Systems and methods for dual-trimming catalysts for polymerization processes

Abstract

The present disclosure relates to a method including 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 comprises a first catalyst solution comprising a second, catalyst compound and a. third catalyst compound. The modified catalyst slurry comprises a modified supported catalyst incorporating the first catalyst compound, the second catalyst compound, and the third catalyst compound. The method includes feeding the modified catalyst slurry to a fluidized bed gas-phase reactor. The method includes polymerizing an a-olefin in the fluidized bed gas-phase reactor under polymerization conditions to obtain a polyolefin.

Description

SYSTEMS AND METHODS FOR DUAL-TRIMMING CATALYSTS FOR POLYMERIZATION PROCESSES CROSS-REFERENCED TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Application number63 / 635030, filed April 17, 2024, entitled “SYSTEMS AND METHODS FOR DUAL- TRIMMING CATALYSTS FOR POLYMERIZATION PROCESSES”, the entirety of which is incorporated by reference herein. FIELD

[0002] The present disclosure generally relates to catalyst slurry mixtures. In particular,this disclosure relates to trimming catalyst slurry mixtures with one or more trimming catalyst solutions in polymerization processes, such as gas-phase polyethylene (GPPE) polymerization processes and slurry-phase polymerization processes. BACKGROUND

[0003] Supported multi-component catalysts are widely used in commercial scalepolymer production as multi-component catalysts enable the production of multi-modal polymer resins. For example, supported dual-component catalysts include a support with two types of active sites disposed thereon. The relative contribution to polymerization between the first and second active sites determines the composition of the resulting multi-modal polymer resin, where the relative contribution of each active site is dependent upon the ratio of the active sites on the supported dual-component catalyst.

[0004] In some instances, additional catalysts are added to the polymerization process toadjust the catalyst concentration (e.g., trimming), with respect to the multi-component supported catalyst, to adjust one or more properties “in-situ” of polymer being formed in a reactor. However, the degrees of freedom associated with this approach are limited in that the adjustment in catalyst concentration is dictated by the composition of the trimming solution.

[0005] Thus, it would be desirable to develop a trimming process by which two or moredifferent trimming solutions can be independently added to the polymerization process, thereby providing a higher degree of control of the polymerization process and the resulting polymer properties. Trimming processes by which two or more different trimming solutions can be independently added to the polymerization process would be beneficial in a continuous reactor process in that the resulting polymer properties and composition can be tuned in real-time so as to remain within a desired specification.

[0006] References of potential interest in this regard include: U.S. Patent PublicationNumbers US2022 / 0033537, US2020 / 0071437 and US2022 / 0033535, as well as U.S. Patent Numbers 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 US provisional patent application serial nos. 63 / 503,915; 63 / 503,810; and 63 / 503,851. SUMMARY

[0007] The present disclosure relates gas phase polymerizations and methods thereof.

[0008] In at least one embodiment, a method includes providing a catalyst slurrycomprising 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 comprises a first catalyst solution comprising a second catalyst compound and a third catalyst compound. The modified catalyst slurry comprises a modified supported catalyst incorporating the first catalyst compound, the second catalyst compound, and the third catalyst compound. The method includes feeding the modified catalyst slurry to a fluidized bed gas-phase reactor. The method includes polymerizing an ^-olefin in the fluidized bed gas-phase reactor under polymerization conditions to obtain a polyolefin.

[0009] In at least one embodiment, a method includes providing a catalyst slurrycomprising 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 comprises a first catalyst solution comprising a second catalyst compound and a second catalyst solution comprising a third catalyst compound. The modified catalyst slurry comprises a modified supported catalyst incorporating the first catalyst compound, the second catalyst compound, and the third catalyst compound. The method includes feeding the modified catalyst slurry to a fluidized bed gas-phase reactor. The method includes polymerizing an ^-olefin in the fluidized bed gas-phase reactor under polymerization conditions to obtain a polyolefin.

[0010] These and other features and attributes of the disclosed methods and systems ofthe present disclosure and their advantageous applications and / or uses will be apparent from the detailed description that follows. ^BRIEF DESCRIPTION OF THE DRAWINGS

[0011] To assist those of ordinary skill in the relevant art in making and using the subjectmatter hereof, reference is made to the appended drawings, wherein:

[0012] FIG. 1 is a schematic of a gas-phase reactor system, in accordance with certainembodiments of the present disclosure. DETAILED DESCRIPTION

[0013] Disclosed herein are methods of gas-phase polymerization in a fluidized bed usedin polymerizing ethylene and ethylene comonomers to produce polyethylene polymer and copolymer compositions. Properties and performance of polyethylene compositions can be controlled by the combination of: (1) varying one or more reactor conditions such as reactor temperature, hydrogen concentration, and / or comonomer concentration; and (2) selecting a multitrim catalyst feed system where a first catalyst slurry is trimmed with one or more trimming solutions having one or more different catalyst compositions to achieve the desired polyethylene compositions from a continuous production process. For example, a supported catalyst can be trimmed (e.g., in line) with a single trim solution having two or more catalysts different than each other and different than the catalyst of the supported catalyst to provide a multicatalyst system that can be fed to the polymerization reactor. Alternatively, a supported catalyst can be trimmed (e.g., in line) with two trim solutions, where the first trim solution has a catalyst different than the catalyst of the supported catalyst, and where the second trim solution has a catalyst different than the catalyst of the supported catalyst and different than the catalyst of the first trim solution. Such catalyst trim processes can provide controllable adjustment of polyethylene properties by permitting adjustment of ratios of the catalyst compounds provided by the catalyst slurry and the one or more trimming solutions in the multicatalyst system fed to the reactor.

[0014] In such instances, a supported catalyst is added to a diluent to form a catalystslurry and pumped to a polymerization reactor. Additionally, one or more catalyst solutions, having one or more different trimming catalyst compounds, can be added (i.e., “trimmed”) to the catalyst slurry to adjust one or more properties “in-situ” of polymer being formed in a reactor. The feed rate and concentration of the one or more catalyst solutions can be tailored such that the relative ratio of each individual catalyst can be tuned to achieve the desired polymer properties.

[0015] Polyolefins disclosed herein can have long chain branching (LCB), acharacteristic traditionally recognized in low density polyethylene (LDPE) that leads togood processability and optical properties. However, such LCB can hinder the mechanical properties of films having such polyolefins. Polyolefins of the present disclosure provide maintained or improved mechanical properties (i.e., tear resistance and dart impact strength) of films as compared to films having other LDPE polymers, while also maintaining or improving the desirable optical properties and improving processability of such materials.

[0016] As used herein, the indefinite article “a” or “an” shall mean “at least one” unlessspecified to the contrary or the context clearly indicates otherwise. Thus, embodiments using “an alpha-olefin” include embodiments where one, two or more alpha-olefins are used, unless specified to the contrary or the context clearly indicates that only one alpha- olefin is used.

[0017] As used herein, “wt.%” means percentage by weight, “vol%” means percentageby volume, “mol%” means percentage by mole, “ppm” means parts per million, and “ppm wt” are used interchangeably and mean parts per million on a weightbasis. All concentrations herein, unless otherwise stated, are expressed on the basis of the total amount of the composition in question. Unless otherwise stated, temperatures are provided in degrees Celsius (°C).

[0018] An “olefin” is a linear, branched, or cyclic compound of carbon and hydrogenhaving at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as including an olefin, e.g., ethylene and at least one C3to C20^-olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt.% to 55 wt.%, it is understood that the repeating unit / mer unit or simply unit in the copolymer is derived from ethylene in the polymerization reaction, and the derived units are present at 35 wt.% to 55 wt.%, based on a weight of the copolymer. For the purposes of the present disclosure, ethylene shall be considered an ^-olefin.

[0019] A “polymer” has two or more of the same or different repeating units / mer unitsor simply units. A “homopolymer” is a polymer having units that are the same. A “copolymer” is a polymer having two or more units that are different from each other. A “terpolymer” is a polymer having three units that are different from each other. The term “different” as used to refer to units indicates that the units differ from each other by at least one atom or are different isomerically. The definition of copolymer, as used herein, includes terpolymers and the like. Likewise, the definition of polymer, as used herein,includes homopolymers, copolymers, and the like. Furthermore, the terms “polyethylene copolymer”, “ethylene copolymer”, and “ethylene-based polymer” are used interchangeably to refer to a copolymer that includes at least 50 mol% of units derived from ethylene.

[0020] Nomenclature of elements and groups thereof used herein are pursuant to theNEW NOTATION published in HAWLEYS CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced there with permission from IUPAC), unless reference is made to the Previous IUPAC form noted with Roman numerals (also appearing in the same), or unless otherwise noted. IUPAC refers to the International Union of Pure and Applied Chemistry.

[0021] As used herein, the term “slurry catalyst mixture” refers to a contact product thatincludes at least one catalyst compound and a carrier fluid (e.g., mineral oil), and optionally one or more of an activator, a co-activator, and a support. In a preferred embodiment, the slurry catalyst mixture includes a contact product that includes at least two catalyst compounds and the carrier fluid (e.g., mineral oil), and optionally one or more of an activator, a co-activator, and a support.

[0022] As used herein, the term “catalyst system” refers to a combination of at least onecatalyst compound, an optional activator, an optional co-activator, and an optional support material, where if only catalyst compound is present, then two or more different catalyst compounds are present to provide the catalyst system. As such, in some embodiments the catalyst system can include only a single catalyst compound when the optional activator, the optional co-activator, and the optional support material are not present. In other embodiments, the catalyst system can include only two or more catalyst compounds when the optional activator, the optional co-activator, and the optional support material are not present. For the purposes of the present disclosure, when catalyst systems are described as including neutral stable forms of the components, as it is well understood by one of ordinary skill in the art, the ionic form of the component is the form that reacts with the monomers to produce polymers. Catalyst systems, catalysts, and activators of the present disclosure are intended to embrace ionic forms in addition to the neutral forms of the compounds / components.

[0023] A metallocene catalyst is an organometallic compound with at least one π-boundcyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two π-bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties bondedto a transition metal. In the description herein, the metallocene catalyst may be described as a catalyst precursor, a pre-catalyst compound, metallocene catalyst compound or a transition metal compound, 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 purposes of the present disclosure, in relation to metallocene catalyst compounds, the term “substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.

[0024] The term “melt index” (“MI”) is the number of grams extruded in 10 minutesunder the action of a standard load (2.16 kg) and is an inverse measure of viscosity. A high MI implies low viscosity and a low MI implies high viscosity. In addition, polymers can have shear thinning behavior, which means that their resistance to flow decreases as the shear rate increases. This is due to, e.g., molecular alignments in the direction of flow and disentanglements. As provided herein, MI (I2) is determined according to ASTM D1238-E (190 °C / 2.16 kg), also sometimes referred to as I2 or I2.16.

[0025] The term “high load melt index” (“HLMI”), is the number of grams extruded in10 minutes under the action of a standard load (21.6 kg) and is an inverse measure of viscosity. As provided herein, HLMI (I21) is determined according to ASTM D1238 (190 °C / 21.6 kg) and is also sometimes referred to as I21or I21.6.

