm. Alternatively, the amount of the continuous additive or electrostatic control agent can be from 0.05 ppm to 2 ppm, 5 ppm, or 10 ppm, or from 20 ppm to 50 ppm, 75 ppm, 100 ppm, 150 ppm, or 200 ppm.

[0118] In some embodiments, the continuous additive may be or may include aluminum stearate. The continuous additive can be selected based on its ability to receive electrostatic charges in the fluidized bed without negatively impacting productivity. Other suitable continuous additives may be or may include, but are not limited to, aluminum distearate, ethoxylated amines, and combinations thereof. In some embodiments, the continuous additive comprises a mixture of polysulfone copolymers, polymeric polyamines, and oil-soluble sulfonic acids. Any continuous additive may be used alone or in combination.

[0119] In some embodiments, the continuous additive may include fatty acid amines, amide-hydrocarbons or ethoxylated-amide compounds, carboxylic acid esters such as aryl-carboxylic acid esters and long-chain hydrocarbon carboxylic acid esters, and fatty acid-metal complexes; alcohols, ethers, sulfate compounds, metal oxides, and other compounds known in the art. Specific examples of control agents may include, but are not limited to, 1,2-diether organic compounds, magnesium oxide, glycerides, ethoxylated amines (e.g., N,N-bis(2-hydroxyethyl)octadecylamine), alkyl sulfonates and alkoxylated fatty acid esters, chromium N-oleoyl-o-aminobenzoate, calcium salts of N-acylsarcosine and di-tert-butylphenol, α-olefin-acrylonitrile copolymers and polymeric polyamines, sorbitan monooleate, glyceryl monostearate, methyl toluene, dimethyl maleate, dimethyl fumarate, triethylamine, 3,3-diphenyl-3-(imidazol-1-yl)propynyl, and similar compounds. In some embodiments, additional continuous additives may include metal carboxylates, optionally together with other compounds.

[0120] In some embodiments, the continuous additive may include extracted metal carboxylates, which may be combined with amine-containing reagents, such as extracted metal carboxylate salts. For example, the extracted metal carboxylates may be combined with antistatic agents such as fatty amines, such as blends of ethoxylated stearylamine and zinc stearate, or blends of ethoxylated stearylamine, zinc stearate, and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

[0121] Other continuous additives may include ethyleneimine additives, for example, those having the following general formula: -(CH2-CH2-NH n -of polyethyleneimine, where n can be from 10 to 10,000. Polyethyleneimine can be linear, branched, or highly branched (e.g., forming dendritic or tree-like polymer structures). Polyethyleneimine can be a homopolymer or copolymer of ethyleneimine or a mixture thereof (hereinafter referred to as polyethyleneimine (one or more)). Although it can be made of the chemical formula -(CH2-CH2-NH) n - indicates a linear polymer as polyethyleneimine, but materials with primary, secondary, and tertiary branching can also be used.

[0122] Inducing condensate

[0123] In the production process of gas-phase polyethylene, it is desirable to use one or more induced condensers within the reactor. An "induced condenser (iCA)" refers to one or more induced condensable fluids, which are volatile liquid hydrocarbons selected from saturated hydrocarbons containing 2 to 10 carbon atoms, preferably 3 to 10 carbon atoms. Some suitable saturated hydrocarbons are propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane and other saturated C6 hydrocarbons, n-heptane, n-octane and other saturated C7 and C8 hydrocarbons, or mixtures thereof. A preferred class of induced condensable hydrocarbons includes C5 and C6 saturated hydrocarbons. Another preferred class includes C4 to C6 saturated hydrocarbons. Preferred hydrocarbons used as condensable fluids include pentane, such as isopentane. The condensable fluid may also contain polymerizable condensable comonomers, such as olefins, dienes, or mixtures thereof, including some of the monomers mentioned herein, which may be partially or wholly incorporated into the polymer product.

[0124] End use

[0125] Polyolefins obtained by the methods disclosed herein can possess long-chain branching (LCB), a characteristic commonly found in low-density polyethylene grades. Such LCB provides inherent benefits to material processability, such as high melt strength, high shrinkage, and good optical properties. Typically, LCB can lead to unintended detrimental effects on the mechanical properties of the resulting material (i.e., tear resistance and dart impact strength). However, materials produced using polyolefins obtained by the methods disclosed herein exhibit good optical and mechanical properties. Unbound by theory, polyolefin copolymers produced by the methods disclosed herein comprise a balance of LCB and physical entanglement, thereby achieving the desired mechanical properties of the material (e.g., film) while maintaining good optical properties and processability.

