Low-cost preparation of in situ MAO-supported and derived finished polyolefin catalysts.

Abstract

The present disclosure provides a method for preparing a catalyst system comprising contacting at least one support material having absorbed water with trimethylaluminum (TMA) in an organic solvent at a temperature of less than −6° C. to −60° C. to form a supported MAO (catalyst precursor) in situ, and contacting the supported MAO with at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom, wherein the TMA to water ratio and the in situ sMAO formation temperature are controlled so that the supernatant after in situ supported MAO formation, with optional heating, or after finished catalyst formation contains no NMR-detectable TMA or 500 ppm or less TMA.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 355,250, filed June 24, 2022, the disclosure of which is incorporated herein by reference. Field The present disclosure relates to a method for producing a polyolefin catalyst system that improves catalyst operability in either a slurry or gas phase polyolefin reactor and reduces the production cost of the catalyst system. [Background technology]

[0002] Polyolefins are widely used commercially due to their robust physical properties. For example, various types of polyethylene, such as high-density, low-density, and linear low-density polyethylene, are some of the most commercially useful polyolefins. Polyolefins are typically prepared using a catalyst (mixed with one or more other components to form a catalyst system) that promotes the polymerization of olefin monomers in a reactor, such as a gas-phase reactor. Methylalumoxane, or MAO, is the most common activator supported on silica to activate single-site catalyst precursors (e.g., metallocenes) to form active solid catalysts used in commercial gas-phase reactors to produce single-site polyolefin resins. Commercially available MAO is typically sold as a toluene solution because aromatic solvents can dissolve MAO and form homogeneous solutions without the problems observed with other solvents. For example, donor-containing solvents (e.g., ether or THF) inactivate MAO, active proton-containing solvents (e.g., alcohols) react with MAO and decompose it, and aliphatic solvents (e.g., hexane) precipitate it. However, MAO toluene solutions are thermally unstable, and to obtain a more homogeneous (i.e., less gelling) MAO solution within a given period, e.g., approximately 3 months, storage at low temperatures, e.g., −20°C to −30°C, is required to shorten the gelation process commonly observed with this kinetic product. MAO molecules begin dimerization / oligomerization immediately after formation, even under cooling, eventually forming an insoluble gel. Therefore, MAO products stored at -20°C for different periods, for example, 1 month and 3 months, may have significantly different molecular compositions, with the fresher MAO product having a smaller and more numerous MAO molecule population, while the older product has a larger and fewer MAO molecule population due to the gelation process. To obtain a catalyst with superior performance, such as superior productivity and ease of use, it is highly desirable to obtain MAO molecules with a low gel content, thereby more uniformly distributing them within the pores of the catalyst support material (e.g., silica). Furthermore, polyolefin products are often used as plastic packaging for delicate products, and it is desirable to minimize the amount of non-polyolefin compounds, such as toluene, present in polyolefin products.

[0003] U.S. Patent No. 11,161,922 demonstrated that MAO can be prepared in situ on a support, such as silica, by adding water-treated silica to a cold trimethylaluminum (TMA) solution. It was discovered that when MAO molecules are supported (immobilized on the pore surface), the gelation process is almost completely blocked, preventing the MAO molecules from migrating to contact and dimerize. Therefore, this in situ supported MAO (sMAO) does not need to be stored at low temperatures, and the resulting sMAO maintains the ratio of large molecules to small molecules and the total MAO molecular population, providing more consistent performance over storage. Formation of in situ sMAO does not require aromatic solvents. The fresh active MAO composition produced from the reaction of TMA with cooling was converted to coordinated TMA (TMA c ), for example, (Al4O3Me6)4(TMA c ) n It has been experimentally verified that TMA (n=1 or 2) is contained in MAO (Sinn, et al., "Formation, Structure, and Mechanism of Oligomeric Methylaluminoxane", Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, pp. 105). c is the actual active species AlMe2 + (Luo, Jain, and Harlan, ACS Annual Meeting, Conference Abstracts PMSE 126 and INOR 1169, April 2-6, 2017). Relevant references include U.S. Patent Nos. 8,354,485, 9,090,720, 7,910,764, 8,575,284, 5,006,500, 4,937,217, U.S. Patent Application Publication No. 2016 / 0355618, and WO 2016 / 170017. TMA on in situ sMAO cTo maximize the MAO formula (Al4O3Me6)4(TMA c A TMA:water ratio of at least 1.5:1 based on the Al:O ratio in the 2-hydroxybenzoic acid catalyst is used (U.S. Pat. No. 11,161,922). Such a ratio is typically used for the synthesis of TMA on MAO. f and TMA c The remaining free TMA (TMA) in the supernatant is f ) (Equation 1). [ka]

[0004] TMA f The residual TMA in the supernatant was removed to avoid fouling of the polymerization reactor, possibly due to the formation of unsupported, soluble, less active species due to the reaction of the TMA with neutral catalyst precursors such as neutral methacelone present in the equilibrium activation process with sMAO. f It is necessary to remove by filtration and wash with a solvent (Equation 2): [ka] Summary of the Invention

[0005] Exemplary embodiments described herein relate to a method for preparing in situ supported MAO, comprising contacting at least one support material having absorbed water with TMA in an organic solvent at a temperature of -6°C to -60°C, using a controlled TMA to water ratio, to obtain a supernatant free of or low in free TMA. This eliminates the need for filtration and washing steps, simplifying both the finished catalyst production equipment / facility and the solid finished catalyst isolation drying steps, such as simple heat and / or vacuum drying. This allows the solvent to be either directly reused in a continuous catalyst production process or conventionally disposed of without further treatment. The resulting finished catalyst also exhibits excellent reactor operability under both gas-phase and slurry-phase polymerization conditions. Exemplary embodiments described herein relate to a method for preparing a catalyst system comprising contacting at least one support material having absorbed water with TMA in an organic solvent at a temperature of less than −6° C. to −60° C., using a controlled ratio of TMA to water, to form an in situ supported MAO, and contacting the supported MAO with at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom. The supported MAO may be heated prior to contact with the catalyst compound. Exemplary embodiments described herein relate to catalyst systems comprising catalyst compounds having Group 3 to Group 12 metal atoms or Lanthanide metal atoms, the catalyst systems further comprising in situ supported MAO, and the catalyst systems do not contain detectable amounts of aromatic solvents when only aliphatic solvents are used. [Brief explanation of the drawings]

[0006] [Figure 1] 1 shows spectra comparing the TMA content of Examples 3 and 4. DETAILED DESCRIPTION OF THE INVENTION

[0007] In catalyst preparation facilities without filtration and washing capabilities, free TMA cannot be removed; even in those with filtration and washing capabilities, residual free TMA in the supernatant complicates disposal of waste solvents, requiring, for example, procedures to inactivate the free TMA prior to normal disposal processes. Therefore, there is a need to obtain a supported finished catalyst with no or at least low concentrations of free TMA in the supernatant, which does not cause serious polymerization reactor operation problems and allows the solvent to be directly recycled as is.

[0008] The present disclosure relates to a method for preparing a catalyst system to obtain a TMA-free or low supernatant, which allows for the production of a dry finished catalyst system with excellent polymerization reactor operability in a simple catalyst preparation facility without filtration and washing capabilities, and allows for the direct reuse of the solvent used in in situ supported MAO formation and / or the resulting finished catalyst formation. An embodiment of the present disclosure includes a method for preparing an in situ supported MAO, which comprises contacting at least one support material having absorbed water with TMA in an organic solvent at a temperature ranging from -6°C to -60°C, with a charge Al:water ratio controlled to obtain a supernatant with no or low free TMA. The supported MAO is formed in situ when TMA reacts with absorbed water on the silica, where the ratio of TMA and absorbed water on the support is controlled at different ratios based on the absorbed water content, and the in situ supported MAO formation temperature is controlled within different ranges. The conditions are as follows: a. For carriers containing 6.5 (mmol / g carrier) or less of absorbed water, the charge TMA:water ratio is controlled in the range of 1.31:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or b. For supports containing less than 5.0 mmol / g of absorbed water, the charge TMA:water ratio is controlled in the range of 1.42:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or c. For carriers containing 7.0-10.0 (mmol / g carrier) of absorbed water, the charge TMA:water ratio is controlled in the range of 1.20:1-1.15:1, and the in situ supported MAO formation temperature is controlled between -12°C and -60°C. Alternatively, to obtain a supernatant with no or little free TMA, the charge TMA:water ratio is controlled to 1.80:1 to 1.42:1, the in situ supported MAO formation temperature is controlled to -6°C to -60°C, and then after the in situ supported MAO formation or the finished catalyst formation, a second support containing hydroxy groups is added to the supernatant to remove free TMA from the supernatant. Here, the support containing hydroxy groups can be a support containing absorbed water or a support containing pore surface hydroxy groups, such as silica calcined at 150°C, 200°C, 400°C, or higher. The present disclosure also includes a method for preparing a catalyst system, which includes heating the in-situ supported MAO prior to contact with a catalyst precursor compound. The catalyst precursor compound has a Group 3 to Group 12 metal atom or a Lanthanide metal atom. The catalyst precursor compound can be a metallocene catalyst compound containing a Group 4 metal. Any organic solvent, including aliphatic solvents, can be used to obtain an aromatic-free (below detection limits) finished catalyst system.