[0026] The “melt index ratio” (“MIR”) provides an indication of the amount of shearthinning behavior of the polymer and is a parameter that can be correlated to the overall polymer mixture molecular weight distribution data obtained separately by using Gel Permeation Chromatography (“GPC”) and possibly in combination with another polymer analysis including TREF. MIR is the ratio of I21 / I2 (also referred to as HLMI / MI).

[0027] The properties and performance of polyethylene compositions can be advancedby the combination of: (1) varying one or more reactor conditions such as reactor temperature, hydrogen concentration, comonomer concentration, and so on; and (2) selecting a double trim 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 compositions from a continuous production process. For example, a supported catalyst can be trimmed (e.g., in line) with a single trim solution having two or more catalysts different than each other and different than the catalyst of the supported catalyst to provide a multicatalyst system that can be fed to the polymerization reactor. Alternatively, a supported catalyst can be trimmed (e.g., in line)with two trim solutions, where the first trim solution has a catalyst different than the catalyst of the supported catalyst, and where the second trim solution has a catalyst different than the catalyst of the supported catalyst and different than the catalyst of the first trim solution. Such catalyst trim processes provide for ready adjustment of polyethylene properties by permitting adjustment of ratios of the catalyst compounds provided by the catalyst slurry and the one or more trimming solutions in the multicatalyst system fed to the reactor.

[0028] In various embodiments in accordance with the present disclosure, the slurrycatalyst mixture can include a first catalyst compound that can provide a polymer with a first molecular weight range. Consistent with the above note regarding trimming solutions, one or more catalyst compounds can be added to the polymerization process in the form of in-line addition of one or more trimming solutions. In some embodiments, two or more trimming catalysts can be added to the polymerization process via trimming using two or more trimming solutions. In one or more embodiments, a first trimming catalyst can be provided to the polymerization process via a first trim pot. In one or more embodiments, a second trimming catalyst can be provided to the polymerization process via a second trim 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, such as 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 a metallocene catalyst compound. GAS PHASE REACTOR

[0029] FIG. 1 is a schematic of a gas-phase reactor system 100, showing the addition ofat least two catalysts, at least one of which is added as a trim catalyst. The catalyst slurry mixture from catalyst pot 102 and solution catalyst mixture from trim pot 104A can be mixed in-line. For example, the solution catalyst mixture and catalyst slurry mixture can be mixed by utilizing a mixer, such as static mixer 108 and / or an agitating vessel. Alternatively, any suitable mixer may be used including mixing in a conduit, mixing using a mixing apparatus, or mixing in a continuously agitated tank, for example. Any mixer capable of contacting the solution catalyst mixture and catalyst slurry mixture can be used.

[0030] Catalyst pot 102 contains a first catalyst slurry mixture. The first catalyst slurrymixture can be prepared by any suitable method, including, for example, by mixing particles of one or more catalyst compounds with mineral oil. The catalyst pot 102 canbe an agitated holding tank configured to keep the solids concentration homogenous. In at least one embodiment, the catalyst pot 102 can be maintained at an elevated temperature (relative to room temperature), such as from 30 °C to 80 °C. Alternatively, the catalyst pot 102 can be maintained from 30 °C to 40 °C, from 40 °C to 50 °C, from 50 °C to 60 °C, from 60 °C to 80 °C, or any ranges therebetween. Elevated temperatures can be obtained by electrically heat tracing the catalyst pot 102 using, for example, a heating blanket. Maintaining the catalyst pot 102 at an elevated temperature can further reduce or eliminate solid residue formation on vessel walls, which could otherwise slide off of the walls and cause plugging in downstream delivery lines. In at least one embodiment, catalyst pot 102 can have a volume from 0.5 cubic meters (m3) to 8.0 m3. Alternatively, the volume of the catalyst pot 106 may range from 0.5 m3to 1.0 m3, 1.0 m3to 2.0 m3, 2.0 m3to 3.0 m3, 3.0 m3to 4.0 m3, 4.0 m3to 5.0 m3, 5.0 m3to 6.0 m3, 6.0 m3to 7.0 m3, 7.0 m3to 8.0 m3, or any ranges therebetween.

[0031] The catalyst pot 102 can be maintained at pressure of 1.0 bar to 4.0 bar.Alternatively, the pressure of the catalyst pot 106 may range from 1.0 bar to 1.5 bar, 1.5 bar to 2.0 bar, 2.0 bar to 2.5 bar, 2.5 bar to 3.0 bar, 3.0 bar to 3.5 bar, 3.5 bar to 4.0 bar, or any ranges therebetween. In at least one embodiment, piping 130 and piping 140 of the gas-phase reactor system 100 can be maintained at an elevated temperature (relative to room temperature), such as from 30 °C to 80 °C. Alternatively, the temperature of the piping 130 and 140 may range from 30 °C to 40 °C, from 40 °C to 50 °C, from 50 °C to 60 °C, from 60 °C to 80 °C, or any ranges therebetween. Elevated temperatures can be obtained by electrically heat tracing the piping 130 and / or the piping 140 using, for example, a heating blanket. Maintaining the piping 130 and / or the piping 140 at an elevated temperature can provide the same or similar benefits as described for an elevated temperature of catalyst pot 102.

[0032] A solution catalyst mixture, prepared by mixing a solvent and at least one secondcatalyst and / or activator, can be placed in another vessel, such as a trim pot 104A. Trim pot 104A can have a volume of 0.5 m3to 1.0 m3, 1.0 m3to 2.0 m3, 2.0 m3to 3.0 m3, 3.0 m3to 4.0 m3, 4.0 m3to 5.0 m3, 5.0 m3to 6.0 m3, 6.0 m3to 7.0 m3, 7.0 m3to 8.0 m3, or any ranges therebetween. The trim pot 104A can be maintained at an elevated temperature (relative to room temperature), such as from 30 °C to 80 °C. Alternatively, the temperature of the trim pot 108 may range from 30 °C to 40 °C, from 40 °C to 50 °C, from 50 °C to 60 °C, from 60 °C to 80 °C, or any ranges therebetween. The trim pot 104A can be heated by electrically heat tracing the trim pot 104A, for example, via aheating blanket. Maintaining the trim pot 104A at an elevated temperature can provide reduced or eliminated foaming in piping 130 and or piping 140 when the catalyst slurry mixture from catalyst pot 102 is combined in-line (also referred to herein as “on-line”) with the solution catalyst mixture from trim pot 104A.

[0033] The catalyst slurry mixture can then be combined in-line with the solution catalystmixture of trim pot 104A and / or a second trim pot (trim pot 104B) to form a slurry / solution catalyst mixture or final catalyst composition. Trim pot 104A can have one or more trim catalysts. Trim pot 104B can have one or more trim catalysts different than the trim catalysts of trim pot 104A.

[0034] In some embodiments, one or more additional trim pots, represented by Trim pot104B of FIG. 1, can have a volume of 0.5 m3to 1.0 m3, 1.0 m3to 2.0 m3, 2.0 m3to 3.0 m3, 3.0 m3to 4.0 m3, 4.0 m3to 5.0 m3, 5.0 m3to 6.0 m3, 6.0 m3to 7.0 m3, 7.0 m3to 8.0 m3, or any ranges therebetween. The trim pot 104B can be maintained at an elevated temperature (relative to room temperature), such as from 30 °C to 80 °C. Alternatively, the temperature of the trim pot 108 may range from 30 °C to 40 °C, from 40 °C to 50 °C, from 50 °C to 60 °C, from 60 °C to 80 °C, or any ranges therebetween. The trim pot 104B can be heated by electrically heat tracing the trim pot 104B, for example, via a heating blanket.

[0035] Optionally, a nucleating agent 106, such as silica, alumina, fumed silica or anyother suitable particulate matter can be added to the slurry, and / or the solution in-line, and / or in catalyst pot 102 or trim pot 104A. Similarly, additional activators or catalyst compounds can be added in-line. For example, a second solution catalyst mixture can be introduced from the second trim pot 104B. In some embodiments, the second solution catalyst mixture includes at least one catalyst compound that is different from the first solution catalyst mixture. Additionally, any one or more solution catalyst mixtures can include a combination of two or more catalyst compounds. In other words, a solution catalyst mixture can include, 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), with the first solution catalyst mixture to form a slurry / solution catalyst mixture or final catalyst composition, wherein the second solution catalyst mixture is provided from and / or stored within one or more secondary trim pots 104B. Additionally or alternatively, the second solution catalyst mixture is provided via line 183 to the main line 130 (downstream of addition into the line 130 of the first solution catalystmixture)(shown) or line 140 (downstream of static mixer 108)(not shown). If the second solution catalyst mixture is provided to line 140 downstream of static mixer 108, a second static mixer (not shown) can be used to mix the second solution catalyst mixture with the already supported catalyst provided by static mixer 108. In general, such sequential additional of trim catalyst can provide suitable trim processes where order of addition of catalysts onto the support material is desired. It will be appreciated by one of ordinary skill in the art to implement multiple trim pots having one or more different solution catalyst mixture compositions such that the reaction conditions and resulting polymer properties can be tuned to desired specification (this optional addition is illustrated 104B in the example of FIG.1). Furthermore, the in-line addition of each of the one or more solution catalyst mixtures can be metered separately so as to independently tune and control the relative catalyst composition and concentration within the gas phase reaction vessel. Such independent control provides benefit in that the process can be tuned in real-time in response to monitoring polymer properties and reactor conditions and parameters.

[0036] The catalyst slurry mixture and solution catalyst mixture(s) can be mixed in-line.For example, the solution catalyst mixture(s) and catalyst slurry mixture can be mixed by utilizing a mixer 108, such as static mixer and / or an agitation mixer. In some embodiments, the mixer may include static mixer 108 followed by an agitation mixer. The mixing of the catalyst slurry mixture and the solution catalyst mixture(s) is sufficient to allow the catalyst compound in the solution catalyst mixture to disperse in the catalyst slurry mixture, such that the catalyst components (originally in the solution) migrate to the supported activator (originally present in the slurry). The combination can form a uniform dispersion of catalyst compounds on the supported activator forming the catalyst composition. The length of time that the slurry and the solution can be contacted can be in a range of 1 minute to 4 hours. Alternatively, this length of time may range from 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 ranges therebetween.

[0037] Static mixer 108 of the gas-phase reactor system 100 can be maintained at anelevated temperature (relative to room temperature), such as from 30 °C to 80 °C. Alternatively, the temperature of the static mixer 109 may range from 30 °C to 40 °C, from 40 °C to 50 °C, from 50 °C to 60 °C, from 60 °C to 80 °C, or any ranges therebetween. The elevated temperature of the static mixer 108 can be obtained byelectrically heat tracing the static mixer 108 using, for example, a heating blanket. Maintaining static mixer 108 at an elevated temperature can provide reduced or eliminated foaming in static mixer 108 and can promote mixing of the catalyst slurry mixture and catalyst solution(s) (as compared to lower temperatures), which reduces run times in the static mixer and for the overall polymerization process.