[0126] Polymers and their blends produced by the methods disclosed herein can be used in molding operations such as film, sheet, and fiber extrusion and co-extrusion, as well as blow molding, injection molding, and rotational molding. Films include blown or cast films formed by co-extrusion or lamination, which can be used as shrink films, cling films, stretch films, sealing films, oriented films, snack packaging, heavy-duty bags, grocery bags, baked and frozen food packaging, medical packaging, industrial linings, and membranes in food and non-food contact applications. Fibers include melt-spinning, solution-spinning, and meltblown fiber operations used to manufacture filters, diaper fabrics, medical clothing, geotextiles, etc., in woven or nonwoven forms. Extruded products include medical tubing, wire and cable coatings, pipes, geomembranes, and pool liners. Molded products include single-layer and multi-layer constructions in the form of bottles, cans, large hollow products, rigid food containers, and toys.

[0127] In particular, any of the aforementioned polymers, such as ethylene copolymers or blends thereof, can be used for single-layer or multi-layer blow molding, extrusion, and / or shrink films. These films can be formed using any number of known extrusion or co-extrusion techniques, such as blown film processing techniques, in which the composition can be extruded through an annular die in a molten state and then expanded to form a uniaxially or biaxially oriented melt, which is then cooled to form a tubular blown film, which can then be axially cut and unfolded to form a flat film. The film can subsequently be unoriented, uniaxially oriented, or biaxially oriented to the same or different degrees.

[0128] The polymers produced herein can be further blended with one or more second polymers and used in films, molded parts, and other typical applications. In one embodiment, the second polymer can be selected from ethylene homopolymers, ethylene copolymers, and blends thereof. Available second ethylene copolymers may contain one or more comonomers in addition to ethylene and can be random copolymers, statistical copolymers, block copolymers, and / or blends thereof. The method for preparing the second ethylene polymer is not limited, as it can be prepared by slurry, solution, gas phase, high pressure, or other suitable methods, and by using a catalyst system suitable for the polymerization of polyethylene, such as Ziegler-Natta catalysts, chromium catalysts, metallocene catalysts, other suitable catalyst systems, or combinations thereof, or by free radical polymerization.

[0129] Polymer films can be prepared from any one or more polymers and / or additives disclosed herein by any one or more suitable methods known to those skilled in the art. In some embodiments, the polymer film has a melt index (I2; determined by ASTM D-1238) of about 0.8 g / 10 min to about 1 g / 10 min, for example about 0.85 g / 10 min to about 0.95 g / 10 min, for example about 0.89 g / 10 min to about 0.925 g / 10 min. In some embodiments, the polymer film has a high-load melt index (I2) of about 10 g / 10 min to about 25 g / 10 min, for example about 13 g / 10 min to about 23 g / 10 min, for example about 16 g / 10 min to about 18 g / 10 min. 21 (Measured by ASTM D-1238). In some embodiments, the polymer film has a melt index ratio (I) of about 15 to about 25, for example about 16.5 to about 23.5, for example about 19 to about 20. 21 / I2).

[0130] In some embodiments, the polymer film of this disclosure may have a haze of about 5% to about 10%, such as about 5.5% to about 9%, such as about 6% to about 8.5% (measured by ASTM D-1003). In some embodiments, the polymer film may have a transparency of about 95% to about 99.9%, such as about 98.5% to about 99.5%, such as about 98.8% to about 99.4% (measured by ASTM D 1746).

[0131] Example

[0132] Synthesis of metallocene catalyst 1:

[0133]

[0134] Synthesis of (5,5,8,8-tetramethyl-6,7-dihydro-3H-cyclopentadieno[b]naphthyl)lithium(1):

[0135] To a white suspension of 5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthalene (20.18 g, 89.2 mmol, 1.00 equivalent) in diethyl ether (250 mL) under vigorous stirring, n-butyllithium in hexane (36 mL, 90.0 mmol, 1.01 equivalent) was added to give a cold, turbid, pale yellow mixture. The reaction turned turbid and bright yellow after stirring for 20 minutes. The reaction was stirred overnight and then evaporated under vacuum, leaving a dirty white solid. The solid was washed with pentane (100 mL) and filtered to give a bright white solid. The yield was 18.8 g (91%) of bright white powder. 1 H NMR (THF-D8) 7.46 (s, 2H), 6.50 (t, 1H), 5.81 (dt, 1H), 1.72 (S, 4H), 1.34 (S, 12H).