[0009] In at least one embodiment, the disclosure provides a process for producing in situ supported MAO and supported MAO-derived finished catalysts by contacting at least one support material having absorbed water with TMA, wherein the absorbed water and TMA on the support are controlled as follows: a. For supports containing 6.5 (mmol / g support) or less of absorbed water, the charge TMA:water ratio is in the range of 1.31:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or b. For supports containing less than 5.0 mmol / g of absorbed water, the charge TMA:water ratio is in the range of 1.42:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or c. For a carrier containing 7.0-10.0 mmol / g carrier of absorbed water, the charge TMA:water ratio is in the range of 1.20:1-1.15:1, and the in situ sMAO formation temperature is controlled between -12°C and -60°C; and Separating the in situ supported MAO or derived finished catalyst from the organic solvent, i.e., the supernatant, which can be reused as a solvent without further treatment; The present invention also relates to a continuous process for preparing in situ loaded MAO, comprising:

[0010] The present disclosure also relates to a method for polymerizing olefins to produce polyolefin compositions in an in situ supported MAO formation, comprising contacting at least one olefin with a catalyst system prepared as described herein, and obtaining polyolefins free of detectable aromatic hydrocarbon solvents by using one or more aliphatic solvents, such as pentane, isohexane, and / or heptane, as well as a method for preparing the resulting finished catalyst. The present disclosure provides a process for forming supported MAO by contacting at least one support material having absorbed water with TMA in at least one organic solvent at a temperature of less than −8° C. to −60° C., wherein the absorbed water and TMA on the support are controlled as follows: a. For supports containing 6.5 (mmol / g support) or less of absorbed water, the charge TMA:water ratio is in the range of 1.31:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or b. For supports containing less than 5.0 mmol / g of absorbed water, the charge TMA:water ratio is in the range of 1.42:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or c. For a carrier containing 7.0-10.0 mmol / g carrier of absorbed water, the charge TMA:water ratio is in the range of 1.20:1-1.15:1, and the in situ sMAO formation temperature is controlled between -12°C and -60°C; and heating the supported MAO to at least 50°C and up to 140°C, and then contacting with at least one catalyst precursor compound to form a finished catalyst comprising a Group 3 to Group 12 metal atom or a Lanthanide metal atom; The present invention also relates to a method for preparing a catalyst system, comprising:

[0011] The present disclosure provides a process for forming in situ supported MAO by contacting at least one support material having absorbed water with TMA in at least one organic solvent at a temperature of less than −8° C. to −60° C., wherein the absorbed water and TMA on the support are controlled as follows: a. For supports containing 6.5 (mmol / g support) or less of absorbed water, the charge TMA:water ratio is in the range of 1.31:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or b. For supports containing less than 5.0 mmol / g of absorbed water, the charge TMA:water ratio is in the range of 1.42:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or c. For a carrier containing 7.0-10.0 mmol / g carrier of absorbed water, the charge TMA:water ratio is in the range of 1.20:1-1.15:1, and the in situ sMAO formation temperature is controlled between -12°C and -60°C; and contacting the supported MAO with at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom to form a supported catalyst system; and heating the supported catalyst system to at least 50°C and up to 100°C; The present invention also relates to a method for preparing a catalyst system, comprising:

[0012] The present disclosure provides a process for preparing a TMA-based organic solvent solution by adding at least one support material having absorbed water in solid or slurry form at a temperature ranging from -8°C to -60°C, wherein the absorbed water and TMA on the support are controlled as follows: a. For supports containing 6.5 (mmol / g support) or less of absorbed water, the charge TMA:water ratio is in the range of 1.31:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or b. For supports containing less than 5.0 mmol / g of absorbed water, the charge TMA:water ratio is in the range of 1.42:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or c. For carriers containing 7.0-10.0 (mmol / g carrier) of absorbed water, the charge TMA:water ratio is in the range of 1.20:1-1.15:1, and the in situ sMAO formation temperature is controlled between -12°C and -60°C; The present invention also relates to a method for making in situ supported MAO in at least one organic solvent, comprising:

[0013] The present disclosure provides a method for preparing a TMA aliphatic solvent solution by adding at least one carrier material having absorbed water as a solid or an aliphatic solvent slurry to a TMA aliphatic solvent solution at a temperature ranging from -8°C to -60°C, wherein the absorbed water and TMA on the carrier are controlled as follows: a. For supports containing 6.5 (mmol / g support) or less of absorbed water, the charge TMA:water ratio is in the range of 1.31:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or b. For supports containing less than 5.0 mmol / g of absorbed water, the charge TMA:water ratio is in the range of 1.42:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; or c. For carriers containing 7.0-10.0 (mmol / g carrier) of absorbed water, the charge TMA:water ratio is in the range of 1.20:1-1.15:1, and the in situ supported MAO formation temperature is controlled between -12°C and -60°C; The present invention also relates to a method for making in situ supported MAO, and a derived finished catalyst free of aromatic solvents, comprising:

[0014] The present disclosure also relates to a method for making in situ supported MAO, and a derived finished catalyst free from aromatic solvents, comprising adding at least one support material having absorbed water as a solid or an aliphatic solvent slurry to a TMA aliphatic solvent solution at a temperature ranging from -6°C to -60°C, wherein the charge TMA to water ratio is controlled to be 1.80:1 to 1.42:1; and then removing free TMA from the supernatant after in situ supported MAO formation or after finished catalyst formation by adding a second support containing hydroxy groups to the supernatant, wherein the support containing hydroxy groups can be a support containing absorbed water or a support containing pore surface hydroxy groups, such as silica calcined at 150°C, 200°C, 400°C, or higher.

[0015] The present disclosure also relates to any of the methods described herein, wherein the TMA solution concentration is 0.1% to 40% by weight, preferably 1.0% to 20% by weight. The present disclosure also relates to a process that is continuous and includes the steps of isolating the solid-supported MAO or derived finished catalyst product and recycling the organic solvent without further treatment. The present disclosure also relates to any of the methods described herein, wherein the in situ formed supported MAO composition is further heat treated at a temperature selected from 50°C to 140°C for 0.5 to 24 hours prior to contact with the catalyst precursor compound. Embodiments of the present disclosure also include catalyst systems that include a Group 4 metal catalyst compound selected from a metallocene catalyst precursor compound, a half-metallocene catalyst precursor compound, or a post-metallocene catalyst precursor compound.

[0016] The use of an aliphatic solvent such as isohexane in place of an aromatic solvent such as toluene results in a catalyst system (and polyolefin product) that has no detectable aromatic hydrocarbon solvent content while maintaining activity approaching that of catalyst systems prepared with MAO preformed in the required aromatic solvent (e.g., Grace's commercially available MAO product, e.g., 30% MAO in toluene solution). Eliminating aromatic hydrocarbon solvents in the catalyst system results in polyolefin products free of detectable aromatic hydrocarbon solvents (preferably free of detectable toluene) as measured by gas-phase chromatography as described in the Experimental Section below. The polyolefin products may be used as plastic materials for use in toluene-free materials, such as food product packaging, automotive interior materials, and medical devices. Furthermore, because many saturated hydrocarbons, such as pentane (36.1°C) and toluene (110°C), have lower boiling points than aromatic hydrocarbons, the saturated hydrocarbons are easier to remove from the polyolefin product, reducing energy consumption. While solution MAO requires 24 hours a day, 7 days a week, low-temperature conditions for storage of the MAO product prior to use and transportation from the MAO facility site to the user site, the in situ MAO loading technology further reduces energy consumption by eliminating the need for a solution MAO production facility. MAO gel cleaning facilities for gelation routing in both the MAO formation reactor and storage vessel are also eliminated, avoiding wastewater entering rivers and groundwater.

[0017] For purposes of this disclosure, "supernatant" refers to the inert organic solvent used for dilution of the starting materials and remaining in the reactor after the relevant reaction is complete, along with any insoluble products of either the in-situ supported MAO or the derived catalyst system, including any insoluble inert by-products formed from the reaction of TMA with water or the support material, such as CH4 from the reaction of TMA with water, siloxanes from the reaction of TMA with silicon- and oxygen-containing species on the support surface, or dissolved substances, such as oil or grease, from the reactor equipment. "TMA-free supernatant" means that the TMA in the supernatant is below the lower detection limit of NMR. "Supernatant low in hydrocarbyl aluminum compounds" means that the TMA in the supernatant is below 600 ppm as measured by NMR. For purposes of this disclosure, "detectable aromatic hydrocarbon solvent" refers to a solvent containing 0.1 mg / m or less of TMA as measured by gas phase chromatography. 2 For purposes of this disclosure, "detectable toluene" means 0.1 mg / m 2 as measured by gas phase chromatography. 2 That's all it means. As used herein, in situ supported MAO and in situ sMAO have the same meaning, and coordinated TMA = TMA c , and free TMA = TMA f Metallocene, single-site catalyst, or transition metal compound can be used interchangeably, meaning that they are all catalyst precursor compounds and require an activator to become activated prior to being able to polymerize olefins. As used herein, the term "saturated hydrocarbon" includes hydrocarbons that do not contain carbon-carbon double bonds. Saturated hydrocarbons can be straight-chain or cyclic hydrocarbons. Saturated hydrocarbons include hydrocarbons with carbon atoms ranging from C3 to C6. 40 In at least one embodiment, the hydrocarbon may be a C3 to C7 hydrocarbon. 40 The hydrocarbon may be propane, isobutane, isopentane, cyclohexane, isohexane, hexane, heptane, octane, or mixtures thereof.

[0018] In at least one embodiment, a method for polymerizing olefins to produce a polyolefin composition includes contacting at least one olefin with the catalyst system of the present disclosure and obtaining a polyolefin free of detectable aromatic hydrocarbon solvents. The polymerization can be carried out at a temperature of from about 0° C. to about 200° C., at a pressure of from about 0.35 MPa to about 10 MPa, and for a time period of up to about 300 minutes. The at least one olefin can be a C2 to C6 40 Olefins, preferably C2-C 20 It may be an α-olefin, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or mixtures thereof.