[0038] Optionally, an anti-static agent (e.g., an aluminum alkyl, an ethoxylatedaluminum alkyl, and / or an aluminoxane) or a borate activator, such as a C1 to C15 alkyl aluminum (for example tri-isobutyl aluminum, trimethyl aluminum or the like), a C1to C15 ethoxylated alkyl aluminum or methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane, modified aluminoxane or the like can be added to the mixture of the slurry / solution catalyst mixture in line and / or are added directly to the reactor. The antistatic agents, borate activators and / or aluminoxanes can be added from avessel 110 directly to the combination of the solution catalyst mixture and the catalyst slurry mixture, or can be added via an additional alkane (e.g., hexane, heptane, and or octane) carrier stream, for example, from a carrier vessel 112. The additional alkyls, antistatic agents, borate activators and / or aluminoxanes may be present at up to 500 ppm, at 1 to 300 ppm, at 10 ppm to 300 ppm, or at 10 to 100 ppm. A carrier gas 114 such as nitrogen, argon, ethane, propane, and the like, can be added in-line to the mixture of the slurry and the solution. In embodiments, the carrier gas can be added at the rate of 1 kilograms per hour (kg / hr) to 100 kg / hr. Alternatively, the carrier gas addition rate may range from 1 kg / hr to 50 kg / hr, 1 kg / hr to 25 kg / hr, 2 kg / hr to 20 kg / hr, 2.5 kg / hr to 15 kg / hr, or any ranges therebetween.

[0039] A liquid carrier stream can be introduced into the combination of the solutioncatalyst mixture and the catalyst slurry mixture. The mixture of the solution, the slurry, and the liquid carrier stream can pass through a mixer or length of tube for mixing before being contacted with a gaseous carrier stream. Similarly, a comonomer 116, such as hexene, another alpha-olefin, or diolefin, may be added in-line to the mixture of the slurry and the solution.

[0040] A gas stream 126, such as cycle gas, or recycle gas 124, monomer, nitrogen, orother materials can be introduced into an injection nozzle 300, which can include a support tube 128 at least partially surrounded by an injection tube 120. The slurry / solution catalyst mixture can be passed through the injection tube 120 into fluidized bed reactor 122. In at least one embodiment, the injection tube 120 mayaerosolize the slurry / solution mixture. Any number of suitable tubing sizes and configurations may be used to aerosolize and / or inject the slurry / solution mixture.

[0041] Fluidized bed reactor 122 can include a reaction zone 132 and a velocity reductionzone 134. The reaction zone 132 can include a bed 136 that can include growing polymer particles, formed polymer particles, a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer, and diluent to remove the heat of polymerization through the reaction zone. Optionally, a portion of the recycle gas 124 can be cooled and compressed to form liquids that can increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone. A suitable rate of gas flow can be readily determined by experimentation. Make-up of gaseous monomer to the circulating gas stream can be at a rate equal to the rate at which particulate polymer product and monomer associated therewith is withdrawn from the reactor, and the composition of the gas passing through the reactor can be adjusted to maintain an essentially steady state gaseous composition within the reaction zone. The gas leaving the reaction zone 132 can be passed to the velocity reduction zone 134 where entrained particles can be removed, for example, via gravity separation as the entrained particles slow and fall back to the reaction zone 132. The recycle gas 124 can then be compressed in a compressor 142 and passed through a heat exchanger 144 where at least a portion of the heat of polymerization can be removed. The gas can then be returned to the reaction zone 132. To promote formation of particles in fluidized bed reactor 122, a nucleating agent 118 (e.g., fumed silica) can be added directly into fluidized bed reactor 122. Conventional trim polymerization processes include introducing a nucleating agent into the polymerization reactor. Furthermore, when a metallocene catalyst or other similar catalyst is used in the gas phase reactor, oxygen or fluorobenzene can be added to the fluidized bed reactor 122 directly or to the gas stream 126 to control the polymerization rate.

[0042] FIG. 1 is not limiting, as additional solution catalyst mixtures and / or catalystslurry 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. Likewise, the 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. Similarly, two or more catalyst slurry mixtures can be combined with one or more solution catalyst mixtures, for example in-line, where the catalyst slurry mixtures each include the same or differentsupports and can include the same or different catalyst compounds and or activators and the solution catalyst mixtures can include the same or different catalyst compounds and / or activators. For example, the catalyst slurry mixture can contain a supported activator and two different catalyst compounds, and two solution catalyst mixtures, each containing one of the catalysts in the slurry, wherein each can be independently combined, in-line, with the slurry.

[0043] The reactor temperature of the fluid bed process can be in a range of 30 °C to 200°C. Alternatively, the reactor temperature may range from 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 ranges therebetween. In general, the reactor can be operated at a suitable temperature that accounts for the sintering temperature of the polymer product within the reactor. Thus, the upper temperature limit in various embodiments can be the melting temperature of the polyethylene copolymer produced in the reactor. However, higher temperatures can result in narrower molecular weight distributions that can be improved by the addition of a catalyst, or other co-catalysts.

[0044] Hydrogen gas can be used in the polymerization process to help control orotherwise adjust the final properties of the polyolefin. Using certain catalyst systems, increasing concentrations (partial pressures) of hydrogen can increase a flow index such as the melt index of the polyethylene polymer. The melt index can thus be influenced by the hydrogen concentration. The amount of hydrogen in the polymerization can be expressed as a mole ratio relative to the total polymerizable monomer, for example, ethylene, or a blend of ethylene and hexene or propylene. The amount of hydrogen used in the polymerization process can be an amount that achieves the desired melt index of the final polyolefin polymer. For example, the mole ratio of hydrogen to total monomer (H2:monomer) can be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater. Further, the mole ratio of hydrogen to total monomer (H2:monomer) can be 10 or less, 5 or less, 3 or less, or 0.10 or less. A range for the mole ratio of hydrogen to monomer can include any combination of any upper mole ratio limit with any lower mole ratio limit described herein. In various embodiments, the amount of hydrogen in the reactor at any time can range to up to 5,000 ppm, up to 4,000 ppm, up to 3,000 ppm, or from 50 ppm to 5,000 ppm, or from 50 ppm to 2,000 ppm. The amount of hydrogen in the reactor can range from 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. Further, the ratio of hydrogen to total monomer (H2:monomer) can be 0.00001:1 to 2:1, 0.005:1 to 1.5:1, or 0.0001:1 to 1:1. The one or more reactorpressures in a gas phase process (either single stage or two or more stages) can vary from 690 kilopascal (kPa) to 1,379 kPa, or from 1,724 kPa to 2,414 kPa, or from 2,759 kPa to 3,448 kPa.

[0045] In embodiments, the polymer product can have a melt index ratio (MIR) rangingfrom 10 to less than 300, or, in many embodiments, from 20 to 66, such as 25 to 55. The melt index (MI, I2) can be measured in accordance with ASTM D-1238-20, wherein the melt index is determined using a 2.1 kg loading, and the melt index ratio is determined from the ratio of a 21.6 kg loading to the 2.1 kg loading, both at 190 °C.

[0046] The polymer product can have a density ranging from 0.89 grams per cubiccentimeter (g / cm3), 0.90 g / cm3, 0.91 g / cm3, or 0.92 g / cm3to 0.93 g / cm3, 0.95 g / cm3, 0.96 g / cm3, or 0.97 g / cm3. Density of the polymer product can be determined in accordance with ASTM D-792-20. The polymer can have a bulk density, measured in accordance with ASTM D-1895-17 method B, of from 0.25 g / cm3to 0.5 g / cm3. For example, the bulk density of the polymer can be from 0.30 g / cm3, 0.32 g / cm3, or 0.33 g / cm3to 0.40 g / cm3, 0.44 g / cm3, or 0.48 g / cm3.

[0047] The polymerization processes according to various embodiments can includecontacting one or more olefin monomers with a catalyst slurry mixture that can include mineral oil and catalyst particles. The one or more olefin monomers can be ethylene and / or propylene and the polymerization process can include heating the one or more olefin monomers and the catalyst system to 70 °C or more to form ethylene polymers or propylene polymers.

[0048] Monomers useful herein include substituted or unsubstituted C2 to C40 alpha-olefins, such as C2to C20alpha-olefins, such as C2to C12alpha-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. For example, the monomer can include ethylene and one or more optional comonomers selected from propylene or C4 to C40 olefins, such as C4 to C20 olefins, such as C6 to C12 olefins. The C4 to C40 olefin monomers may be linear, branched, or cyclic. The C4to C40cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0049] In some embodiments, the C2 to C40 alpha-olefin monomers and optionalcomonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, 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 homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

[0050] In various embodiments, one or more dienes can be present in the polymerproduct at up to 10 wt.%, such as at 0.00001 to 1.0 wt.%, such as 0.002 to 0.5 wt.%, such as 0.003 to 0.2 wt.%, based upon the total weight of the composition. 500 ppm or less of diene can be added to the polymerization, such as 400 ppm or less, or such as 300 ppm or less; also or instead, at least 50 ppm of diene can be added to the polymerization, or 100 ppm or more, or 150 ppm or more.

[0051] Diene monomers include any hydrocarbon structure, such as C4 to C30, having atleast two unsaturated bonds, where at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). The diene monomers can be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers). The diolefin monomers are linear di-vinyl monomers, such as those containing from 4 to 30 carbon atoms. Examples of dienes can include, but are not limited to, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, 1,6- heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11- dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadienes (e.g., weight-averaged molecular weight (Mw) less than 1000 grams per mol (g / mol)). Cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.

[0052] The catalyst compositions (catalysts and / or catalyst systems) disclosed herein canbe capable of producing ethylene polymers having an Mw from 40,000 g / mol, 70,000 g / mol, 90,000 g / mol, or 100,000 g / mol 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 can have a melt index (MI) of 0.6 or greater g / 10 min, such as 0.7 or greater g / 10 min, such as 0.8 or greater g / 10min, such as 0.9 or greater g / 10 min, such as 1.0 or greater g / 10 min, such as 1.1 or greater g / 10 min, such as 1.2 or greater g / 10 min.

[0053] “Catalyst productivity” is a measure of how many grams of polymer (P) areproduced using a polymerization catalyst comprising W grams of catalyst (cat), over a period of time of T hours; and can be expressed by the following formula: P / (T x W) and expressed in units of gPgcat-1hr-1. The productivity of the catalyst compositions disclosed herein can be at least 50 g(polymer) / g(cat) / hour, such as 500 or more g(polymer) / g(cat) / hour, such as 800 or more g(polymer) / g(cat) / hour, such as 5,000 or more g(polymer) / g(cat) / hour, such as 6,000 or more g(polymer) / g(cat) / hour, such as 7,000 or more g(polymer) / g(cat) / hour. PROCESS FOR MAKING SLURRY CATALYST MIXTURE

[0054] A container or vessel can be used to produce or otherwise make the slurry catalystmixture. 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 a temperature ranging from 30 °C to 40 °C, from 40 °C to 50 °C, from 50 °C to 60 °C, from 60 °C to 80 °C, from 80 °C to 100 °C, or any ranges therebetween, to produce a heated mineral oil. A moisture concentration of the heated mineral oil can be reduced to produce a dried mineral oil. For instance, moisture concentration of the heated mineral oil can be reduced by at least one of: (i) passing a first inert gas through the heated mineral oil, (ii) passing a second inert gas through a 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 embodiments, two or more, three or more, or four or more of the above may be employed in combination; for instance, a combination of (i) and (ii) may be employed per some embodiments; and / or a combination of (iii) and (iv) in particular embodiments.