[0136] Synthesis of (5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium dichloride (2):

[0137] To a vigorously stirred white suspension of zirconium tetrachloride (2.98 g, 12.8 mmol, 1.00 equivalent) in diethyl ether (200 mL) at -35 °C, lithium (1) (6.30 g, 25.6 mmol, 2.00 equivalent) was added to give a cold, turbid, pale yellow mixture. The reaction turned turbid and bright yellow after stirring for 20 minutes. The reaction was stirred overnight and then evaporated under vacuum, leaving a bright yellow solid. The solid was extracted with dichloromethane (100 mL) and the extract was filtered to give a bright yellow solid. The solid was washed with cold pentane (50 mL) and dried under vacuum. The yield was 16.01 g (97%) of bright yellow powder. 1 H NMR (CD2Cl2) 7.52 (S, 4H), 6.15 (dt, 2H), 5.82 (dt, 4H), 1.58 (m, 8H), 1.37 (s, 12H), 1.23 (s, 12H).

[0138] Synthesis of (5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)dimethylzirconium(3):

[0139] 3.28 M MeMgBr (39.7 mL, 0.119 mol, 5.0 equivalent) in Et₂O was added to a bright yellow suspension of (2) (14.6 g, 0.024 mol, 1.0 equivalent) in 100 mL diethyl ether at -35 °C to give a cold, turbid yellow mixture. The reaction mixture was stirred overnight at room temperature. The solvent was removed under vacuum. The product was extracted with pentane and a dark brown solid was filtered off. Removal of pentane under vacuum resulted in the formation of a pale yellow solid, 12.5 g, 91.6%. 1 H NMR (CD2Cl2) 7.37 (S, 4H), 5.82 (dt, 4H), 5.70 (dt, 2H), 1.59 (m, 8H), 1.27 (s, 24H), -0.83 (s, 6H).

[0140] Synthesis of metallocene catalyst 2:

[0141]

[0142] Synthesis of 1H-inden-1-yllithium (4):

[0143] To a vigorously stirred white suspension of indene (17.9 g, 154 mmol, 1.00 equivalent) in diethyl ether (250 mL) at -35 °C, n-butyllithium in hexane (62.3 mL, 156 mmol, 1.01 equivalent) was added to give a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned turbid and bright yellow. The reaction was stirred overnight and then evaporated under vacuum, leaving a dirty white solid. The solid was washed with pentane (100 mL) and filtered to give a bright white solid. The yield was 18.3 g (97%) of bright white powder. 1 H NMR (THF-D8) 7.32 (m, 2H), 6.54 (t, 1H), 6.45 (m, 2H), 5.92 (dt, 2H).

[0144] Synthesis of chloro-(1H-inden-1-yl)-dimethyl-silane (5):

[0145] Pure Me₂SiCl₂ (57.2 g, 443 mmol, 3.0 equivalent) was added dropwise over a period of 5–10 minutes to a suspension of lithium indenide (18.0 g, 148 mmol, 1.0 equivalent) cooled to -25 °C in 250 mL of diethyl ether. The resulting mixture was stirred overnight at room temperature. Volatiles were removed from the mixture under vacuum, and the mixture was then extracted into pentane to remove insoluble material and LiCl. Removal of pentane under vacuum resulted in the formation of a pale yellow oil, 22.7 g, 73.5% yield. 1 H NMR (CD2Cl2) 7.50 (dt, 1H), 7.35 (dt, 1H), 7.20-7.12 (m, 2H), 6.78 (ddt, 1H), 6.43 (ddt, 1H), 3.47 (s, 1H), 0.00 (s, 3H), 0.08 (s, 3H).