[0019] For purposes of this disclosure, the numbering scheme for the Periodic Table Groups will be used as described in Chemical and Engineering News, v. 63(5), pg. 27 (1985). Thus, a "Group 4 metal" is an element in Group 4 of the Periodic Table, such as Hf, Ti, or Zr. "Catalyst productivity" is a measure of how many grams of polymer (P) are produced in T hours using a polymerization catalyst containing W grams of catalyst (cat) and is expressed as P / (T x W) in units of gP / gcat / hr. "Conversion" is the amount of monomer converted to polymer product in a polymerization, reported as a mole percent and calculated based on the polymer yield (mass) and the amount of monomer fed to the reactor. Catalyst activity is a measure of the level of activity of the catalyst and is expressed as the mass of product polymer produced per mass of supported catalyst (cat) (gP / g supported cat). In at least one embodiment, the activity of the catalyst is at least 800 g polymer / g supported catalyst / hour, such as about 1,000 g polymer / g supported catalyst / hour or more, such as about 2,000 g polymer / g supported catalyst / hour or more, such as about 3,000 g polymer / g supported catalyst / hour or more, such as about 4,000 g polymer / g supported catalyst / hour or more, for example about 5,000 g polymer / g supported catalyst / hour or more. An "olefin," also known as an "alkene," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. When a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, if a copolymer is referred to as having an ethylene content of 35% to 55% by weight, it is understood that the monomer ("mer") units in the copolymer are derived from ethylene in a polymerization reaction, and the derived units are present in an amount of 35% to 55% by weight, based on the weight of the copolymer. A "polymer" has two or more mer units, which may be the same or different. A "homopolymer" is a polymer having the same mer unit. A "copolymer" is a polymer having two or more mer units that are different from one another. A "terpolymer" is a polymer having three mer units that are different from one another. "Different," when used in reference to mer units, indicates that the mer units differ from one another by at least one atom or are isomerically different. Thus, the definition of "copolymer" as used herein includes terpolymers, etc. Oligomers are typically polymers having a low molecular weight, such as an Mn of less than 25,000 g / mol, or less than 2,500 g / mol, or a low number of mer units, such as 75 mer units or less, or 50 mer units or less. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene-derived units, etc.

[0020] A "catalyst system" is a combination of at least one catalyst compound and a support material. The catalyst system may have at least one activator and / or at least one co-activator. When a catalyst system is described as comprising the neutral stable form of a component, it is fully understood that the ionic form of the component is the form that reacts with a monomer to produce a polymer. For purposes of this disclosure, "catalyst system" encompasses both the neutral and ionic forms of the components of the catalyst system. As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z-average molecular weight, wt% is mass percentage, and mol% is mole percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mole. In this disclosure, catalysts may be described as catalyst precursors, pre-catalyst compounds, catalyst compounds, or transition metal compounds, and these terms are used interchangeably. An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. A "neutral donor ligand" is a neutrally charged ligand that donates one or more electron pairs to a metal ion. For purposes of this disclosure regarding catalyst compounds, the term "substituted" means that a hydrogen group is replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (MeCp) is a Cp group substituted with a methyl group.

[0021] This disclosure describes transition metal complexes. The term complex is used to describe molecules in which ancillary ligands are coordinated to a central transition metal atom. The ligands are stably bound to the transition metal so as to maintain their influence during use of the catalyst, e.g., during polymerization. The ligands may be coordinated to the transition metal by covalent and / or electron-donating bonds, or by intermediate bonds. Transition metal complexes are generally activated using an activator that is believed to remove an anionic group (often called a leaving group) from the transition metal to create a cation, thereby performing its polymerization function.

[0022] As used in this disclosure, the abbreviations have the following meanings: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, nBu is normal butyl, sBu is secondary butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylalumoxane, sMAO is supported methylalumoxane, Bn is benzyl (i.e., CHPh), THF (also referred to as thf) is tetrahydrofuran, RT is room temperature (23° C. unless otherwise specified), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

[0023] The terms "hydrocarbyl radical," "hydrocarbyl," "hydrocarbyl group," "alkyl radical," and "alkyl" are used interchangeably throughout this disclosure. Similarly, the terms "group," "radical," and "substituent" are also used interchangeably in this disclosure. For purposes of this disclosure, a "hydrocarbyl radical" refers to a C1-C6 alkyl group that may be linear, branched, or cyclic. 100 A cyclic radical is defined as a cyclic group, which, when cyclic, can be aromatic or non-aromatic. Examples of such radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including substituted analogs thereof. A substituted hydrocarbyl radical is one in which at least one hydrogen atom of the hydrocarbyl radical has been replaced with a non-hydrogen group, such as at least one halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as NR * 2, OR * , SeR * , TeR * , PR *2. AsR * 2. SbR * 2. SR * , B.R. * 2. SiR * 3. GeR * 3. SnR * 3. PbR * It is a radical which is substituted with 3 or more heteroatoms or which has at least one heteroatom inserted within the hydrocarbyl ring.

[0024] The term "alkenyl" refers to a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. These alkenyl radicals may be substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and the like, including substituted analogs thereof. The term "aryl" or "aryl group" refers to carbon-containing aromatic rings and substituted variants thereof, including, but not limited to, phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which one ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, preferably N, O, or S. As used herein, the term "aromatic" also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents that have similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but which are not aromatic by definition. "Aromatic" refers to a hydrocarbyl compound containing a planar, unsaturated ring of atoms stabilized by the interaction of the bonds that form the ring. Such compounds are often six-membered rings, such as benzene and its derivatives. As used herein, the term "aromatic" also refers to pseudoaromatics, which are compounds that have similar properties and structure (nearly planar) to aromatics but are not aromatic by definition; similarly, the term aromatic also refers to substituted aromatics. Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), a reference to one group within that group (e.g., n-butyl) is intended to explicitly disclose the remaining isomers of the family (e.g., iso-butyl, sec-butyl, and tert-butyl). Similarly, a reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

[0025] The term "ring atom" refers to an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms, and tetrahydrofuran has 5 ring atoms. A heterocycle is a ring that has a heteroatom in the ring structure, and is different from a heteroatom-substituted ring in which a hydrogen atom on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. As used herein, "complex" is often also referred to as a catalyst precursor, pre-catalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. The above terms are used interchangeably. Activator and co-catalyst are also used interchangeably. A scavenger is a compound that can be added to a catalyst system to promote polymerization by scavenging impurities. Some scavengers also act as activators and are sometimes called co-activators. Co-activators that are not scavengers can also be used in combination with activators to form an active catalyst system. In at least one embodiment, the co-activator can be premixed with the transition metal compound to form an alkylated transition metal compound.

[0026] In this disclosure, catalysts may be described as catalyst precursors, pre-catalyst compounds, catalyst compounds, or transition metal compounds, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into polymers. The term "continuous" refers to a system that operates without interruption or cessation for any period of time. For example, a continuous process for producing a polymer involves continuous introduction of reactants into one or more reactors and continuous discharge of polymer product. "Bulk polymerization" refers to a polymerization process in which the monomers and / or comonomers to be polymerized are used as solvents or diluents, with little or no inert solvent or diluent. Small amounts of inert solvent may also be used as carriers for catalysts and scavengers. A bulk polymerization system contains less than about 25% by weight, e.g., less than about 10% by weight, e.g., less than about 1% by weight, e.g., 0% by weight, of inert solvent or diluent. The term "σ bond" refers to a two-electron single bond formed by two atoms, with each atom donating one electron. The term "coordinate bond" refers to a two-electron single bond formed by two atoms, with one of the atoms donating all two electrons, called an electron-pair donor bond.

[0027] Carrier material In at least one embodiment, the catalyst system comprises a support material capable of absorbing water in an amount of at least 0.5 millimole of water per gram of support material. The support material may be a porous support material (e.g., silica) or other inorganic oxides such as alumina, zeolites, talc, clays, organoclays, etc., or may be an inorganic support material containing functional groups such as Bronsted sites, e.g., OH groups, Lewis basic sites, e.g., electron donor groups such as amine or phosphine groups, or Lewis acid sites, e.g., unsaturated metal centers such as three-coordinate aluminum sites, or mixtures thereof. In at least one embodiment, the support material is a finely divided inorganic oxide. Suitable inorganic oxide materials for use in the catalyst system herein include oxides of Groups 2, 4, 13, and 14 metals, such as silica and alumina, and mixtures thereof. Other inorganic oxides that may be used alone or in combination with silica or alumina include magnesia, titania, zirconia, and the like. However, other suitable support materials can be used, such as finely divided functionalized polyolefins, e.g., finely divided polyethylene, polypropylene, and polystyrene having oxygen- or nitrogen-containing groups, such as -OH, -RC=O, -OR, and -NR2, that are capable of absorbing water. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicates, zeolites, talc, clays, silica clays, silicon oxide clays, and the like. Combinations of these support materials, such as silica-chromium, silica-alumina, silica-titania, and the like, may also be used. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O2, silica clay, silicon oxide / clay, or mixtures thereof. The support material may be fluorided.

[0028] As used herein, "fluorided support" and "fluorided support composition" refer to a support, preferably particulate and porous, that has been treated with at least one inorganic fluorine-containing compound. For example, the fluorided support composition can be a silicon dioxide support in which a portion of the silica hydroxy groups have been replaced with fluorine or a fluorine-containing compound. Suitable fluorine-containing compounds include, but are not limited to, inorganic fluorine-containing compounds and / or organic fluorine-containing compounds. Fluorine compounds suitable for providing fluorine to the support may be organic or inorganic fluorine compounds, preferably inorganic fluorine-containing compounds. Such inorganic fluorine-containing compounds may be any compound containing fluorine atoms as long as they do not contain carbon atoms. Particularly desirable are inorganic fluorine-containing compounds selected from NHBF, (NH)SiF, NHPF, NHF, (NH)TaF, NNHNbF, (NH)GeF, (NH)SmF, (NH)TiF, (NH)ZrF, MoF, ReF, GaF, SOClF, F, SiF, SF, ClF, ClF, BrF, IF, NF, HF, BF, NHF, NHHF, and combinations thereof. In at least one embodiment, ammonium hexafluorosilicate and ammonium tetrafluoroborate are used.