[0055] Regarding (i) and (ii), the first and / or second inert gases can independently be orinclude, but are not limited to, nitrogen, carbon dioxide, argon, or any mixture thereof. Amounts of first and / or second inert gas (passed through the mineral oil or into the head space of the vessel) can be gauged in terms of volumetric turnovers (where each turnover equals the volume of the vessel), and can range from a low of 5, 10, 15, or 20 volumetric turnovers to a high of 30, 40, 45, 50, 55, or 60 volumetric turnovers (with ranges from any low to any high contemplated). Vessel volume is not limited but may, for instance, range from a low of any one of 0.75, 1.15, 1.5, 1.9, or 2.3 cubic meters (m3) to a high of 3, 3.8, 5.7, or 7.6 m3. Regarding (iii), the heated mineral oil can be subjected to a vacuum(e.g., a pressure of less than 101 kPa-absolute, less than 75 kPa-absolute, less than 60 kPa-absolute, or less than 55 kPa-absolute). Vacuum pressures in various embodiments may range from a low of any one of 0.67, 1, 10, 15, or 20 kPa-absolute to a high of any one of 30, 40, 55, 60, 65, or 80 kPa-absolute, with ranges from any foregoing low end to any foregoing high end contemplated herein. The heated mineral oil can be subjected to the vacuum for at time period of 1 hour (hr), 2 hr, 3 hr, 4 hr, or 5 hr to 6 hr, 8 hr, 10 hr, 12 hr, 24 hr, or longer. Regarding (iv), the aluminum-containing compound can be or can include, but is not limited to, a compound represented by the formula AlR(3-a)Xa, where R is a branched or straight chain alkyl, cycloalkyl, heterocycloalkyl, aryl, or a hydride radical having from 1 to 30 carbon atoms, X is a halogen, and a is 0, 1, or 2. For instance, the aluminum-containing compound can be or can include tri-hexyl-aluminum, triethylaluminum, trimethylaluminum, tri-isobutylaluminum, di-isobutylaluminum bromide, di-isobutylaluminum hydride, methyl aluminoxane, modified methyl aluminoxane, ethylaluminoxane, isobutylaluminoxane, or any mixture thereof. The modified methyl aluminoxane can be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum, such as triisobutylaluminum. Modified methyl aluminoxanes are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of well-known processes for preparing aluminoxanes and modified aluminoxanes.

[0056] The moisture concentration of the dried mineral oil can be less than or equal to100 parts-per-million-water (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, as measured according to ASTM D1533-12. The dried mineral oil can have a density of 0.85 g / cm3, 0.86 g / cm3, or 0.87 g / cm3to 0.88 g / cm3, 0.89 g / cm3, or 0.9 g / cm3at 25°C, according to ASTM D4052-18a; and / or the dried mineral oil can have a kinematic viscosity at 40 °C of 50 centistokes (cSt), 75 cSt, or 100 cSt to 150 cSt, 200 cSt, 250 cSt, or 300 cSt, according to ASTM D341-20e1. Optionally, the dried mineral oil can also or instead 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, according to ASTM D2502-14(2019)e1.

[0057] Once the dried mineral oil has been produced, catalyst particles can be introducedinto the dried mineral oil to produce a mixture. The mixture can be mixed, blended,stirred, or otherwise agitated for at least 2 hours to remove at least a portion of any gas that can be present within the pores of the catalyst particles, to produce the slurry catalyst mixture. In some embodiments, the mixture can be agitated for 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or more to produce the slurry catalyst mixture; and / or the temperature of the mixture can be maintained at a temperature of 50 °C, 55 °C, 60 °C, or 65 °C to 75 °C, 80 °C, 85 °C, or 90 °C during agitation of the mixture. In other embodiments, the temperature of the mixture can be allowed to cool down. For example, the mixture can be allowed to cool down to a temperature of 45 °C, 40 °C, 35 °C, or 30 °C during agitation of the mixture.

[0058] The vessel can include one or more mixing apparatus that can be configured tomix, blend, stir, or otherwise agitate the mixture within the vessel. For instance, the mixing apparatus can be a rotatable mixing apparatus. Suitable rotatable mixing apparatus can include one or more blades or impellers configured to agitate one or more components of the slurry catalyst mixture within the vessel when rotated. The rotatable mixing apparatus can be rotated at 40 rotations per minute (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 can be agitated via ultrasonic waves; and / or it can be agitated by moving the vessel, e.g., rolling the vessel or rotating the vessel back and forth along an axis thereof.

[0059] The mineral oil may also be agitated during introduction into the vessel; duringheating of the mineral oil; during reduction of the moisture concentration in the mineral oil; and / or during introduction of the catalyst particles to the mineral oil.

[0060] The mineral oil in the slurry catalyst mixture can also be referred to as a diluent.Further, in addition to the mineral oil, the slurry catalyst mixture can also optionally include one or more additional diluents. Additional diluents can be or can include, but are not limited to, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof.

[0061] The slurry catalyst mixture can have a solids content of 1 wt.% to 40 wt.%. Forinstance, the slurry catalyst mixture can have a solids content ranging from 1 wt.% to 5 wt.%, from 5 wt.% to 10 wt.%, from 10 wt.% to 15 wt.%, from 15 wt.% to 20 wt.%, from 20 wt.% to 25 wt.%, from 25 wt.% to 30 wt.%, from 35 wt.% to 40 wt.%, or any ranges therebetween.

[0062] Although wax has heretofore been considered necessary for many slurry catalystmixtures, e.g., for stability (especially for storage and transport), it is noted that slurry catalyst mixtures of various embodiments herein may advantageously omit the wax.Thus, according to such embodiments, the slurry catalyst mixture can be free of any wax having a melting point, at atmospheric pressure, of greater than or equal to 25 °C, based on a total weight of the slurry catalyst mixture. More generally, the slurry catalyst mixture can include less than or equal to 3 wt.%, less than or equal to 2.5 wt.%, less than or equal to 2 wt.%, less than or equal to 1.5 wt.%, less than or equal to 1 wt.%, less than or equal to 0.9 wt.%, less than or equal to 0.8 wt.%, less than or equal to 0.7 wt.%, less than or equal to 0.6 wt.%, less than or equal to 0.5 wt.%, less than or equal to 0.4 wt.%, less than or equal to 0.3 wt.%, less than or equal to 0.2 wt.%, or less than or equal to 0.1 wt.% of any wax having a melting point, at atmospheric pressure, of greater than or equal to 25 °C, based on a total weight of the slurry catalyst mixture. As used herein, the term “wax” includes a petrolatum also known as petroleum jelly or petroleum wax. Petroleum waxes include paraffin waxes and microcrystalline waxes, which include slack wax and scale wax. The wax, if present, can have a density (at 100 °C) of 0.7 g / cm3, 0.73 g / cm3, or 0.75 g / cm3to 0.87 g / cm3, 0.9 g / cm3, or 0.95 g / cm3. The wax, if present, can have a kinematic viscosity at 100 °C of 5 cSt, 10 cSt, or 15 cSt to 25 cSt, 30 cSt, or 35 cSt. The wax, if present, can have a melting point, at atmospheric pressure, of 25 °C, 35 °C, or 50 °C to 80 °C, 90 °C, or 100 °C. The wax, if present can have a boiling point of 200 °C or greater, 225 °C or greater, or 250 °C or greater.

[0063] The term “wax” also refers to or otherwise includes any wax not considered apetroleum wax, which include animal waxes, vegetable waxes, mineral fossil or earth waxes, ethylenic polymers and polyol ether-esters, chlorinated naphthalenes, and hydrocarbon type waxes. Animal waxes can include beeswax, lanolin, shellac wax, and Chinese insect wax. Vegetable waxes can include carnauba, candelilla, bayberry, and sugarcane. Fossil or earth waxes can include ozocerite, ceresin, and montan. Ethylenic polymers and polyol ether-esters include polyethylene glycols and methoxypolyethylene glycols. The hydrocarbon type waxes include waxes produced via Fischer-Tropsch synthesis.

[0064] Once the slurry catalyst mixture has been produced, the slurry catalyst mixturecan be transferred from the vessel into a catalyst pot or cat pot configured to introduce the slurry catalyst mixture into a gas phase polymerization reactor, such as the gas phase polymerization reactor described in FIG.1. As such, in various embodiments, the vessel can be located on-site at a manufacturing facility that includes a gas phase polymerization reactor. By making the slurry catalyst mixture on-site at the manufacturing facility, the use of slurry catalyst cylinders to transport the slurry catalyst mixture can be avoidedbecause the slurry catalyst mixture, upon preparation, can be introduced into the catalyst pot or “cat pot” from which the slurry catalyst mixture can be introduced into the gas phase polymerization reactor. By making 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, upon initiation of agitation of the mixture. On the other hand, by making 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 upon ceasing or stopping agitation of the mixture.

[0065] Although, as noted above, wax advantageously may be omitted where storageand / or transport stability are not required for certain catalyst mixtures, it was surprisingly discovered that wax and / or additional diluent in certain catalyst mixtures can aid in the polymerization process in certain cases, e.g., depending on identity(ies) of catalyst compound(s) in the slurry catalyst mixture. Thus, surprisingly, even when one would otherwise think that omitting wax or other diluents is desired (e.g., because there is no need for added storage / transportation stability), it is found that certain catalyst slurries should include wax or other diluents. Thus, processes according to various embodiments may include identifying slurry catalyst mixture(s) for which wax and / or additional diluent is desired and including wax in such slurry catalyst mixture(s) (preferably also while not including wax and / or additional diluent in slurry catalyst mixtures where no processing advantage is obtained by the presence of the wax and / or diluent).

[0066] Accordingly, polymerization processes per some embodiments can include, at afirst time, introducing a carrier gas, one or more olefins, and a first slurry catalyst mixture into a polymerization reactor. The first slurry catalyst mixture can include a contact product of one or more catalysts selected from a first group of catalysts, a first support, a first activator, a first mineral oil, and a wax having a melting point, at atmospheric pressure, of greater than or equal to 25 °C. The first slurry catalyst mixture can include greater than 1 wt.% of the wax, based on a total weight of the first slurry catalyst mixture.The one or more olefins can be polymerized in the presence of the first catalyst within the polymerization reactor to produce a first polymer product. CATALYSTS

[0067] The catalyst or catalyst compounds can be or can include, but are not limited to,one or more metallocene catalyst compounds. In some embodiments, the catalyst can include at least a first metallocene catalyst compound and a second metallocene catalyst compound, where the first and second metallocene catalyst compounds have different chemical structures from one another. Metallocene catalyst compounds can include catalyst compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one metal atom. In further embodiments, the catalyst further includes a third and / or a fourth metallocene catalyst compound where the third and fourth metallocene catalyst compounds have different chemical structures from one another and different chemical structures than the first and second metallocene catalyst compounds.