[0146] Synthesis of 1H-inden-1-yl-dimethyl-[3-(trimethylsilylmethyl)cyclopent-2,4-dien-1-yl]silane (6):

[0147] Solid trimethylsilyl methylcyclopentadienyl lithium (11.7 g, 74.2 mmol, 1.1 equivalent) was added to a solution of chloro-(1H-inden-1-yl)-dimethylsilane (5) (12.9 g, 61.8 mmol, 1.0 equivalent) in THF (200 ml) cooled at 25 °C. The resulting mixture was stirred overnight at room temperature. All volatiles were removed under vacuum and the mixture was ground with hexane (100 ml). The crude material was then extracted with hexane (100 ml) and the hexane was removed, giving a pale yellow oil, 19.6 g, 97.7%. 1H NMR(C6D6)7.45(dt,2H),7.27(t,1H),7.15(s,1H),6.87(s,1H),6.55(s,1H),6.40(dt,1H),6.0 9-5.69 (s, 2H), 3.43 (s, 1H), 3.19 (s, 1H), 1.27 (m, 1H), 0.03 (s, 9H), -0.13 (s, 3H), -0.31 (s, 3H).

[0148] Synthesis of (1H-inden-1-yl-dimethyl-[3-(trimethylsilylmethyl)cyclopent-2,4-dien-1-yl]silyl)lithium (7):

[0149] To a vigorously stirred, pale yellow solution (6) (20.1 g, 61.8 mmol, 1.00 equivalent) in diethyl ether (250 ml) at -35 °C, n-butyllithium in hexane (49.7 ml, 124.0 mmol, 2.01 equivalent) was added to give a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned to a turbid, bright yellow. The reaction was stirred overnight and then evaporated under vacuum, leaving a dirty white solid. The solid was washed with pentane (100 ml) and filtered to give a bright white solid. The yield was 18.8 g (91%) of bright white powder. 1 H NMR(THF-D8)7.76(m,1H),7.36(m,1H),6.83(d,1H),6.53(d,1H),6.06(d, 1H), 5.91(dt, 1H), 5.81(dt, 1H), 5.59(dt, 1H), 0.47(S, 6H), 0.00(S, 9H).

[0150] Synthesis of dimethylsilyl(indenyl)(trimethylsilylmethylcyclopentadienyl)hafnium dichloride (8):

[0151] Adding (7) (20.7 g, 61.5 mmol, 1.00 equivalent) to a vigorously stirred white suspension of hafnium tetrachloride (21.7 g, 67.7 mmol, 1.10 equivalent) in diethyl ether (200 ml) at -35 °C yielded a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned to a turbid, bright yellow. The reaction was stirred overnight and then evaporated under vacuum, leaving a bright yellow solid. The solid was extracted with dichloromethane (100 ml) and the extract was filtered to give a bright yellow solid. The solid was washed with cold pentane (50 ml) and dried under vacuum. The yield was 21.2 g (60.6%) of bright yellow powder. 1H NMR(CD2Cl2)7.71(m,1H),7.58-7.48(m,1H),7.38(m,1H),7.13-6.95(m,1H),6.21(d,1H),6.11(d,1H),5.79-5.74 (dt, 1H), 5.30-5.21 (dt, 1H), 2.20 (dt, 1H), 2.16 (m, 1H), 1.82 (dt, 1H), 1.03 (dt, 3H), 0.83 (dt, 3H), -0.03 (d, 9H).

[0152] Synthesis of dimethylsilyl(tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl)hafnium dichloride (9):

[0153] 0.050 g of PtO2 (540 mg, 2.38 mmol, 0.12 equivalents) was added to a turbid yellow solution (8) (10.1 g, 17.7 mmol, 1.0 equivalents) in 200 mL of CH2Cl2 to give a dirty yellow mixture in the Parr reactor. Hydrogen gas was applied at 1000 psi and the reaction mixture was stirred vigorously over the entire weekend. Excess hydrogen gas was purged and the black solid was filtered to give a pale yellow solid. Yield: 7.23 gg (79%). 1 H NMR(CD2Cl2)7.15-7.08(m, 1H), 7.08(m, 2H), 7.00-6.78(m, 1H), 6.57-6.32 (m, 2H), 2.88-2.02 (m, 8H), 1.05-0.64 (m, 2H), 0.44 (dt, 6H), 0.06 (dt, 9H).