[0029] In at least one embodiment, the support material comprises a support material treated with an electron-withdrawing anion, which can be silica, alumina, silica-alumina, silica-zirconia, alumina-zirconia, aluminum phosphate, heteropolytungstate, titania, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; the electron-withdrawing anion is selected from fluoride, chloride, bromide, phosphate, triflate, hydrogen sulfate, sulfate, or any combination thereof. An electron-withdrawing component can be used to treat the support material. The electron-withdrawing component can be any component that, upon treatment, increases the Lewis or Bronsted acidity of the support material (compared to a support material not treated with at least one electron-withdrawing anion). In at least one embodiment, the electron-withdrawing component is an electron-withdrawing anion derived from a salt, acid, or other compound that serves as a source or precursor of the anion, such as a volatile organic compound. The electron-withdrawing anion can be sulfate, hydrogen sulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phosphotungstate, or a mixture or combination thereof. In at least one embodiment of the present disclosure, the electron-withdrawing anion can be fluoride, chloride, bromide, phosphate, triflate, hydrogen sulfate, sulfate, or the like, or any combination thereof. In at least one embodiment, the electron-withdrawing anion is sulfate, hydrogen sulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or a combination thereof.

[0030] Thus, for example, a support material suitable for use in the catalyst system of the present disclosure can be one or more of fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, etc., or combinations thereof. In at least one embodiment, the activator-support can be or include fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof. In another embodiment, the support material includes hexafluorotitanic acid-treated alumina, hexafluorotitanic acid-treated silica-coated alumina, hexafluorozirconic acid-treated silica-alumina, trifluoroacetic acid-treated silica-alumina, fluorided boria-alumina, tetrafluoroboric acid-treated silica, tetrafluoroboric acid-treated alumina, hexafluorophosphoric acid-treated alumina, or combinations thereof. Additionally, any of the above activator-supports can optionally be treated with metal ions.

[0031] Non-limiting examples of cations suitable for use in the present disclosure in salts of electron-withdrawing anions include ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H, [H(OEt)], [HNR] (R=C-C) 20 hydrocarbyl groups, which may be the same or different, or combinations thereof. Additionally, combinations of one or more different electron-withdrawing anions can be used in various ratios to tailor the inherent acidity of the support material to a desired level. The combination of electron-withdrawing components can be contacted with the support material simultaneously or individually in any order that provides the desired acidity to the chemically treated support material. For example, in at least one embodiment, two or more electron-withdrawing anion sources are compounded in two or more separate contacting steps.

[0032] An example of a process for preparing a chemically treated support material is as follows: a selected support material, or combination of support materials, can be contacted with a first electron-withdrawing anion source compound to form a first mixture; the first mixture can be calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture can then be calcined to form a treated support material. In such a process, the first and second electron-withdrawing anion source compounds can be either the same or different compounds. Methods for contacting the oxide with the electron-withdrawing component, usually a salt or acid of an electron-withdrawing anion, include gelation, co-gelation, impregnation of one compound onto another, etc., or combinations thereof. After the contacting process, the mixture of the contacted support material, electron-withdrawing anion, and optional metal ion can be calcined.

[0033] According to another embodiment of the present disclosure, the support material can be treated by a method including: (i) contacting the support material with a first electron-withdrawing anion source compound to form a first mixture; (ii) calcining the first mixture to produce a first calcined mixture; (iii) contacting the first calcined mixture with a second electron-withdrawing anion source compound to form a second mixture; and (iv) calcining the second mixture to form a treated support material. The support material, most preferably an inorganic oxide, has a surface area of about 10 m 2 / g~about 800m 2 / g (700m 2 / g), a pore volume of about 0.1 cc / g to about 4.0 cc / g, and an average particle size of about 5 μm to about 500 μm. In at least one embodiment, the surface area of the support material is about 50 m 2 / g to about 500 m2 / g, pore volume about 0.5 cc / g to about 3.5 cc / g, average particle size about 10 μm to about 200 μm. The surface area of the support material is about 100 m 2 / g~about 400m 2 The support material may have a pore size of about 10 Å to about 1000 Å, e.g., about 50 Å to about 500 Å, e.g., about 75 Å to about 350 Å. In at least one embodiment, the support material has a pore size of 300 to 400 μm. 2 / g and a surface area of 0.9 to 1.8 cm 3 / g。 In at least one embodiment, the support material may optionally be a silica containing subparticles having an average subparticle size of 0.05 to 5 microns, for example, spray-dried from small particles having an average particle size of 0.05 to 5 microns to form larger primary particles having an average particle size of 5 to 200 microns. In at least one embodiment of the support material, at least 20% of the total pore volume (as defined by the BET method) has a pore size of 100 angstroms or greater. Non-limiting examples of silica include 952, 955, and 948 from Grace Davison; ES70 series, PD17062, PD14024, PD16042, and PD16043 from PQ Corporation (Ecovyst); D70-120A, DM-H302, DM-M302, DM-M402, DM-L302, DM-L303, DM-L402, and DM-L403 from Asahi Glass Chemica (AGC); P-10 / 20 or P-10 / 40 from Fuji, and the like.

[0034] As used in this application, the terms "silica" and "support" are used interchangeably to describe support materials, i.e., when silica is used for purposes of description, it is not meant to limit the support to silica. Other support materials may also be used.

[0035] Support material with absorbed water In embodiments of the present disclosure, the support material contains between 0.5 millimoles of absorbed water per gram of support material and 10 millimoles of absorbed water per gram of support material. To determine the amount of absorbed water, a known amount of water is added to a hydrocarbon slurry of the support, which has been heat-treated, for example, at 150°C, 200°C, 400°C, 600°C, or 875°C to remove pre-absorbed water, and the slurry is stirred in a closed vessel to ensure uniform distribution of the added water within the pores of the support. The amount of water loaded onto the support can be quantified / verified by standard thermogravimetric analysis, for example, loss on drying (LOD) at a temperature of 300°C for 4 hours. Most commercially available support materials contain some absorbed water, and in some cases the amount of absorbed water may be sufficient. In other cases, additional water may be required; for example, the pre-absorbed amount of water may be first determined using the LOD method described above, and then additional water may be added to obtain the desired total amount of water absorbed onto the support. In an embodiment of the present disclosure, a support material containing 0.5 millimoles of absorbed water per gram of support material to 10 millimoles of absorbed water per gram of support material can be prepared in a sealed container as described above, except that no solvent is used. The solids in the sealed container can then be placed in an environment where the container is uniformly heated, i.e., an environment without cold spots where water can condense. The heating temperature can be between 30°C and 100°C, preferably between 45°C and 65°C. The heating time can be at least 30 minutes, e.g., 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or longer. Preferably, the support material is silica, alumina, alumina-silica, or a derivative thereof. Preferably, the support material has an average particle size of 1 to 200 microns, an average pore volume of 0.05 to 5 mL / g, and a surface area of 50 to 800 m 2 / g. Preferably, the support material has been treated with one or more of a Bronsted acid, a Lewis acid, a salt and a Lewis base. Preferably, the support material comprises a silylating agent. Preferably, the support material comprises a hydrocarbyl aluminum compound. Preferably, one or more of the support materials comprises an electron-withdrawing anion.

[0036] organic solvents Suitable organic solvents are materials in which all of the reactants used herein, e.g., the carrier and TMA, may or may not be soluble, and which are liquid at the reaction temperature. Non-limiting examples of solvents include those represented by the formula C n H (n+2) Acyclic alkanes in which n=3 to 30, such as propane, isobutene, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and compounds of the formula C n H n and n=5-30, such as cycloalkanes, e.g., cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc. Aromatic solvents, e.g., benzene, toluene, and xylene, can also be used, but aliphatic solvents are more preferred because the solubility of MAO in aromatic solvents, such as toluene, causes the MAO to dissolve in the supernatant, necessitating removal, e.g., by a filtration step, to avoid reactor fouling and to reuse the solvent.

[0037] TMA Although TMA is used exclusively for in situ supported MAO formation, a portion of other alkylaluminum compounds, such as trialkylaluminum compounds or heteroatom-substituted alkylaluminum compounds, may be present, for example, up to 50 mole % based on total Al. The alkyl substituents are alkyl groups of up to 10 carbon atoms, and minor groups such as octyl, isobutyl, ethyl, or methyl may be present. Thus, suitable trialkylaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri(2-methylpentyl)aluminum, trihexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and AlH i Bu2, AlEt2 iExamples of suitable heteroatom-substituted alkylaluminum compounds include any mixed alkylaluminum compounds such as AlF, AlRF, AlR(OCF), AlR(OCF), and the like. Preferred hydrocarbylaluminum compounds are trimethylaluminum and tri-n-octylaluminum. Thus, suitable heteroatom-substituted alkylaluminum compounds include, but are not limited to, AlRF, AlRF, AlR(OCF), AlR(OCF), and the like. In one embodiment of the method of the present disclosure, to obtain a TMA-free or low-level supernatant, the ratio of water absorbed by the support material to the amount of hydrocarbyl aluminum compound is 1:1.25 to 1:1.42 when the in situ supported MAO formation temperature is in the range of -6°C to -60°C, provided that when the in situ supported MAO is formed at a relatively high cooling temperature, for example, -6°C to -12°C, the water:TMA ratio is controlled to 1:1.25 to 1:1.31, and at a lower cooling temperature, for example, -12°C or below, the water:TMA ratio is controlled to 1:31 to 1:1.42. It should be understood that when the first drop of water-absorbing carrier is added to the TMA solution, the water:TMA ratio is close to 1:∞; therefore, theoretically, the water:TMA ratio to form an active in situ-loaded MAO composition can be 1:1.5 (the O:Al ratio in active MAO of formula (Al4O3Me6)4(AlMe3)2) or greater, e.g., 1:3, 1:5, 1:10, 1:100, 1:1,000, 1:10,000, or greater. However, the final supernatant will contain significant free TMA, e.g., >600 ppm, >1 wt%, >5 wt%, or greater. In some embodiments of the present process, the TMA with other optional aluminum alkyl compounds is present in an amount of about 1.5 to 30 wt.% aluminum, excluding Al in the support material, such as alumina, based on the weight of the isolated solid product. Preferably, the amount of aluminum is 4 to 25 wt.%, more preferably 6 to 15 wt.%, based on the total weight of the isolated solid product. More preferably, the optional aluminum alkyl compound is a compound that reduces the solubility of the modified supported MAO, resulting in a supernatant that is low in or free of soluble aluminum alkyl species, such as AlRF, e.g., AlMeF, AlEtF, Al(CF), AlMe(CF).