[0068] Also suitable are catalyst systems employing a mix of three metallocene catalysts,and in particular, a mix of (1) a bis-cyclopentadienyl hafnocene (preferably a bridged bis-cyclopentadienyl hafnocene), (2) an unbridged zirconocene, such as an unbridged indenyl-cyclopentadienyl zirconocene (preferably an unbridged indenyl- cyclopentadienyl zirconocene), and (3) a bridged zirconocene, such as a bridged indenyl- cyclopentadienyl zirconocene.

[0069] In some embodiments, the metallocene catalyst compounds include a hafnocene.Suitable hafnocenes can include bridged or unbridged hafnocenes, preferably bridged hafnocenes. Bridged hafnocene compounds can include dimethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium dimethyl, dimethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium diethyl, diethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium dimethyl, diethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium diethyl, dimethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium diethyl, dimethylsilyl (tetrahydroindenyl)(triethylsilylmethyl cyclopentadienyl)hafnium dimethyl, dimethylsilyl (tetrahydroindenyl)(triethylsilylmethyl cyclopentadienyl)hafnium diethyl, diethylsilyl (tetrahydroindenyl)(triethylsilylmethyl cyclopentadienyl)hafnium diethyl, dimethylsilyl(tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium dichloride, dimethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium dichloride, and combinations thereof.

[0070] As noted above, suitable catalyst compounds additionally or alternatively mayinclude one or more zirconocenes, such as an unbridged zirconocene including bis(5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium dimethyl, bis(5,5,8,8-pentaethyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium dimethyl, bis(5,5,8,8-pentapropyl-6,7-dihydro-1H-cyclopenta[b]naphthalen- 1-yl) zirconium dimethyl, bis(5,5,8,8-pentabutyl-6,7-dihydro-1H- cyclopenta[b]naphthalen-1-yl) zirconium dimethyl, bis(5,5,8,8-pentamethyl-6,7- dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium diethyl, bis(5,5,8,8-pentaethyl- 6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium diethyl, bis(5,5,8,8- pentapropyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium diethyl, bis(5,5,8,8-pentabutyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium diethyl, bis(5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium dichloride, bis(5,5,8,8-pentaethyl-6,7-dihydro-1H-cyclopenta[b]naphthalen- 1-yl) zirconium dichloride, bis(5,5,8,8-pentapropyl-6,7-dihydro-1H- cyclopenta[b]naphthalen-1-yl) zirconium dichloride, bis(5,5,8,8-pentabutyl-6,7- dihydro-1H-cyclopenta[b]naphthalen-1-yl) zirconium dichloride, and combinations thereof.

[0071] In some embodiments, suitable catalyst compounds additionally or alternativelymay include one or more zirconocenes, such as a bridged zirconocene including dimethylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindenyl)]zirconium dichloride, diethylsilyl[tetramethylcyclopentadienyl (3- methyltetrahydroindenyl)]zirconium dichloride, dipropylsilyl[tetramethylcyclopentadienyl(3-methyltetrahydroindenyl)]zirconium dichloride, diisopropylsilyl[tetramethylcyclopentadienyl (3- methyltetrahydroindenyl)]zirconium dichloride, dimethylsilyl[tetraethylcyclopentadienyl (3-methyltetrahydroindenyl)]zirconium dichloride, dimethylsilyl [tetrapropylcyclopentadienyl (3- methyltetrahydroindenyl)]zirconium dichloride, dimethylsilyl[tetramethylcyclopentadienyl (3-ethyltetrahydroindenyl)]zirconium dichloride, diethylsilyl[tetramethylcyclopentadienyl(3- ethyltetrahydroindenyl)]zirconium dichloride, diethylsilyl[tetraethylcyclopentadienyl(3-ethyltetrahydroindenyl)]zirconium dichloride, dimethylsilyl[tetramethylcyclopentadienyl (3-propyltetrahydroindenyl)]zirconium dichloride, dimethylsilyl[tetramethylcyclopentadienyl(3- isopropyltetrahydroindenyl)]zirconium dichloride, and combinations thereof.

[0075] In some embodiments, a catalyst is represented by Formula (I):wherein:M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R1, R2, R3, R4, R5, R6, R7, R7’, R8, R8’, R9, R9’, R10and R10’is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, one or more of R5and R6, R7and R8, R8and R9, and R9and R10are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring, or one or more of R7’and R8’, R8’and R9’, and R9’and R10’are absent such that a carbon- carbon double bond is present between the corresponding carbon atoms of the hydroindenyl ring shown in Formula (I); T represents the formula Ra2J, (Ra)4J2, or (Ra)6J3wherein each J is independently C, Si, or Ge, and each Rais independently hydrogen, halide, a substituted or unsubstituted C1 to C40hydrocarbyl, or two Racan form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; andeach of X1and X2is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1and X2are joined to form a metallocyclic ring. Each of X1and X2can be independently a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group. In at least one embodiment, each of X1and X2is independently C1to C20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X1and X2join together to form a C4to C62cyclic or polycyclic ring structure. In at least one embodiment, each of X1and X2is independently selected from hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (each of X1and X2may form a part of a fused ring or a ring system), such as X1and X2is independently selected from halides, aryls, and C1 to C5 alkyl groups, such as phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloride group. In at least one embodiment, each of X1and X2are chloride.

[0076] The catalyst of Formula (I) can be the catalyst of catalyst pot 102 or a trim catalystof trim pot 104A or 104B. Catalyst of Formula (I) may be synthesized according to the procedures described in US Application Ser. No. 63 / 503,869, incorporated herein by reference.

[0077] In at least one embodiment, R7, R7’, R8, R8’, R9, R9’, R10 and R10’ is independentlyselected from hydrogen, halogen, C1-C40hydrocarbyl, substituted C1-C40hydrocarbyl, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements (such as –NR'2, –SR', –OR’, –OSiR'3, or –PR'2, wherein each R' is independently hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl), or two of R7, R7’, R8, R8’, R9, R9’, R10and R10’are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring, such as a substituted or unsubstituted C4 to C62cyclic or polycyclic ring. In at least one embodiment, each of R7, R8, R9, R10, R11, R12, and R13is hydrogen.

[0078] In at least one embodiment, R1, R2, R3, R4, R5, R6, R7, R7’, R8, R8’, R9, R9’,R10and R10’is independently hydrogen, halide, alkoxide or C1to C40substituted or unsubstituted hydrocarbyl (such as C1 to C12 substituted or unsubstituted hydrocarbyl), or – R''–SiR'3or –R''–CR'3where R'' is C1to C4hydrocarbyl (such as –CH2–; –CH2CH2–; – (Me)CHCH2–; or –(Me)CH–, and each R' is independently C1 to C20 substituted orunsubstituted hydrocarbyl and at least one R' is C1to C20substituted or unsubstituted hydrocarbyl. In at least one embodiment, each R' is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or an isomer thereof, R' is a C1toC20alkyl or aryl, such as methyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl, or di-t-butylphenyl, provided that at least one R' is not H, alternatively 2 R' are not H, alternatively 3 R' are not H.

[0079] In at least one embodiment, C1-C40 hydrocarbyl, C1-20 hydrocarbyl, or C1-C12hydrocarbyl 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, isononyl, sec-nonyl, n-decyl, isodecyl, or sec-decyl.

[0080] In at least one embodiment, R1, R2, R3, R4, R5, R6, R7, R7’, R8, R8’, R9, R9’, R10and R10’is 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, –CH2–SiPh3, –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.

[0081] In at least one embodiment, R7, R7’, R8, R8’, R9, R9’, R10 and R10’ is hydrogen andeach of R1, R2, R3, R4, R5, and R6is 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 at least one of R1, R2, R3, R4, R5, or R6is not hydrogen.

[0082] In at least one embodiment, a catalyst can be represented by Formula (I) whereinM is hafnium (Hf), each of R1, R2, R4, R5, R6, R7, R7’, R8, R8’, R9, R9’, R10and R10’is independently hydrogen or C1-C5alkyl, R3is -CH2-SiMe3, each of X1and X2is methyl or a halogen, and T is represented by the formula Ra2J wherein J is Si and each Rais C1- C5alkyl. In at least one embodiment, a catalyst can be represented by ^embodiment, a catalyst can be represented by Formula (I) whereinM is zirconium (Zr), each of R5, R7, R7’, R8, R8’, R9, R9’, R10and R10’is independently hydrogen or C1-C5 alkyl, each of R1, R2, R3, R4, and R6is C1-C5 alkyl, each of X1and X2is methyl or a halogen, and T is represented by the formula Ra2J wherein J is Si and each Rais C1-C5 alkyl. In at least one embodiment, a catalyst can be represented by . embodiments, a catalyst is represented by Formula (II):M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R21’, R22, R22’, R23, R23’, R24, R24’, R25, R25’, R26, R26’, R27, R27’, R28, and R28’is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; and each X is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, phosphide, or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

[0085] In some embodiments, each of R14, R15, R19, R20, R21, R21’, R22, R22’, R23, R23’,R24, R24’, R25, R25’, R26, R26’, R27, R27’, R28, and R28’of Formula (II) is independently hydrogen or C1-C10 alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R21, R21’, R24, R24’, R25, R25’, R28,and R28’is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R21, R21’, R24, R24’, R25, R25’, R28, and R28’is hydrogen. In some embodiments, each of R21, R21’, R24, R24’, R25, R25’, R28, and R28’is C1-C10 alkyl (such as methyl). In some embodiments, each of R14, R15, R19, R20, R22, R22’, R23, R23’, R26, R26’, R27, R27’is hydrogen.

[0086] In some embodiments, each of R11, R12, R13, R16, R17, and R18 of Formula (II)is independently hydrogen or C1-C10 alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R11, R12, R13, R16, R17, and R18is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R11, R12, R13, R16, R17, and R18is hydrogen. In some embodiments, each of R11, R12, R13, R16, R17, and R18is methyl. In some embodiments, at least one of R13and R18is C1-C10 alkyl. In some embodiments, each of R13and R18is independently C1-C10 alkyl. In some embodiments, R13and R18are C1-C10 alkyl (such as methyl), and R11, R12, R16, and R17are hydrogen.

[0087] 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 halide, such as chloro. In yet other embodiments, each X is independently a C1-C4 alkyl, such as methyl. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbyl, a heteroatom or substituted or unsubstituted heteroatom-containing group, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido. In some embodiments of Formula (II), (1) M is Zr or Hf, (2) X is chloro, (3) R11, R12, R13, R14, R15, R21, R21’, R22, R22’, R23, R23’, R24, and R24’is independently hydrogen or substituted or unsubstituted C1-C10alkyl, (4) R16, R17, R18, R19, R20, R25, R25’, R26, R26’, R27, R27’, R28, and R28’is independently hydrogen orR18is C1-C10 alkyl.