[0154] Synthesis of dimethylsilyl(tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl)dimethylhafnium(10):

[0155] Add 3.28M MeMgBr (20.8 mL, 624 mmol, 4.0 equivalence) of Et₂O to a bright yellow suspension of 9 (8.99 g, 156 mmol, 1.0 equivalence) in 100 mL diethyl ether at -35 °C to give a cold, cloudy yellow mixture. Stir the reaction mixture overnight at room temperature. Remove the solvent under vacuum. Extract the product with pentane and filter out a dark brown solid. Removal of pentane under vacuum results in a pale yellow solid, 7.09 g, 85.0%. 1 H NMR (C2D2) 7.12-6.94 (m, 3H), 5.95-5.69 (m, 3H), 2.74-1.59 (m, 10H), 0.26 (s, 9H), 0.17 (dt, 6H), -0.03 (dt, 6H).

[0156] Synthesis of metallocene catalyst 3:

[0157]

[0158] Synthesis of 3-methyl-indene(11):

[0159] Adding 1H-inden-1-yllithium (4) (8.08 g, 66 mmol, 1 equivalent) to a colorless solution of MeI (18.8 g, 133 mmol, 2 equivalents) in diethyl ether (200 ml) at -35 °C yielded a turbid white mixture. The reaction mixture was stirred overnight at room temperature. Adding 1,2-dimethoxyethane (6 g) to the clear yellow reaction mixture resulted in the formation of a white precipitate. The solvent was removed under vacuum, leaving a white solid. The product was extracted with pentane (100 ml) and filtered, yielding an amber solution and a white precipitate. Drying the amber solution under vacuum yielded a yellow viscous oil. (Yield: 5.73 g, 66%). 1 H NMR (C6D6) 7.8 (m, 4H), 6.65 (dd, 1H), 6.21 (dd, 1H), 3.22 (m, 1H), 1.07 (d, 3H).

[0160] Synthesis of 3-methyl-inden-1-yllithium (12):

[0161] To a white suspension of 3-methylindene (11) (10.1 g, 77.6 mmol, 1.00 equivalent) in diethyl ether (250 mL) under vigorous stirring at -35 °C, n-butyllithium in hexane (31.3 mL, 78.4 mmol, 1.01 equivalent) was added to give a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned turbid and bright yellow. The reaction was stirred overnight and then concentrated under vacuum to give a dirty white solid. The solid was washed with pentane (100 mL) and separated by filtration to give a bright white powder (yield 10 g, 95%). 1 H NMR (THF-D) 8 )7.24(m, 2H), 6.43(m, 2H), 6.33(d, 2H), 5.71(dd, 2H), 2.42(d, 3H).

[0162] Synthesis of dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyl trifluoromethanesulfonate (13):

[0163] AgOTf (39.9 g, 155 mmol, 1.05 equivalent) was added aliquoted to a yellow solution of Me4CpSiMe2Cl (31.8 g, 148 mmol, 1.0 equivalent) in 100 mL of toluene. Upon addition of AgOTf, the reaction mixture became cloudy white and warm. The reaction rapidly turned grayish-pink, then grayish-purple. After stirring for 15 minutes, the reaction mixture became a dark, muddy-colored mixture with a large amount of solids. The reaction mixture was stirred at room temperature for 3 hours. The solvent was removed under vacuum to give the dark mixture, which was then used in the next step.

[0164] Synthesis of dimethyl(3-methyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane (14):

[0165] 3-Methyl-inden-1-yllithium (12) (5.61 g, 41.2 mmol, 1.0 equivalent) was added to a solution of dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyl trifluoromethanesulfonate (Me4CpSiMe2OTf, 13) (13.5 g, 41.2 mmol, 1.0 equivalent) in Et2O at -35 °C. The reaction mixture was stirred overnight at room temperature. The solvent was removed under vacuum. The product was extracted with pentane and subsequently concentrated under vacuum to give a golden solid in a yield of 12.1 g (96%). 1 HNMR(C6D6)7.47(dq,1H),7.39(dt,1H),7.38-7.27(m,1H),7.22(td,1H),6.23(p,1H),3.59-3.5 4(s, 1H), 2.95(s, 1H), 2.18-2.10(m, 3H), 1.93(s, 6H), 1.83(s, 6H), -0.15(s, 3H), -0.37(s, 3H).