[0038] In situ loaded MAO The supported MAO of the present disclosure is prepared by contacting a water-saturated support, such as silica, as a slurry in an organic solvent or as a solvent-free solid, with TMA as a solution in an organic solvent. A preferred method of forming in situ sMAO is to slowly add the support slurry to the TMA solution at a temperature ranging from -6°C to -60°C, preferably -10°C to -50°C, e.g., -12°C up to -40°C, or below -15°C, -20°C, or -30°C, such that the internal temperature of the reactor is maintained within a desired range, e.g., within 4°C, e.g., -10°C ± 1°C, -15°C ± 2°C, or -25°C ± 2°C; e.g., below -6°C. In at least one embodiment of the present disclosure, a high viscosity hydrocarbon solvent, such as mineral oil, is used, at least in part, to create a viscous slurry that reduces or avoids carrier settling over a short period of time. In at least one embodiment of the present disclosure, a mixture of hydrocarbyl aluminum and water-saturated silica is agitated.

[0039] Controlling the gel ratio of active and inactive MAO Formula (Al4O3Me6)4(TMA c ) 1-2 The active MAO is the target MAO composition, which is theoretically derived from 17-18 eq of TMA and 12 eq of HO, giving a TMA:water ratio of 1.42 or 1.50:1. c ) is in equilibrium with free TMA (Sinn, et al., "Formation, Structure, and Mechanism of Oligomeric Methylaluminoxane," Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, pp. 105). Experimental evidence suggests that coordinated TMA is a key catalyst for the ionization of the catalyst precursor compound AlMe2. +This strongly suggests that free TMA functions as an alkylating agent (see Luo, Jain, and Harlan, ACS Annual Meeting, Conference Abstracts PMSE126 and INOR 1169, April 2-6, 2017; Luo, Wu, and Diefenbach, U.S. Pat. No. 9,090,720 (2015)). It has been discovered that two key prerequisites are necessary to form activated MAO as the major product: 1) low temperature, e.g., below -8°C; and 2) an excess of TMA around the water molecule, e.g., the formula of activated MAO with at least one coordinated TMA, i.e., (Al4O3Me6)4(TMA c ) A TMA:water ratio of at least 1.42:1, consistent with 1. If either of the above two conditions is not met, the active MAO molecules are kinetic products that tend to form more stable MAO gel molecules, as shown in the energy profile below, resulting in the inactive MAO gel molecules (AlOMe). n can be formed as the major product (Scheme 1): [ka]

[0040] Experimental results are consistent with the energy profile described above, demonstrating that active MAO molecules in solution are unstable at ambient conditions. For example, a 30% by weight MAO solution in toluene can produce >30% by weight of MAO gel after 3–4 days at ambient conditions. Therefore, to shorten the gelation process and thereby maintain performance with a more practical storage period (e.g., several months) and limited gel content (e.g., <5% by weight of the total MAO content), MAO solutions must be stored at low temperatures, e.g., within the practical cooling range of −20°C to −30°C. The experimental observation of a gradual increase in free TMA content suggests that the gelation process proceeds through successive MAO molecule dimerization steps: two monomers dimerize to form a dimer, a monomer and a dimer dimer dimerize to form a trimer, and two dimers dimerize to form a tetramer, etc., accompanied by the removal of coordinated TMA, leading to the formation of progressively larger MAO molecules (and thus a progressively smaller total number of MAO molecules). On the other hand, when MAO molecules are loaded, the gelation process is almost completely blocked, presumably because the MAO molecules have difficulty moving to meet and dimerize. Therefore, loaded MAO has a long shelf life even under ambient conditions, maintaining an activation efficiency of over 90% for 3 years under ambient conditions in an inert environment. Theoretically, the lower the reaction temperature, the smaller the energy barrier (E in Scheme 1). * ), the population of active MAO molecules capable of forming more stable MAO gel molecules becomes smaller. However, it is not practical to reach ultra-low temperatures, such as -60°C, in commercial reactors. Therefore, in designing commercial manufacturing conditions, there is a compromise between a practical cooling temperature and the amount of MAO gel molecules that can be tolerated in the system. The supported MAO can also be heated to alter the performance of the supported MAO, for example, to dimerize the unsupported small MAO molecules and the supported MAO molecules to reduce the amount of unsupported MAO molecules for improved operability in slurry polymerization processes due to the solubility of the unsupported small MAO molecules, to increase the MAO molecular size and weaken the ion pairing when supported MAO is used to activate more positively charged meta centers and / or more open ligand frameworks of catalyst precursor compounds, or to control the ratio of supported MAO molecules to unsupported large MAO molecules to match the desired comonomer distribution.

[0041] In at least one embodiment of the present disclosure, a portion of the gel molecules can be produced under more practical reaction conditions, resulting in a supported catalyst system that still has reasonable activity. For example, at a reaction temperature of -8 ° C, -10 ° C, or -12 ° C, less than about 40 wt %, less than about 30 wt %, or less than about 20 wt % of gel can be formed, based on the total MAO loaded on the support. Because gel MAO molecules have a TMA:water uptake ratio close to 1:1, supported MAO systems with a low proportion of MAO gel can exhibit a total TMA:water uptake ratio that is less than the Al:O ratio in the active MAO formula, i.e., <1.5:1 for an active MAO with two coordinated TMAs, or <1.42:1 for an active MAO with one coordinated TMA, e.g., about 1.25:1, about 1.30:1, or about 1.35:1. For example, a mixture of 3 eq of supported active MAO molecules (one coordinated TMA) and 1 eq of supported gelling MAO molecules would result in a final TMA:water uptake ratio of 3 / 4 (1.42:1) + 1 / 4 (1:1) = 1.32:1. In at least one embodiment of the present disclosure, the water-absorbed silica is added to the cold TMA solution at a controlled addition rate, such that the reaction temperature can be maintained at a low temperature, e.g., −10° C.±1° C., −20° C.±2° C., −30° C.±4° C., or −60° C.±6° C., such that a majority of the total water-absorbed silica, e.g., 60%, 70%, or 80% by weight, has a significant excess of TMA around the water molecules, e.g., a TMA:water ratio of about 100:1, 80:1, 60:1, 40:1, 20:1, or 10:1, thereby maximizing coordinated TMA formation. In at least one embodiment of the present disclosure, the charge TMA:water ratio is adjusted to H 1 The supernatant is controlled to have no detectable TMA or 600 ppm or less TMA as measured by NMR spectroscopy. In at least one embodiment of the present disclosure, the charge TMA:water ratio does not exceed the Al:O ratio in a composition containing both supported active MAO and supported inactive MAO gel molecules, i.e., for example, the charge TMA:water ratio does not exceed the TMA:water uptake ratio determined by the active MAO to inactive MAO gel ratio.

[0042] Optional Heat Treatment of Supported Aluminoxane After preparation in situ, the supported alumoxanes of the present disclosure can be further treated at higher temperatures for a specified period of time, either in organic solvent slurry or solid form. In at least one embodiment, the high-temperature treatment can range from 60°C to 140°C, preferably 70°C to 120°C, and more preferably 85°C to 110°C. The heating time can range from 30 minutes up to 12 hours, preferably 2 to 8 hours, and more preferably 3 to 6 hours. After such heat treatment, some finished catalyst systems can exhibit significant activity improvements for hafnocenes and other open-chain zirnonocene catalyst precursor compounds, e.g., dimethylsilyl-bridged zirconocenes, while others, such as closed-chain zirconocenes, e.g., unbridged zirconocenes, can exhibit significant activity improvements. After such heat treatment, soluble MAO is limited, thereby improving catalyst operability, especially in slurry polymerization processes. This is likely due to dimerization of small, unanchored soluble MAO molecules into large, insoluble MAO molecules, and / or unanchored MAO molecules becoming anchored by dimerization with anchored MAO molecules, as suggested by the observation that the finished catalyst system after heat treatment has less THF-extractable MAO. Heat treatment also reduces the hydroxyl groups in the finished catalyst system, as shown by IR spectroscopy; unreacted hydroxyl groups are considered deactivators of the finished catalyst system. After contacting the carrier material having absorbed water with TMA in an organic solvent at low temperature, the reaction mixture can be spray-dried in a spray-drying reactor at a higher temperature to evaporate the solvent / volatiles and form a solid product having the desired average particle size and particle size distribution. The preferred temperature range is 60°C to 200°C, more preferably 80°C to 190°C, and most preferably 90°C to 160°C.