[0088] In at least one embodiment, a catalyst can be represented by Formula (II)wherein M is zirconium (Zr), each of R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R21’, R22, R22’, R23, R23’, R26, R26’, R27, and R27’are independently hydrogen or C1-C5 alkyl, each of R21, R21’, R24, R24’, R24, R24’, R25, R25’, and R28’are methyl, and each of X2are methyl. In at least one embodiment, a catalyst can be represented by . can be the catalyst of catalyst pot 102 or a trimcatalyst of trim pot 104A or 104B. Catalyst of Formula (II) may be synthesized according to the procedures described in US Application Ser. No. 63 / 503,893, incorporated herein by reference. SLURRY CATALYST MIXTURE INCLUDING ACTIVATORS AND SUPPORTS

[0090] As noted above, the slurry catalyst mixture can include one or more activatorsand / or supports in addition to one or more catalysts. The term “activator” refers to any compound or combination of compounds, supported or unsupported, which can activate a single site catalyst compound or component, such as by creating a cationic species of the catalyst component. For example, this can include the abstraction of at least one leaving group (the ‘X’ group in the single site catalyst compounds described herein) from the metal center of the single site catalyst compound / component. The activator may also be referred to as a “co-catalyst”. For example, the slurry catalyst mixture can include two or more activators (e.g., aluminoxane and a modified aluminoxane) and a catalyst compound, or the slurry catalyst mixture can include a supported activator and more than one catalyst compound. In particular embodiments, the slurry catalyst mixture can include at least one support, at least one activator, and at least two catalyst compounds. For example, the slurry can include at least one support, at least one activator, and two different catalyst compounds that can be added separately or in combination to produce the slurry catalyst mixture. For instance, a mixture of a support (e.g., silica), and an activator (e.g., aluminoxane) can be contacted with a first catalyst compound, allowed to react, and thereafter the mixture can be contacted with second, different, catalyst compound, for example, in a trim system. And, additional catalyst compounds (third, fourth, etc.) could be contacted in a similar manner, in series or together with the first and / or second catalyst compounds.

[0091] The molar ratio of metal in the activator to metal in the catalyst compound inthe slurry catalyst mixture can be 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 can include a support material which can be any inert particulate carrier material known in the art, including, but not limited to, silica, fumed silica, alumina, clay, talc or other support materials, such as disclosed above. In one embodiment, the slurry can include silica and an activator, such as methyl aluminoxane (“MAO”), modified methyl aluminoxane (“MMAO”), as discussed further below. In embodiments, activators include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds that abstract a reactive, σ-bound, metal ligand, making the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.

[0092] As noted above, one or more organo-aluminum compounds, such as one or morealkylaluminum compounds, can be used in conjunction with the aluminoxanes. For example, alkylaluminum species that can be used include diethylaluminum ethoxide, diethylaluminum chloride, and / or disobutylaluminum hydride. Examples of trialkylaluminum compounds include, but are not limited to, trimethylaluminum, triethylaluminum (“TEAL”), triisobutylaluminum “TiBAl”), tri-n-hexylaluminum, tri-n- octylaluminum, tripropylaluminum, tributylaluminum, and the like.

[0093] Suitable supports include, but are not limited to, active and inactive materials,synthetic or naturally occurring zeolites, as well as inorganic materials such as clays and / or oxides such as silica, alumina, zirconia, titania, silica-alumina, cerium oxide, magnesium oxide, or combinations thereof. In particular, the support may be silica- alumina, alumina and / or a zeolite, particularly alumina. Silica-alumina may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.

[0094] In some embodiments, at least a portion of the slurry catalyst mixture can becontacted with a solution catalyst mixture to produce or otherwise form a slurry / solution catalyst mixture.

[0095] In some embodiments, the slurry catalyst mixture can include one or moresupported metallocenes. For example, a metallocene catalyst can be contacted with a co- catalyst, such as MAO, and allowed to react. A support structure can then be added to produce a supported metallocene catalyst. The supported catalyst can be added to a sufficient amount of slurry mixture to produce the slurry catalyst mixture. In at least oneembodiment, the metallocene catalyst can be any one or more catalyst previously described in Formulas I and II. In some embodiments, the supported metallocene can include one or more metallocene catalysts on the support structure. In at least one embodiment, the metallocene catalyst of the supported metallocine catalyst is any one or more of dimethylsilyl (tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl)hafnium dimethyl, dimethylsilyl [tetramethylylcyclopentadienyl(3-methyltetrahydroindenyl)]zirconium dichloride, (5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1- yl)zirconium dimethyl, and combinations thereof. In at least one embodiment, the metallocene catalyst of the supported metallocene catalyst is dimethylsilyl(tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium dimethyl. SOLUTION CATALYST MIXTURE – TRIM SOLUTION

[0096] The solution catalyst mixture can include a solvent and only catalystcompound(s) (e.g., no support material), such as one or more metallocene catalyst compounds as previously described in Formulas (I) and (II), or can also include an activator. In some embodiments, the solution catalyst mixture can be or can include, but is not limited to, a contact product of a solvent / diluent and a first catalyst and / or a second catalyst compounds. In some embodiments, the solution catalyst mixture can include the contact product of solvent / diluent and any one or more of the first, second, third, etc. catalyst compounds. The catalyst compound(s) in the solution catalyst mixture are unsupported. Further, the slurry / solution catalyst mixture can be introduced into the gas phase polymerization reactor. The solution catalyst mixture may be a single solution catalyst mixture (e.g., provided by trim pot 104A or trim pot 104B) or can be the sum of two or more solution catalyst mixtures (e.g., provided by each of trim pot 104A and trim pot 104B to line 130). A catalyst mixture of trim pot 104A or trim pot 104B can include one catalyst compound, two catalyst compounds, three catalyst compounds, or more.

[0097] A solution catalyst mixture can be prepared by dissolving the metallocenecatalyst compound(s), previously described in Formulas (I) and (II), and optional activators in a liquid solvent. The liquid solvent can be an alkane, such as a C5to C30alkane, or a C5 to C10 alkane. Cyclic alkanes (e.g., cyclohexane) and aromatic compounds (e.g., toluene) can also be used. Mineral oil can be used as a solvent alternatively or in addition to other alkanes such as one or more C5 to C30 alkanes. The mineral oil in the solution catalyst mixture, if used, can have the same properties as themineral oil that can be used to make the slurry catalyst mixture, as described above. The solvent should be liquid under the conditions of polymerization and relatively inert. Optionally, the solvent utilized in the solution catalyst mixture can be different from the diluent used in the slurry catalyst mixture. Or, on the other hand, the solvent utilized in the solution catalyst mixture can be the same as the diluent, i.e., the mineral oil(s) and any additional diluents used in the slurry catalyst mixture.

[0098] If the solution catalyst mixture includes both one or more metallocene catalystcompound(s) and an activator, the ratio of metal in the activator to metal in all catalyst compound(s) in the solution catalyst mixture can be 1000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. In various embodiments, the activator and catalyst compound(s) can, together, be present in the solution catalyst mixture at up to 90 wt.%, at up to 50 wt.%, at up to 20 wt.%, such as at up to 10 wt.%, at up to 5 wt.%, at less than 1 wt.%, or between 100 ppm and 1 wt.%, based on the weight of the solvent, the activator, and the catalyst. The one or more activators in a solution catalyst mixture, if used, can be the same or different as the one or more activators used in a slurry catalyst mixture.

[0099] The solution catalyst mixture can include any one of the catalyst compound(s) ofthe present disclosure. As the catalyst is dissolved in the solution, a higher solubility can be desirable. Accordingly, the catalyst in the solution catalyst mixture can often include a metallocene, which may have higher solubility than other catalysts. In the polymerization process, any of the above described solution catalyst mixtures can be combined with any of the slurry catalyst mixtures described above. In addition, more than one solution catalyst mixture can be utilized (for example, a first trim solution and a second trim solution which can have the same or different catalysts as one another and can be provided at the same or different flow rates as one another). CONTINUITY ADDITIVE – STATIC CONTROL AGENT

[0100] In gas-phase polyethylene production processes, it can be desirable to use one ormore static control agents to help facilitate the regulation of static levels within the reactor. A continuity additive is a chemical composition that, when introduced into the fluidized bed within the reactor, can influence or drive a static charge (negative, positive, or to zero) in the fluidized bed. The continuity additive used can depend, at least in part, on the nature of the static charge, and the choice of static control agent can vary depending, at least in part, on the polymer being produced and / or the single site catalyst compounds being used. In some embodiments, the continuity additive or static control agent can be introduced into the reactor in an amount of 0.05 ppm to 200 ppm.Alternatively, the amount of the continuity additive or static control agent may range from 0.05 ppm to 2 ppm, 5 ppm, or 10 ppm, or range from 20 ppm to 50 ppm, 75 ppm, 100 ppm, 150 ppm, or 200 ppm.

[0101] In some embodiments, the continuity additive can be or can include aluminumstearate. The continuity additive can be selected for its ability to receive the static charge in the fluidized bed without adversely affecting productivity. Other suitable continuity additives can be or can include, but are not limited to, aluminum distearate, ethoxylated amines, and combinations thereof. In some embodiments, the continuity additive includes a mixture of a polysulfone copolymer, a polymeric polyamine, and oil soluble sulfonic acid. Any of the continuity additives can be used either alone or in combination.

[0102] In some embodiments, the continuity additive can include fatty acid amines,amide-hydrocarbon or ethyoxylated-amide compounds, carboxylate compounds such as aryl-carboxylates and long chain hydrocarbon carboxylates, and fatty acid-metal complexes; alcohols, ethers, sulfate compounds, metal oxides and other compounds known in the art. Some specific examples of control agents can be or can include, but are not limited to, 1,2-diether organic compounds, magnesium oxide, glycerol esters, ethoxylated amines (e.g., N,N-bis(2-hydroxyethyl)octadecylamine), alkyl sulfonates, and alkoxylated fatty acid esters, chromium N-oleylanthranilate salts, calcium salts of a Medialan acid and di-tert-butylphenol, an ^-olefin-acrylonitrile copolymer and polymeric polyamine, sorbitan-monooleate, glycerol monostearate, methyl toluate, dimethyl maleate, dimethyl furnarate, triethylamine, 3,3-diphenyl-3-(imidazol-1-yl)- propin, and like compounds. In some embodiments, another continuity additive can include a metal carboxylate salt, optionally, with other compounds.

[0103] In some embodiments, the continuity additive can include an extracted metalcarboxylate salt that can be combined with an amine containing agent, such an extracted carboxylate metal salt. For example, the extracted metal carboxylate salt can be combined with antistatic agents such as fatty amines, such as a blend of ethoxylated stearyl amine and zinc stearate, or a blend of ethoxylated stearyl amine, zinc stearate and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate.