[0166] Synthesis of dilithium [tetramethylcyclopentadienyldimethylsilyl(3-methylindenyl)] ether (15):

[0167] To a solution of dimethyl(3-methyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane (14) (12.1 g, 39.4 mmol, 1.0 equivalent) in Et₂O at -35 °C, n-butyllithium in hexane (32.3 mL, 80.7 mmol, 2.05 equivalent) was slowly added. The reaction mixture was stirred overnight at room temperature. The solvent was then removed under vacuum. The resulting crude material was washed with pentane to give a white powder (15.1 g, 97% yield). 1 H NMR (THF-D)8 )7.60-7.53(d, 1H), 7.26-7.19(d, 1H), 6.57(s, 1H), 6.45(m, 2H), 3.61(s, 1H), 3.43( q, 3H), 2.40 (s, 3H), 2.17 (s, 6H), 1.91 (s, 6H), 1.76 (s, 1H), 1.16 (t, 5H), 0.63 (s, 6H).

[0168] Synthesis of tetramethylcyclopentadienyldimethylsilyl(3-methylindenyl)zirconium dichloride (16):

[0169] ZrCl4(OEt2)2 (10.56 g, 45.3 mmol, 1.20 equivalence) was added to a suspension of dilithium [tetramethylcyclopentadienyldimethylsilyl(3-methylindenyl)] ether (15) (12.1 g, 37.8 mmol) in Et2O under vigorous stirring at -35 °C. The reaction mixture was stirred overnight at room temperature. The ether was removed under vacuum. The product was extracted with CH2Cl2 and filtered to give a yellow solution. The solvent was removed under vacuum, leaving a yellow solid. The solid was washed with pentane. Yield: 15.6 g, 88%. 1 H NMR (CD2Cl2) 7.50 (ddt, 2H), 7.31 (ddd, 1H), 7.02 (ddd, 1H), 5.55 (d, J =0.9Hz, 1H), 2.46 (d, J =0.6Hz, 3H), 1.98(s, 3H), 1.91(d, J =2.2Hz, 6H), 1.88(s, 3H), 1.17(s, 3H), 0.92(s, 3H).

[0170] Synthesis of [tetramethylcyclopentadienyldimethylsilyl(3-methyltetrahydroindenyl)]zirconium dichloride (17):

[0171] PtO2 (0.55 g, 2.42 mmol, 0.10 equivalent) was added to a solution of tetramethylcyclopentadienyldimethylsilyl(3-methylindenyl)zirconium dichloride (16) (11.4 g, 24.3 mmol, 1.0 equivalent) in 200 mL of CH2Cl2. Hydrogen gas (500 psi) was added, and the reaction was stirred overnight in a Parr reactor at room temperature. The pressure was released, and the reaction solution was separated from the black solid by filtration. The solvent was then removed under vacuum to give the solid. Yield: 10.1 g (88%). 1H NMR(CD2Cl2)5.06(s,1H),2.67(m,1H),2.53(m,2H),2.34(m,2H),2.07(s,3H),2.04(s,3H), 2.02 (s, 3H), 1.93 (s, 3H), 1.85 (s, 3H), 1.58 (m, 1H), 1.47 (m, 1H), 0.90 (s, 3H), 0.79 (s, 3H).

[0172] Preparation of supported catalysts:

[0173] Anhydrous toluene (1800 g) and 30% MAO (894 g) in toluene were added to a 4 L conical mixing vessel. The vessel was sealed and stirring was started at 120 rpm. Then, metallocene in toluene (metallocene catalyst 2) (15.0 g, 29.03 mmol) was added through a funnel at the top of the mixer. The reaction mixture was stirred at room temperature for 1 hour. After this time, silica was added over 10 minutes through the same funnel as before. Stirring was continued for another hour, after which the stirring rate was reduced and the solvent was removed under vacuum to obtain the supported metallocene. The supported catalyst was then added to a vessel with a sufficient amount of slurry mixture (SJCS-380, Sonneborn) to obtain 20 wt% of the slurry catalyst.

[0174] Preparation of trimming solution:

[0175] For individual catalyst trimming (hereinafter referred to as "trimmed solution 1"), metallocene (metallocene catalyst 1) is added in pure form to an open vessel. Anhydrous isohexane is added in sufficient quantity to produce a solution having a total metallocene composition of 0.04 wt%. For mixed catalyst trimming (hereinafter referred to as "trimmed solution 2"), metallocene (metallocene catalyst 1:metallocene catalyst 3) in a 5:1 molar ratio is added in pure form to an open vessel. Anhydrous isohexane is added in sufficient quantity to produce a solution having a total metallocene composition of 0.04 wt%.