[0043] Catalyst Precursor Compound In at least one embodiment, the present disclosure provides a catalyst system including a catalyst precursor compound having a metal atom. The catalyst precursor compound can be a metallocene, half-metallocene, or post-metallocene single-site catalyst precursor compound. The metal can be a Group 3-12 metal atom, such as a Group 3-10 metal atom, or a lanthanide atom. The catalyst compound having a Group 3-12 metal atom can be monodentate or polydentate, such as bidentate, tridentate, or tetradentate, and a heteroatom of the catalyst, such as phosphorus, oxygen, nitrogen, or sulfur, is chelated to the metal atom of the catalyst. Non-limiting examples include bis(phenolates). In at least one embodiment, the Group 3-12 metal atom is selected from a Group 5, 6, 8, or 10 metal atom. In at least one embodiment, the Group 3 to Group 10 metal atoms are selected from Cr, Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni. In at least one embodiment, the metal atoms are Group 4, 5, and 6 metal atoms. In at least one embodiment, the metal atoms are Group 4 metal atoms selected from Ti, Zr, or Hf. The oxidation state of the metal atoms can range from 0 to +7, e.g., +1, +2, +3, +4, or +5, e.g., +2, +3, or +4. The catalyst compound of the present disclosure can be chromium or a chromium-based catalyst. Chromium-based catalysts include chromium oxide (CrO) and silylchromate catalysts. Chromium catalysts have been the subject of much development in the field of continuous fluidized bed gas-phase polymerization for the production of polyethylene polymers. Such catalysts and polymerization processes are described, for example, in U.S. Patent Application Publication No. 2011 / 0010938 and U.S. Patent Nos. 7,915,357; 8,129,484; 7,202,313; 6,833,417; 6,841,630; 6,989,344; 7,504,463; 7,563,851; 8,420,754; and 8,101,691.

[0044] As used herein, metallocene catalyst compounds include metallocenes having Group 3 to Group 12 metal complexes, preferably Group 4 to Group 6 metal complexes, such as Group 4 metal complexes. The metallocene catalyst compounds of the catalyst systems of the present disclosure may be unbridged metallocene catalyst compounds represented by the formula: Cp A Cp B M'X' n In the formula, Cp A and Cp B are each independently selected from cyclopentadienyl ligands and ligands isotropic to cyclopentadienyl; Cp A and Cp B One or both of may contain heteroatoms, and Cp A and Cp Bwherein one or both of the groups may be substituted with one or more R″ groups. M′ is selected from a Group 3 to Group 12 atom or a Lanthanide atom. X′ is an anionic leaving group. n is 0 or an integer from 1 to 4. R″ is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkylthio, lower alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, ether, and thioether. In at least one embodiment, Cp A and Cp B are each independently selected from cyclopentadienyl, indenyl, fluorenyl, cyclopentaphenanthreneyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, and hydrogenated forms thereof.

[0045] Non-limiting examples of unbridged metallocenes include: bis(n-propylcyclopentadienyl)hafnium dichloride, bis(n-propylcyclopentadienyl)hafnium dimethyl, bis(n-propylcyclopentadienyl)zirconium dichloride, bis(n-propylcyclopentadienyl)zirconium dimethyl, bis(n-propylcyclopentadienyl)titanium dichloride, bis(n-propylcyclopentadienyl)titanium dimethyl, (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dimethyl, (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride, (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dimethyl, (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)titanium dichloride, (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)titanium dimethyl, (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dimethyl, (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)hafnium dichloride, (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)hafnium dimethyl, (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)titanium dichloride, (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)titanium dichloride, bis(n-butylcyclopentadienyl)titanium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride, Bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, Bis(1-methyl-3-n-butylcyclopentadienyl)titanium dichloride, and Bis(1-methyl-3-n-butylcyclopentadienyl)titanium dimethyl.

[0046] The metallocene catalyst compound may be a bridged metallocene catalyst compound represented by the formula: Cp A (A)Cp B M'X' n , In the formula, each Cp A and Cp B are independently selected from cyclopentadienyl ligands and ligands isotropic to cyclopentadienyl. A and Cp B One or both of may contain heteroatoms, and Cp A and Cp Bone or both of which may be substituted with one or more R" groups. M' is selected from Group 3 to Group 12 atoms or Lanthanide atoms. X' is an anionic leaving group. n is 0 or an integer from 1 to 4. (A) is a divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, or divalent heteroalkynyl. , divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbyl, divalent lower hydrocarbyl, divalent R" is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkylthio, lower alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, germanium, ether, and thioether. In at least one embodiment, Cp A and Cp Bare each independently selected from cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl. (A) may be O, S, NR', or SiR'2, where each R' is independently hydrogen or C1-C 20 It is a hydrocarbyl.

[0047] Non-limiting examples of bridged metallocenes include: Ethylene-bis(indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(4,5,6,7-indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(4,5,6,7-tetrahydro-indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-(4-(3',5'-di-tert-butyl-4'-methoxy-phenyl)indenyl)(2-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr(CH3)2; Dimethylsilanediyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-ethyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-propyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-butyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl;Dimethylsilanediyl(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl;and Dimethylsilanediyl(2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl. Dimethylsilanediyl(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)(1,5,6,7-tetrahydro-s-indacenyl))(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-phenyl-(1,5,6,7-tetrahydro-s-indacenyl))(2-isopropyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(4'-t-butylphenyl)indenyl)(2-isopropyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-ethyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-propyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-butyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-methyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-ethyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-propyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediyl(2-butyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Dimethylamidoborane (2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-methyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-ethyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-propyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Dimethylamidoborane (2-tert-butyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylamidoborane (2-methyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Dimethylamidoborane (2-ethyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Dimethylamidoborane (2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Dimethylamidoborane (2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-methyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-ethyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-propyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-isopropylamidoborane (2-tert-butyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-ethyl-4-(3',5'-di-phenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Di-iso-propylamidoborane (2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl) (2-n-hexyl-4-(o-biphenyl)indenyl) Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-propyl-4-(3',5'-di-t-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-methyl-4-(3',5'-bis-trifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-ethyl-4-(3',5'-bis-trifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-propyl-4-(3',5'-bis-trifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-butyl-4-(3',5'-bis-trifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-methyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane(2-ethyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane(2-propyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane(2-butyl-4-(3',5'-di-iso-propyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane(2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Bis(trimethylsilyl)amidoborane (2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-methyl-4-phenyl-indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-methyl-4-(3',5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-methyl-4-(3',5-di-t-butyl-4-methoxyphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-methyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-ethyl-4-phenyl-indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-ethyl-4-(3',5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-ethyl-4-(3',5-di-t-butyl-4-methoxyphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-ethyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-propyl-4-phenylindenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-propyl-4-(3',5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-propyl-4-(3',5-di-t-butyl-4-methoxyphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-propyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-isopropyl-4-phenylindenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-isopropyl-4-(3',5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-isopropyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-cyclopropyl-4-phenylindenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-cyclopropyl-4-(3',5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-cyclopropyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-butyl-4-phenylindenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-butyl-4-(3',5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-butyl-4-(4'-t-butylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-methyl-4-(2'-methylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-isopropyl-4-(2'-methylphenyl)indenyl)Zr dichloride or dimethyl; Dimethylsilanediylbis(2-methyl-4-carbozolidinyl)Zr dichloride or dimethyl; and Dimethylsilanediylbis(2-isopropyl-4-carbozolidinyl)Zr dichloride or dimethyl.

[0048] In at least one embodiment, a number of C1 symmetric bis-Cp metallocene catalysts capable of high TmPP and / or diene incorporation can be represented by formula (C1a) by bridging substituted cyclopentadienyl and substituted indenyl catalyst precursor compounds: [ka] (C1a), During the ceremony: M is a transition metal atom; T is a bridging group; X 1 and X 2 are each a monovalent anionic ligand, or X 1 and X 2 are bonded to form a metallocycle ring; R 1 is hydrogen, halogen, unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is a C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 is aryl; R 3 is unsubstituted C4-C 62 Cycloalkyl, substituted C4-C 62 Cycloalkyl, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl or substituted C4-C 62 is heteroaryl; R 2 and R 4 are each independently hydrogen, halogen, or unsubstituted C1-C 40 Hydrocarbyl, C1-C 40Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is a C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 is aryl; R 5 , R 6 , R 7 , and R 8 are each independently hydrogen, halogen, or unsubstituted C1-C 40 Hydrocarbyl, C1-C 40 Substituted Hydrocarbyl, Unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is a C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 aryl, or R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 One or more of the following are bonded to a substituted or unsubstituted C4-C 62 capable of forming saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof; and J 1 and J 2 each of which is bonded to a substituted or unsubstituted C4-C 62 It forms saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0049] In some embodiments of the present disclosure, M is a transition metal, such as a transition metal from Group 3, 4, or 5 of the periodic table, for example, a Group 4 metal, such as Zr, Hf, or Ti. In some embodiments of the present disclosure, X 1 and X 2 are each independently unsubstituted C1 to C 40 Hydrocarbyl (e.g., unsubstituted C-C 20 Hydrocarbyl), substituted C1-C 40 Hydrocarbyl (e.g., substituted C-C 20 Hydrocarbyl), unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, and combinations thereof, such as X 1 and X 2 are each independently a halide or a C1-C5 alkyl, such as methyl. 1 and X 2 are each independently chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. 1 and X 2 forms part of a fused ring or ring system.