[0104] Other continuity additives can include ethyleneimine additives, such aspolyethyleneimines having the following general formula: —(CH2—CH2—NH)n—, where n can be from 10 to 10,000. The polyethyleneimines can be linear, branched, or hyper branched (e.g., forming dendritic or arborescent polymer structures). The polyethyleneimines can be a homopolymer or copolymer of ethyleneimine or mixturesthereof (referred to as polyethyleneimine(s) hereafter). Although linear polymers represented by the chemical formula —(CH2—CH2—NH)n— can be used as the polyethyleneimine, materials having primary, secondary, and tertiary branches can also be used. INDUCED CONDENSING AGENT

[0105] In gas-phase polyethylene production processes, it can be desirable to use one ormore induced condensing agents within the reactor. “Induced condensing agent (iCA),” as used herein, refers to one or more induced condensable fluids, which are readily volatile liquid hydrocarbons that may be selected from saturated hydrocarbons containing from 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 class of preferred induced condensable hydrocarbons includes C5 and C6 saturated hydrocarbons. Another class of preferred hydrocarbons includes C4 to C6 saturated hydrocarbons. Preferred hydrocarbons for use as condensable fluids include pentanes, such as isopentane. The condensable fluids may also include polymerizable condensable comonomers such as olefins, diolefins or mixtures thereof, including some of the monomers mentioned herein, which may be partially or entirely incorporated in the polymer product. END USES

[0106] Polyolefins obtained from processes disclosed herein can have long chainbranching (LCB), a characteristic commonly found in grades of low density polyethylene. Such LCB provides inherent benefits to material processability, such as high melt strength, high shrink, and good optical properties. Oftentimes, LCB can cause unintended deleterious effects to the resulting material’s mechanical properties (i.e., tear resistance and dart impact strength). However, materials produced using polyolefins obtained from processes disclosed herein exhibit good optical and mechanical properties. Without being bound by theory, polyolefin copolymer produced by processes disclosed herein comprise a balance of LCB and physical entanglements so as to achieve the desired mechanical properties of the material (e.g., film) while maintaining the good optical properties and processability as well.

[0107] The polymers produced by the processes disclosed herein and blends thereof canbe useful in forming operations, such as film, sheet, and fiber extrusion and co-extrusionas well as blow molding, injection molding, and rotary molding. Films include blown or cast films formed by co-extrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc., in food-contact and non-food contact applications. Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non- woven form to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.

[0108] Specifically, any of the foregoing polymers, such as ethylene copolymers orblends thereof, can be used in mono- or multi-layer blown, extruded, and / or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents.

[0109] The polymers produced herein may be further blended with one or more secondpolymers and used in film, molded parts, and other typical applications. In one embodiment, the second polymer can be selected from ethylene homopolymer, ethylene copolymers, and blends thereof. Useful second ethylene copolymers can include one or more comonomers in addition to ethylene, and can be a random copolymer, a statistical copolymer, a block copolymer, and / or blends thereof. The process of making the second ethylene polymer is not limited, as it can be made by slurry, solution, gas phase, high pressure or other suitable processes, and by using catalyst systems appropriate for the polymerization of polyethylene, such as Ziegler-Natta-type catalysts, chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof, or by free-radical polymerization.

[0110] Polymer films can be prepared from any one or more polymers and / or additivesdisclosed herein, by any one or more appropriate methods known to one of ordinary skill in the art. In some embodiments, a polymer film has a melt index (I2; as determined by ASTM D-1238) of about 0.8 g / 10 min to about 1 g / 10 min, such as about 0.85 g / 10 min to about 0.95 g / 10 min, such as about 0.89 g / 10 min to about 0.925 g / 10 min. In someembodiments, a polymer film has a high load melt index (I21; as determined by ASTM D-1238) of about 10 g / 10 min to about 25 g / 10 min, such as about 13 g / 10 min to about 23 g / 10 min, such as about 16 g / 10 min to about 18 g / 10 min. In some embodiments, a polymer film has a melt index ratio (I21 / I2) of about 15 to about 25, such as about 16.5 to about 23.5, such as about 19 to about 20.

[0111] In some embodiments, a polymer film of the present disclosure can have a haze(as determined by ASTM D-1003) of about 5 % to about 10 %, such as about 5.5 % to about 9 %, such as about 6 % to about 8.5 %. In some embodiments, a polymer film can have a clarity (as determined by ASTM D 1746) 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%. Examples Synthesis of metallocene catalyst 1:cyclopenta[b]naphthalen-3-yl)lithium (1):

[0113] To a vigorously stirred white suspension of 5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopenta[b]naphthalene (20.18 g, 89.2 mmol, 1.00 equiv.) in diethylether (250 mL) at -35oC was added n-Butyl Lithium in hexane (36 ml, 90.0 mmol, 1.01 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving dirty white solid. The solid was washed with pentane (100 mL) and the solid was filtered to give a bright white solid. The yield was 18.8 g (91%) bright white powder.1H NMR (THF-D8) 7.46 (s, 2H), 6.50 (t, 1H), 5.81 (dt, 1H), 1.72 (S, 4H), 1.34 (S, 12H). Synthesis of (5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) Zirconium dichloride (2):

[0114] To a vigorously stirred white suspension of zirconium tetrachloride (2.98 g, 12.8mmol, 1.00 equiv.) in diethylether (200 mL) at -35oC was added (5,5,8,8-pentamethyl- 6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl)lithium (1) (6.30 g, 25.6 mmol, 2.00equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving bright yellow solid. The solid was extracted with dichloromethane (100 mL) and the extracts were 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%) bright yellow powder.1H 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). Synthesis of (5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopenta[b]naphthalen-1-yl) Zirconium dimethyl (3):

[0115] To a bright yellow suspension of (2) (14.6 g, 0.024 mol, 1.0 equiv) in 100 mLdiethylether at -35°C was added 3.28 M MeMgBr (39.7 ml, 0.119 mol, 5.0 equiv) in Et2O to give a cold, cloudy yellow mixture. The reaction mixture was allowed to stir at room temperature overnight. Solvent was removed under vacuum. The product was extracted with pentane and dark brown solid was filtered out. Pentane was removed under vacuum resulted in the formation of pale yellow solid, 12.5 g, 91.6%1H 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). Synthesis of metallocene catalyst 2: Synthesis of 1H-inden-1-

[0116] To a vigorously stirred white suspension of Indene (17.9 g, 154 mmol, 1.00equiv.) in diethylether (250 mL) at -35oC was added n-Butyl Lithium in hexane (62.3 ml, 156 mmol, 1.01 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving dirty white solid. The solid was washed with pentane (100 mL) and the solid was filtered to give a bright white solid. The yield was 18.3 g (97%) bright white powder.1H NMR (THF-D8) 7.32 (m, 2H), 6.54 (t, 1H), 6.45 (m, 2H), 5.92(dt, 2H). ^Synthesis of chloro-(1H-inden-1-yl)-dimethyl-silane (5):

[0117] To the suspension of Lithium indenide (18.0 g, 148 mmol, 1.0 equiv) in 250 mldiethylether cooled to -25 °C, neat Me2SiCl2 (57.2 g, 443 mmol, 3.0 equiv) was added dropwise over a period of 5-10 minutes. The resulting mixture was stirred at room temperature overnight. Volatiles from the resulting mixture were removed in vacuum and then extracted into pentane to get rid of insoluble materials and LiCl. Pentane was removed under vacuum resulted in the formation of pale yellow oil, 22.7 g, 73.5% yield.1H 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). Synthesis of 1H-inden-1-yl-dimethyl-[3-(trimethylsilylmethyl)cyclopenta-2,4-dien- 1-yl]silane (6):

[0118] To the solution of chloro-(1H-inden-1-yl)-dimethyl-silane (5) (12.9 g, 61.8mmol, 1.0 equiv) in THF (200 ml) chilled at 25 °C, Solid lithium trimethylsilylmethyl cyclopentadienide (11.7 g, 74.2 mmol, 1.1 equiv) was added. The resulting mixture was stirred at room temperature overnight. All volatiles were removed in vacuum and triturated with hexane (100 ml). The crude materials were then extracted with hexane (100 ml) and Hexane removal gave 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), 6.09 – 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). Synthesis of (1H-inden-1-yl-dimethyl-[3-(trimethylsilylmethyl)cyclopenta-2,4-dien- 1-yl]silyl)Lithium (7):

[0119] To a vigorously stirred pale yellow solution of (6) (20.1 g, 61.8 mmol, 1.00equiv.) in diethylether (250 mL) at -35oC was added n-Butyl Lithium in hexane (49.7ml, 124.0 mmol, 2.01 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving dirty white solid. The solid was washed with pentane (100 mL) and the solid was filtered to give a bright white solid. The yield was 18.8 g (91%) bright white powder.1H 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). ^Synthesis of Dimethylsilyl (indenyl)(trimethylsilylmethyl cyclopentadienyl)Hafnium Dichloride (8):

[0120] To a vigorously stirred white suspension of Hafnium tetrachloride (21.7 g, 67.7mmol, 1.10 equiv.) in diethylether (200 mL) at -35oC was added to (7) (20.7 g, 61.5 mmol, 1.00 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving bright yellow solid. The solid was extracted with dichloromethane (100 mL) and the extracts were 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%) 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). Synthesis of Dimethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)Hafnium Dichloride (9):

[0121] To a hazy yellow solution of (8) (10.1 g, 17.7mmol, 1.0 equiv) in 200 mL CH2Cl2was added 0.050 g PtO2(540 mg, 2.38 mmol, 0.12 equiv) to give a dirty yellow mixture in a Parr reactor. 1000 psi of hydrogen was applied and stirred the reaction mixture over the weekend vigorously. The excess hydrogen was vented out and filtered the black solid yielded pale yellow solid, Yield 7.23 g g (79%).1H NMR (CD2Cl2) 7.15-7.08 (m, 1H), 7.08 (m, 2H), 7.00-6.78 (m, 1H), 6.57-6.32 (m, 2 H), 2.88-2.02 (m, 8H), 1.05-0.64(m, 2H), 0.44 (dt, 6H), 0.06(dt, 9H). Synthesis of Dimethylsilyl (tetrahydroindenyl)(trimethylsilylmethyl cyclopentadienyl)hafnium dimethyl (10):

[0122] To a bright yellow suspension of 9 (8.99 g, 156 mmol, 1.0 equiv) in 100 mLdiethylether at -35°C was added 3.28 M MeMgBr (20.8 ml, 624 mmol, 4.0 equiv) in Et2O to give a cold, cloudy yellow mixture. The reaction mixture was allowed to stir at room temperature overnight. Solvent was removed under vacuum. The product was extracted with pentane and dark brown solid was filtered out. Pentane was removed under vacuum resulted in the formation of pale yellow solid, 7.09 g, 85.0%1H NMR (C2D2) 7.12-6.94 (m, 3H), 5.95-5.69 (m, 3H), 2.74-1.59 (m, 10 H), 0.26 (s, 9H), 0.17 (dt, 6H), -0.03 (dt, 6H). ^Synthesis of metallocene catalyst 3:

[0123] To a colorless solution of MeI (18.8 g, 133 mmol, 2 equiv.) in diethyl ether (200mL) at -35oC was added 1H-inden-1-yllithium (4) (8.08 g, 66 mmol, 1 equiv.) to give a cloudy white mixture. The reaction mixture was stirred at room temperature overnight. 1,2-Dimethoxyethane (6 g) was added to the clear yellow reaction mixture resulting in the formation of white precipitate. The solvent was removed under vacuum, leaving a white solid. The product was extracted with pentane (100 mL) and filtered, resulting in an amber solution and white precipitate. The amber solution was dried under vacuum yielding a yellow viscous oil. Yield 5.73 g, 66%).1H NMR (C6D6) 7.8 (m, 4H), 6.65 (dd, 1H), 6.21 (dd, 1H), 3.22 (m, 1H), 1.07 (d, 3H). Synthesis of 3-methyl-inden-1-ylithium (12):