[0176] polymerization:

[0177] Polymerization takes place in a 22-foot-high gas-phase fluidized bed reactor with a 13-inch straight inner diameter and a wider conical extension section above. Recirculated gas and feed gas are fed into the reactor body through a porous distribution plate, maintaining the reactor at 290 psig and 64 mol% ethylene. The reactor temperature is maintained constant throughout the polymerization by controlling the temperature of the recirculated gas loop.

[0178] Optionally, the supported catalyst (20 wt% slurry) is brought into online contact with a trimmed catalyst solution (0.04 wt% total trimming) at an adjustable ratio, mixed to homogenize, and given sufficient time to allow the trimmed catalyst to diffuse, anchor, and activate, thereby adjusting the active catalyst ratio. In some respects, the adjustment of the active catalyst ratio can be measured and used as a control variable.

[0179] Table 1 shows the control and trimmed portions. The control was predominantly single-peaked (low, ~17 MIR), and adding trimmed solution 1 in increasing amounts (Comparative Examples C2 and C3) affected the density but only moderately increased the MIR. Adding trimmed solution 2 at the same overall trimmed flow rate as C3, but with a smaller amount containing a trimmed catalyst containing LCB (Catalyst 3), produced a greater increase in MIR (Example 2 compared to Comparative Example 3).

[0180] Table 1: Summary of Conditions

[0181]

[0182] Table 2

[0183]

[0184] In general, the methods disclosed herein provide gas-phase reactor polymerization using multiple trimming catalysts (as one or more trimming solutions) to obtain desired process conditions and to produce polymers with specified properties. By implementing two or more trimming solutions that can be separately metered and independently controlled, a greater degree of freedom and control over the gas-phase reaction method and its polymer properties can be obtained.

[0185] Unless otherwise specified, the phrases "consist essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not they are specifically mentioned in this specification, provided that such steps, elements, or materials do not affect the essential and novel features of this disclosure. Furthermore, they do not exclude impurities and variations commonly associated with the elements and materials used.

[0186] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range defined by any lower limit can be combined with any upper limit to describe a range not explicitly described, and a range defined by any lower limit can be combined with any other lower limit to describe a range not explicitly described, just as a range defined by any upper limit can be combined with any other upper limit to describe a range not explicitly described. Furthermore, each point or individual value between its endpoints is included within a range, even if not explicitly described. Therefore, each point or individual value can serve as its own lower or upper limit, combined with any other point or individual value or any other lower or upper limit, to describe a range not explicitly described.

[0187] All literature described herein is incorporated herein by reference, including any priority documents and / or test procedures, provided they are not inconsistent with this document. It will be apparent from the foregoing general description and specific embodiments that various modifications may be made without departing from the spirit and scope of the invention, although the forms of the invention have been shown and described. Therefore, it is not intended to limit this disclosure. Similarly, for the purposes of U.S. law, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements is preceded by the transitional phrase “comprising,” it should be understood that we also contemplate the same composition or group of elements preceded by the transitional phrases “substantially constitutes,” “consisting of,” “selected from the group of,” or “is,” and vice versa.

[0188] Although this disclosure has been described with reference to various embodiments and examples, those skilled in the art who benefit from this disclosure will understand that other embodiments can be devised without departing from the scope and spirit of this disclosure.

Claims

1. A method comprising: A catalyst slurry comprising a supported catalyst is provided, said supported catalyst comprising a support material, at least a first catalyst compound, and at least one activator; The catalyst slurry is contacted with one or more catalyst solutions to obtain a modified catalyst slurry, wherein: The one or more catalyst solutions comprise a first catalyst solution, the first catalyst solution comprising a second catalyst compound and a third catalyst compound, and The modified catalyst slurry comprises a modified supported catalyst, which comprises a first catalyst compound, a second catalyst compound, and a third catalyst compound. The modified catalyst slurry is fed into a fluidized bed gas-phase reactor; and α-olefins are polymerized in the fluidized bed gas-phase reactor under polymerization conditions to obtain polyolefins.