[0050] In some embodiments, T is a group of formula (R * 2G) g wherein each G is C, Si, or Ge, g is 1 or 2, and each R * are independently hydrogen, halogen, or unsubstituted C1-C 20 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), substituted C1-C 20 hydrocarbyl, or two or more R *are linked to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic cyclic or polycyclic substituent. In some embodiments of the present disclosure, T is a bridging group and is selected from the group consisting of R'C, R'Si, R'Ge, R'CCR', R'CCR'CR', R'CCR'CR', R'CCR'CR', R'C=CR', R'C=CR'CR', R'CCR'=CR'CR', R'C=CR'CR', R'CSiR' , R'2SiSiR'2, R2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R'2CGe R'2CR'2, R'2GeCR'2GeR'2, R'2SiGeR'2, R'C=CR'GeR'2, R'B, R'2C-BR', R'2C-BR'-CR'2, R'2C-O- CR'2, R'2CR'2C-O-CR'2CR'2, R'2C-O-CR'2CR'2, R'2C-O-CR'=CR', R'2C-S-CR'2, R'2CR'2C-S-C R'2CR'2, R'2C-S-CR'2CR'2, R'2C-S-CR'=CR', R'2C-Se-CR'2, R'2CR'2C-Se-CR'2CR'2, R'2C-Se- R' is independently hydrogen or an unsubstituted C1-C1 alkyl group; ... 20 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), substituted C-C 20 Hydrocarbyl, C1-C 20 Halocarbyl, C1-C 20 Silylcarbyl or C1-C 20or two or more adjacent R' are joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent. In some embodiments of the present disclosure, T is a carbon or silicon containing bridging group such as a dialkylsilyl, e.g., T is CH, CHCH, C(CH), (Ph)C, (p-(Et)SiPh)C, SiMe, SiPh, SiMePh, Si(CH), Si(CH), or Si(CH). In some embodiments, R 1 is hydrogen, substituted C1 to C 20 Hydrocarbyl or unsubstituted C1-C 20 Hydrocarbyl, e.g., substituted C1-C 12 Hydrocarbyl or unsubstituted C1-C 12 It is a hydrocarbyl (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as hydrogen, a substituted C1-C6 hydrocarbyl, or an unsubstituted C1-C6 hydrocarbyl. In some embodiments, R 2 and R 4 are each independently hydrogen, substituted C1 to C 20 Hydrocarbyl or unsubstituted C1-C 20 Hydrocarbyl, e.g., substituted C1-C 12 Hydrocarbyl or unsubstituted C1-C 12 It is a hydrocarbyl (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as hydrogen, a substituted C1-C6 hydrocarbyl, or an unsubstituted C1-C6 hydrocarbyl. In some embodiments, R 5 , R 6 , R 7 , and R 8 are each independently hydrogen, substituted C1 to C 20 Hydrocarbyl or unsubstituted C1-C 20 Hydrocarbyl, e.g., substituted C1-C 12 Hydrocarbyl or unsubstituted C1-C 12hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example, a substituted C1-C6 hydrocarbyl, or an unsubstituted C1-C6 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 At least one of the following is bonded to a substituted or unsubstituted C4-C 20 It may form saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof. In some embodiments, R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 can be linked to form a substituted or unsubstituted C5-C8 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof. In some embodiments, R 3 is unsubstituted C4-C 20 Cycloalkyl (e.g., cyclohexane, cyclopentane, cyclooctane, adamantane), or substituted C4-C 20 It is cycloalkyl. In some embodiments, R 3 is substituted or unsubstituted phenyl, benzyl, carbazolyl, naphthyl, or fluorenyl. In some embodiments, R 3 is a substituted or unsubstituted aryl group represented by the formula: [ka] In the formula, R 9 , R 10 , R 11 , R 12 , and R 13 are each independently hydrogen, unsubstituted C1-C 40Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, a heteroatom, a heteroatom-containing group, or R 9 , R 10 , R 11 , R 12 , and R 13 Two or more of these are bonded to form C4 to C 62 Forming a cyclic or polycyclic ring structure, or a combination thereof. In some embodiments of the present disclosure, R 9 , R 10 , R 11 , R 12 , and R 13 are each independently hydrogen, halogen, or unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, unsubstituted C4-C 62 Aryl (e.g., unsubstituted C4-C such as phenyl) 20 aryl), substituted C4-C 62 Aryl (e.g., substituted C4-C 20 aryl), unsubstituted C4-C 62 Heteroaryl (e.g., unsubstituted C-C 20 Heteroaryl), substituted C4-C 62 Heteroaryl (e.g., substituted C4-C 20 heteroaryl), -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 Aryl. For example, R 9 , R 10 , R 11 , R 12 , and R 13 are each independently hydrogen, substituted C1 to C 20 Hydrocarbyl or unsubstituted C1-C 20 Hydrocarbyl, e.g., substituted C1-C 12 Hydrocarbyl or unsubstituted C1-C 12hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example, a substituted C1-C6 hydrocarbyl, or an unsubstituted C1-C6 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 9 , R 10 , R 11 , R 12 , and R 13 Two or more of these are bonded to form substituted or unsubstituted C4-C 20 It may form saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof. In some embodiments of the present disclosure, R 9 , R 10 , R 11 , R 12 , and R 13 At least one of is phenyl.

[0051] In some embodiments of the present disclosure, J 1 and J 2 Each of the bonds is unsubstituted C4 to C 20 In some embodiments, each J is joined to form a substituted C4-C6 ring. 20 They form cyclic or polycyclic rings, any of which may be saturated or unsaturated. Examples include: [ka] In at least one embodiment, the C1 symmetric bis-Cp metallocene catalyst may also be represented by formula (C1b) by bridging a substituted cyclopentadienyl with a substituted indenyl catalyst precursor compound: [ka] (C1b), In the formula, M, T, J 1 , J 2 , X 1 , X 2 , R 1 , R2 , and R 4 ~R 13 is described above. In at least one embodiment, the C1 symmetric bis-Cp metallocene catalyst may also be represented by formula (C1c) by bridging a substituted cyclopentadienyl with a substituted indenyl catalyst precursor compound: [ka] (C1c), During the ceremony: R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are each independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, a heteroatom, a heteroatom-containing group, or R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 two or more of which are linked to form a cyclic or polycyclic ring structure, or a combination thereof; M, T, X 1 , X 2 , R 1 , R 2 , and R 4 ~R 13 is described above.

[0052] In some embodiments, R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are each independently hydrogen, halogen, or unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 Aryl. For example, R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are each independently hydrogen, substituted C1 to C 20 Hydrocarbyl or unsubstituted C1-C 20 Hydrocarbyl, e.g., substituted C1-C 12 Hydrocarbyl or unsubstituted C1-C 12 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example, a substituted C1-C6 hydrocarbyl, or an unsubstituted C1-C6 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 Two or more of these are bonded to form substituted or unsubstituted C4-C 20 It may form saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0053] In at least one embodiment, the C1 symmetric bis-Cp metallocene catalyst may also be represented by formula (C1d) by bridging a substituted cyclopentadienyl with a substituted indenyl catalyst precursor compound: [ka] (C1d), During the ceremony: R 20 , R 21 , R 22 , R 23 , R 24, R 25 , R 26 , R 27 are each independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 is a hydrocarbyl, a heteroatom, a heteroatom-containing group, or R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 two or more of are linked to form a cyclic or polycyclic ring structure, or a combination thereof; and M, T, X 1 , X 2 , R 1 , R 2 , and R 4 ~R 13 is described above. In some embodiments, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 are each independently hydrogen, halogen, or unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is a C1-C 10 alkyl, and each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 Aryl. For example, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R27 are each independently hydrogen, substituted C1 to C 20 Hydrocarbyl or unsubstituted C1-C 20 Hydrocarbyl, e.g., substituted C1-C 12 Hydrocarbyl or unsubstituted C1-C 12 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example, a substituted C1-C6 hydrocarbyl, or an unsubstituted C1-C6 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 Two or more of these are bonded to form substituted or unsubstituted C4-C 20 It may form saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof. Useful examples of bridged C1 metallocenes used in polyolefin production, particularly propylene and diene polymerization and copolymerization, include, but are not limited to: [ka]

[0054] In another embodiment, the metallocene catalyst compound is represented by the formula: T y Cp m MG n X q , wherein Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or a substituted or unsubstituted ligand isotropic to cyclopentadienyl, such as indenyl, fluorenyl, and indacenyl; M is a Group 4 transition metal, such as Hf, Ti, or Zr; G is a group of the formula JR * z wherein J is N, P, O, or S; and R * is linear, branched, or cyclic C1-C20 is hydrocarbyl. z is 1 or 2. T is a bridging group. y is 0 or 1. X is a leaving group. m=1, n=1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q equals the oxidation state of the transition metal, preferably 2, 3 or 4, preferably 4. In at least one embodiment, J is N and R * is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl, or an isomer thereof. * z Groups include t-butylamido and cyclododecylamido. Preferred examples of bridging groups T include CH2, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me2SiOSiMe2, and PBu. In a preferred embodiment of the invention, in any embodiment of any formula described herein, T is a group of the formula ER d 2 or (ER d 2) 2, where E is C, Si, or Ge, and each R d are independently hydrogen, halogen, C1-C 20 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), or C1-C 20 Substituted hydrocarbyl, two R d may form a ring structure, such as an aromatic, partially saturated, or saturated cyclic or fused ring system. Each X is independently selected from the group consisting of a hydrocarbyl radical having 1 to 20 carbon atoms, aryl, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, and combinations thereof (two X may form part of a fused ring or ring system), preferably each X is independently selected from a halide, aryl, and a C1-C5 alkyl group, preferably each X is phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloro group.

[0055] The half metallocene catalyst precursor compound is Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride; Dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; Dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride; Dimethylsilyl(cyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilyl(3-tertbutylcyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilyl(tetramethylcyclopentadienyl)(1-adamantylamide)M(R)2; μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilyl(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)2; Dimethylsilyl(fluorenyl)(1-tertbutylamide)M(R)2; (tetramethylcyclopentadienyl)(1-cyclododecylamide)M(R)2; μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamide)M(R)2; and Dimethylsilyl(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamide) M(R)2; wherein M is selected from Ti, Zr, and Hf; and each R is selected from halogen or C1-C5 alkyl (preferably chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, or an isomer thereof).