[0124] To a vigorously stirred white suspension of 3-methyl-indene (11) (10.1 g, 77.6mmol, 1.00 equiv.) in diethyl ether (250 mL) at -35oC was added n-butyl lithium in hexane (31.3 mL, 78.4 mmol, 1.01 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was concentrated under vacuum to give a dirty white solid. The solid was washed with pentane (100 mL) and the solid was isolated by filtration to give a bright white powder (yield 10 g, 95%).1H NMR (THF-D8) 7.24 (m, 2H), 6.43 (m, 2H), 6.33 (d, 2H), 5.71 (dd, 2H), 2.42 (d, 3H). Synthesis of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate (13):

[0125] To a yellow solution of Me4CpSiMe2Cl (31.8 g, 148 mmol, 1.0 equiv) in 100 mLtoluene was added AgOTf (39.9 g, 155 mmol, 1.05 equiv) in portions. The reaction mixture turned cloudy white and warmed upon addition of AgOTf. The reaction quickly turned grey-pink, then grey-violet. The reaction mixture changed to a dark, muddy- colored mixture with significant solids after stirring for 15 min. The reaction mixturewas stirred for 3 hours at room temperature. The solvent was removed under vacuum, resulting in a dark mixture, which subsequently used in the next step. Synthesis of dimethyl(3-methyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopenta-2,4- dien-1-yl)silane (14):

[0126] To a solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyltrifluoromethanesulfonate (Me4CpSiMe2OTf, 13) (13.5 g, 41.2 mmol, 1.0 equiv) in Et2O at -35°C was added 3-methyl-inden-1-ylithium (12) (5.61 g, 41.2 mmol, 1.0 equiv). The reaction mixture was allowed to stir at room temperature overnight. The solvent was removed under vacuum. The product was extracted with pentane, and the extracts were subsequently concentrated under vacuum resulting in a golden yellow solid, yield 12.1 g (96%).1H NMR (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 – 3.54 (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). Synthesis of dillithium [tetramethylylcyclopentadienyldimethylsilyl(3- methylindenyl)] etherate (15):

[0127] To a solution of dimethyl(3-methyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane (14) (12.1 g, 39.4 mmol, 1.0 equiv.) in Et2O at -35°C was slowly added n-butyl lithium in hexane (32.3 mL, 80.7 mmol, 2.05 equiv.). The reaction mixture was allowed to stir at room temperature overnight. 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).1H NMR (THF-D8) 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). Synthesis of Tetramethylylcyclopentadienyldimethylsilyl(3-methylindenyl) zirconium dichloride (16):

[0128] To a vigorously stirred suspension of dillithium[tetramethylylcyclopentadienyldimethylsilyl(3-methylindenyl)] etherate (15) (12.1 g,37.8 mmol) in Et2O at -35°C was added ZrCl4(OEt2)2 (10.56 g, 45.3 mmol, 1.20 eq). Thereaction mixture was allowed to stir at room temperature overnight. Ether was removed under vacuum. The product was extracted with CH2Cl2and 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%.1H NMR (CD2Cl2) 7.50 (ddt, 2H), 7.31 (ddd, 1H), 7.02 (ddd, 1H), 5.55 (d, J = 0.9 Hz, 1H), 2.46 (d, J = 0.6 Hz, 3H), 1.98 (s, 3H), 1.91 (d, J = 2.2 Hz, 6H), 1.88 (s, 3H), 1.17 (s, 3H), 0.92 (s, 3H).Synthesis of [Tetramethylylcyclopentadienyldimethylsilyl(3- methyltetrahydroindenyl)]zirconium dichloride (17):

[0129] To a solution of tetramethylylcyclopentadienyldimethylsilyl(3-methylindenyl)zirconium dichloride (16) (11.4 g, 24.3 mmol, 1.0 equiv) in 200 mL CH2Cl2was added PtO2 (0.55 g, 2.42 mmol, 0.10 equiv). Hydrogen (500 psi) was added and the reaction was stirred at room temperature in a Parr reactor overnight. The pressure was vented, and the reaction solution was filtered away from black solid. The solvent was then removed under vacuum to afford a 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) (s, 3H), 2.02 (s, 3H),1.93 (s, 3H), 1.85 (s, 3H), 1.58 (m, 1H), 1.47 (m, 1H), 0.90 , 0.79 (s, 3H). Supported catalyst preparation:

[0130] Anhydrous toluene (1800 g) and 30% MAO in toluene (894 g) were added to a 4L conical mixing vessel. The vessel was sealed and stirring commenced at 120 rpm. The metallocene (metallocene catalyst 2) (15.0 g, 29.03 mmol) in toluene was then added through a funnel in the top of the mixer. The reactants were left to stir at room temperature for 1 h. After such time, the silica was added over the course of 10 min. through the same funnel as before. Stirring continued for another hour, after which the stirring rate was reduced and the solvent was removed under vacuum to yield the supported metallocene. The supported catalyst was then added to a container with a sufficient amount of slurry mixture (SJCS-380, Sonneborn) to yield 20 wt% slurried catalyst. Trim solution preparation:

[0131] For the single-catalyst trim (hereinafter referred to as “trim solution 1”),metallocene (metallocene catalyst 1) was added neat to an open container. Anhydrousisohexane was added in sufficient quantity to produce a solution that had a total metallocene composition of 0.04 wt%. For the mixed catalyst trim (hereinafter referredto as “trim solution 2”), a 5:1 mol ratio of metallocenes (metallocene catalyst 1:metallocene catalyst 3) were added neat to an open container. Anhydrous isohexane wasadded in sufficient quantity to produce a solution that had a total metallocene composition of 0.04 wt%. Polymerization:

[0132] Polymerization was performed in a 22 foot tall gas-phase fluidized bed reactorwith a 13 inch straight section inner diameter and a wider conical expanded section above. Cycle and feed gases were fed into the reactor body through a perforateddistributor plate, and the reactor was controlled at 290 psig and 64 mol% ethylene. The reactor temperature was maintained at constant temperature throughout the polymerization by controlling the temperature of the cycle gas loop.

[0133] The supported catalyst (20 wt% slurry) was optionally contacted in line with trim5 catalyst solution (0.04 wt% total trim) at an adjustable ratio, mixed to homogenize, and given sufficient time to enable trim catalyst diffusion, anchoring, and activation to thereby adjust the active catalyst ratio. In some aspects, the active catalyst ratio adjustment could be measured and used as a control variable.

[0134] The control and trimmed parts are shown in Table 1. The control was a largely10 unimodal (low, ~17 MIR), and adding trim solution 1 (comparative examples C2 and C3) in incrementing amounts impacted density but only had modest increases in MIR. Adding trim solution 2 at the same overall trim flow rate as C3 but with inclusion of an LCB-containing trim catalyst in smaller amounts (Catalyst 3) yielded a larger increase in MIR (example 2 compared to comparative example 3). 15 Table 1: Condition summaries C1 C2 C3 Ex.1 Ex.2 Control Control Control Control with onTRIM soln / CAT slurry g / hr / cc / hr 0.000 1.511 3.027 2.021 3.177Table 2 C1 C2 C3 Ex.1 Ex.25

[0135] Overall, processes of the present disclosure provide gas phase reactorpolymerizations using multiple trim catalysts (as one or more trim solutions) to obtain desired process conditions and provide polymers with specified properties. By implementing two or more trimming solutions, which can be metered separately and independently controlled, higher degrees of freedom and control over the gas phase 10 reaction processes and polymer properties thereof can be obtained.

[0136] The phrases, unless otherwise specified, "consists essentially of" and "consistingessentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure,additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0137] For the sake of brevity, only certain ranges are explicitly disclosed herein.However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0138] All documents described herein are incorporated by reference herein, includingany priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including” for purposes of United States law. Likewise, whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

[0139] While the present disclosure has been described with respect to a number ofembodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

CLAIMS:

1. A method comprising: 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; contacting the catalyst slurry with one or more catalyst solutions to obtain a modified catalyst slurry, wherein: the one or more catalyst solutions comprises a first catalyst solution comprising a second catalyst compound and a third catalyst compound, and the modified catalyst slurry comprises a modified supported catalyst incorporating the first catalyst compound, the second catalyst compound, and the third catalyst compound; feeding the modified catalyst slurry to a fluidized bed gas-phase reactor; and polymerizing an ^-olefin in the fluidized bed gas-phase reactor under polymerization conditions to obtain a polyolefin.

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

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

4. A method comprising: 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; contacting the catalyst slurry with two or more catalyst solutions to obtain a modified catalyst slurry, wherein: the two or more catalyst solutions comprises a first catalyst solution comprising a second catalyst compound and a second catalyst solution comprising a third catalyst compound, and the modified catalyst slurry comprises a modified supported catalyst incorporating the first catalyst compound, the second catalyst compound, and the third catalyst compound; feeding the modified catalyst slurry to a fluidized bed gas-phase reactor; andpolymerizing an ^-olefin in the fluidized bed gas-phase reactor under polymerization conditions to obtain a polyolefin.

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

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

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 of claims 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): wherein:M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R1, R2, R3, R4, R5, R6, R7, R7’, R8, R8’, R9, R9’, R10and R10’is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, one or more of R5and R6, R7and R8, R8and R9, and R9and R10are joined to form a substituted or unsubstituted completely saturated ringor a substituted or unsubstituted aromatic ring, or one or more of R7’and R8’, R8’and R9’, and R9’and R10’are absent such that a carbon-carbon double bond is present between the corresponding carbon atoms of the hydroindenyl ring shown in Formula (I); T represents the formula Ra2J, (Ra)4J2, or (Ra)6J3wherein each J is independently C, Si, or Ge, and each Rais independently hydrogen, halide, a substituted or unsubstituted C1 to C40 hydrocarbyl, or two Racan form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and each of X1and X2is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1and X2are joined to form a metallocyclic ring.

10. The method of claim 9, wherein each of R7, R7’, R8, R8’, R9, R9’, R10and R10’is hydrogen.

11. The method of claim 10, wherein T is Ra2J, wherein J is Si and each Rais a methyl group.

12. The method of claim 11, wherein at least one of the first catalyst compound, the second catalyst compound, or the third catalyst ^^ ^13. The method of claim 11, wherein at least one of the first catalyst compound, the second catalyst compound, or the third catalyst .

14. The method of 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) wherein: M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R21’, R22, R22’, R23, R23’, R24, R24’, R25, R25’, R26, R26’, R27, R27’, R28, and R28’is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; and each X is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, phosphide, or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

15. The method of claim 14, wherein each of R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R21’, R22, R22’, R23, R23’, R24, R24’, R25, R25’, R26, R26’, R27, R27’, R28, and R28’are independently16. The method of claim 15, wherein at least one of the first catalyst compound, the second catalyst compound, or the third catalyst .

17. The method of claims 1 or 4, wherein the polyolefin obtained is a copolymer derived from monomers comprising ethylene and an ^-olefin comonomer, wherein the ^-olefin comonomer is any one or more C3-C12^-olefin monomers.

18. The method of claim 17, wherein the ^-olefin comonomer is selected from the group consisting of 1-butene, 1-hexene, 1-octene, and combinations thereof.

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

20. The method of claims 1 or 4, wherein the catalyst slurry further comprises a wax. ^

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