2. The method according to claim 1, wherein the first catalyst solution further comprises a fourth catalyst compound.

3. The method according to claim 1, wherein the supported catalyst further comprises a fourth catalyst compound.

4. A method comprising: A catalyst slurry comprising a supported catalyst is provided, said supported catalyst comprising a support material, at least a first catalyst compound, and at least one activator; The catalyst slurry is contacted with two or more catalyst solutions to obtain a modified catalyst slurry, wherein: The two or more catalyst solutions comprise a first catalyst solution and a second catalyst solution, the first catalyst solution comprising a second catalyst compound, the second catalyst solution comprising a third catalyst compound, and... The modified catalyst slurry comprises a modified supported catalyst, which comprises a first catalyst compound, a second catalyst compound, and a third catalyst compound. The modified catalyst slurry is fed into a fluidized bed gas-phase reactor; and α-olefins are polymerized in the fluidized bed gas-phase reactor under polymerization conditions to obtain polyolefins.

5. The method of claim 4, wherein the first catalyst solution comprises a fourth catalyst compound.

6. The method of claim 4, wherein when the first and second catalyst solutions are brought into contact with the catalyst slurry, the first and second catalyst solutions are metered and controlled independently.

7. The method of claim 4, wherein the second catalyst solution comprises a fourth catalyst compound.

8. The method of claim 4, wherein the supported catalyst further comprises a fourth catalyst compound.

9. The method according to claim 1 or 4, wherein one or more of the first catalyst compound, the second catalyst compound, or the third catalyst compound are independently represented by formula (I): (I) in: M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' Each of the following is independently hydrogen, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; R 5 and R 6 R 7 and R 8 R 8 and R 9 and R 9 and R 10 One or more pairs of rings in R are coupled to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, or R 7' and R 8' R 8' and R 9' and R 9' and R 10' One or more pairs of such pairs do not exist such that there are carbon-carbon double bonds between the corresponding carbon atoms of the hydride indenyl ring shown in formula (I); T represents R a 2J、(R a )4J2 or (R a )6J3, where each J is independently C, Si, or Ge, and each R a Independently hydrogen, halogenated, substituted or unsubstituted C1-C 40 Hydrocarbon group, or two Rs a It can form substituted or unsubstituted cyclic structures, including substituted or unsubstituted fully saturated rings, substituted or unsubstituted partially saturated rings, or substituted or unsubstituted aromatic rings; and X 1 and X 2 Each can be independently a monovalent anionic ligand, diene ligand, alkylidene ligand, or X. 1 and X 2 Joined to form a metal ring.

10. The method of claim 9, wherein R 7 R 7' R 8 R 8' R 9 R 9' R 10 and R 10' Each is hydrogen.

11. The method of claim 10, wherein T is R a 2J, where J is Si and each R a It is a methyl group.

12. The method according to claim 11, wherein at least one of the first catalyst compound, the second catalyst compound, or the third catalyst compound is .

13. The method according to claim 11, wherein at least one of the first catalyst compound, the second catalyst compound, or the third catalyst compound is .

14. The method according to claim 9, wherein one or more of the first catalyst compound, the second catalyst compound, the third catalyst compound, or combinations thereof are represented by formula (II): (II) in: M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 21' R 22 R 22' R 23 R 23' R 24 R 24' R 25 R 25' R 26 R 26' R 27 R 27' R 28 and R 28' Each of the following is independently hydrogen, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; and Each X is independently a halogen, a substituted or unsubstituted hydrocarbon, a hydrogen, an amino, a substituted or unsubstituted alkoxy, a thio, a phosphorus, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metal ring, or two Xs are joined together to form a chelate ligand, a diene ligand, or an alkylidene group.

15. The method of claim 14, wherein R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 21' R 22 R 22' R 23 R 23' R 24 R 24' R 25 R 25' R 26 R 26' R 27 R 27' R 28 and R 28' Each can be either hydrogen or methyl.

16. The method of claim 15, wherein at least one of the first catalyst compound, the second catalyst compound, or the third catalyst compound is .

17. The method according to claim 1 or 4, wherein the obtained polyolefin is a copolymer derived from monomers comprising ethylene and α-olefin comonomers, wherein the α-olefin comonomer is any one or more C3-C 12 α-olefin monomers.

18. The method according to claim 17, wherein the α-olefin comonomer is selected from 1-butene, 1-hexene, 1-octene, and combinations thereof.

19. The method of claim 17, wherein the α-olefin comonomer is 1-hexene.

20. The method according to claim 1 or 4, wherein the catalyst slurry further comprises wax.

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