[0056] In at least one embodiment, the catalyst precursor compound is a post-metallocene single-site catalyst compound, e.g., a Group 3 to Group 12 transition metal bonded directly to at least two heteroatoms (e.g., O, N, P, S, CN, etc.) via σ-bonds and / or coordinate bonds in at least one organic ligand, and optionally also having σ-bonds between carbon on the organic ligand and the transition metal center, such as: [ka] has one ligand with two nitrogen donors forming one N-Hf σ bond and one N-Hf coordinate bond, whereas [ka] has one ligand with two nitrogen donors, forming one N-Hf σ bond and one N-Hf coordinate bond plus one C-Hf σ bond. Two of the at least two heteroatoms on the organic ligand may form a 4-, 5-, 6-, 7-, 8-, or more-membered ring with the transition metal center, for example, the two compounds above have a 5-membered ring formed by two N atoms and two C atoms on the ligand and the metal center; for example, the compound having the formula below has two 6-membered rings formed by N, O, three C atoms, and the metal center: [ka] (R 1 ~R 5are independently H or C1 to C 20 an organic group, M is Ti, Zr, or Hf, and X is C l or alkyl such as Me); for example, the two Hf compounds below have two 7-membered rings and one 6-membered ring formed by two O and three or four C atoms on the ligand and the metal center: [ka] JPEG2025525402000015.jpg4536 (Bz = benzyl); for example, the following three compounds have two 8-membered rings formed from the N, O, and five C atoms on the ligand and the metal center: [ka] (M=Ti, Zr, or Hf; X=C l or alkyl such as Bz or Me); etc. Multiple catalyst precursors can be used, for example, one bridged and one unbridged metallocene, one metallocene and one half-metallocene, one metallocene and one post-metallocene, or two post-metallocenes.

[0057] catalyst system formation Embodiments of the present disclosure include a method for preparing a catalyst system comprising contacting in situ supported MAO with at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom in an organic solvent. The catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom can be a metallocene or post-metallocene catalyst precursor compound containing a Group 4 metal. In at least one embodiment, the in situ supported MAO is heated prior to contact with the catalyst precursor compound. The in-situ supported MAO formed as a slurry in an organic solvent can be immediately contacted with at least one catalyst precursor compound, or can be stored as is or isolated as a solid-supported MAO for later use in preparing a finished catalyst. The catalyst precursor compound can also be added to the in-situ supported MAO as a solid or as a slurry in an organic solvent. In at least one embodiment, the in-situ supported MAO slurry is contacted with the catalyst precursor compound for a time period of about 0.02 hours to about 24 hours, e.g., about 0.1 hours to 1 hour, 0.2 hours to 0.6 hours, 2 hours to about 16 hours, or about 4 hours to about 8 hours. The mixture of catalyst precursor compound and in situ supported MAO may be heated to about 30°C to about 100°C, e.g., about 45°C to about 70°C, or may be unheated, e.g., at room temperature. The contact time may be about 0.02 hours to about 24 hours, e.g., about 0.1 hours to 1 hour, 0.2 hours to 0.6 hours, 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0058] Useful organic solvents are those in which all or a portion of the reactants used herein, such as the in situ supported MAO and catalyst precursor compounds, are at least partially soluble (or suspended in the case of a solid support) and are liquid at the reaction temperature. Non-limiting examples of solvents include those represented by the formula C n H (n+2) Acyclic alkanes in which n is 3 to 30, such as propane, isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and compounds of the formula C n H n and n is 5 to 30, such as cycloalkanes, e.g., cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc. Suitable organic solvents also include mixtures of any of the above. While aromatic solvents, e.g., benzene or toluene, can produce finished catalysts with excellent performance, MAO that is not supported on a support is likely to dissolve in these solvents, potentially resulting in high levels of MAO residue in the supernatant, which must be removed prior to contact with the catalyst precursor compound and before solvent reuse to avoid catalyst operability problems. If the in situ supported MAO is isolated as a solid for later use, to prepare a finished catalyst using the isolated supported MAO solid, a solvent can be charged to the reactor, followed by the solid-supported MAO. The catalyst precursor compound can then be charged to the reactor, for example, as a solution in an organic solvent, or as a solid. The mixture can be stirred at a temperature such as room temperature. Additional solvent can be added to the mixture to form a slurry having a desired consistency, for example, about 2 cc / g silica to about 20 cc / g silica, for example, about 4 cc / g. The solvent is then removed. Solvent removal can be accomplished by drying the mixture, under vacuum, purging with an inert atmosphere, heating the mixture, or a combination thereof. Heating the mixture at any suitable temperature that will evaporate the organic solvent can be used. It will be understood that reduced pressure under vacuum will lower the boiling point of the organic solvent, depending on the pressure in the reactor. The solvent removal temperature can be about 10°C to about 100°C, such as about 60°C to about 90°C, for example, about 60°C to about 80°C, for example, about 75°C or less, for example, about 65°C or less. In at least one embodiment, solvent removal includes heating, applying a vacuum, purging with nitrogen from the bottom of the vessel by bubbling nitrogen through the mixture, etc. The mixture is dried.

[0059] How to obtain TMA-free or low-level supernatant Embodiments of the present disclosure include methods for preparing an in situ supported MAO or derived finished catalyst system having a supernatant after formation of the in situ supported MAO or derived finished catalyst that is free or low in free TMA, for the purpose of: 1) to eliminate or reduce potential fouling factors caused by free TMA in the supernatant reacting with catalyst precursor compounds to form unsupported, soluble, less active species; and 2) To allow the supernatant to be directly reused as a solvent without further treatment. Charge TMA:water (or water:TMA) ratio The term refers to the ratio of TMA and water starting materials charged to the in situ sMAO formation reactor. TMA:water uptake ratioThe term sMAO refers to an indirect measure of the ratio of charged water to TMA that reacts to form MAO molecules loaded on silica, and the H of free TMA remaining in the supernatant after the in situ sMAO formation reaction. 1 Assuming that all water molecules are converted into MAO molecules, as estimated by NMR quantification and that there are more water-reactive Al-Me units than reactive OH units of the charged water, the following can be calculated: TMA:water uptake ratio = (charged TMA - residual TMA):charged water For example, for a charge TMA:water ratio of 1.30:1, the water-reactive Al-Me units (AlMe3) on TAM are 1.30 × 3 eq = 3.90 eq, and the OH units of water are 2 eq.

[0060] Method 1 In the case of a carrier containing 6.5 (mmol / g carrier) or less of absorbed water, as shown in Table 2, when the charge TMA:water ratio is controlled in the range of 1.31:1 to 1.25:1 and the in situ supported MAO formation temperature is controlled to -8°C or less, for example, -10±2°C, -12±4°C, -15±7°C, -20±12°C, or -8°C or less and -60°C or more, no TMA (H 1 NMR detection limit) or TMA concentration is 600 ppm or less (H described in Example 22 1 In situ sMAO (quantified by NMR) can be obtained from the supernatant of the derivatized finished catalyst slurry. The data in Table 2 were generated from a catalyst prepared from a TMA concentration of approximately 20 wt. % and a water-absorbed silica slurry of approximately 22 wt. %. However, higher or lower concentrations of the two components can be used, e.g., 30-80 wt. % or 1-3 wt. % TMA and 23-25 wt. % or 1-10 wt. % water-absorbed silica slurry. The water-absorbed silica may be added as a solid.

[0061] Method 2 In the case of a carrier containing 5.0 (mmol / g carrier) or less of absorbed water, as shown in Table 2, when the charge TMA:water ratio is controlled in the range of 1.42:1 to 1.25:1 and the in situ supported MAO formation temperature is controlled to -12°C or less, e.g., -14±2°C, -20±8°C, -30±18°C, or -12°C or less and -60°C or more, no TMA (H 1 NMR detection limit) or TMA concentration is 600 ppm or less (H described in Example 22 1 The supernatant of the finished catalyst slurry can be obtained (quantitated by NMR). The data in Table 2 were generated from a catalyst prepared from a slurry containing approximately 20% by weight of TMA and approximately 22% by weight of water-absorbed silica. However, higher or lower concentrations of the two components can be used, e.g., 30% to 80% by weight, or 1% to 3% by weight of TMA, and 23% to 25% by weight, or 1% to 10% by weight of water-absorbed silica slurry. The water-absorbed silica may be added as a solid.

[0062] Method 3 For carriers containing 7.0 to 10.0 (mmol / g carrier), e.g., 7.0, 7.5, 8.0, 9.0, or 10.0 (mmol / g silica), when the charge TMA:water ratio is 1.20:1 or less, e.g., 1.15:1, and the in situ supported MAO formation temperature is controlled to -12°C or less, the carriers are free of TMA (below the H NMR detection limit) or have a TMA concentration of 600 ppm or less (H as described in Example 22). 1The supernatant of the finished catalyst slurry can be obtained with a water content (quantified by NMR). However, the higher the water content, the lower the cooling temperature required. For example, as shown in Table 2, columns 15 and 16, for a loading of 7.8 (mmol water / g support), the sMAO formation temperature should be limited to -12°C or below. For a loading of 9.0 (mmol water / g support), the sMAO formation temperature should be controlled to -20°C or below. The data in Table 2 were generated from a catalyst prepared from a TMA concentration of approximately 20 wt% and a water-absorbed silica slurry of approximately 22 wt%, but higher or lower concentrations of the two components, such as 30 wt% to 80 wt%, or 1 wt% to 3 wt%, and a water-absorbed silica slurry of 23 wt% to 25 wt%, or 1 wt% to 10 wt%, can be used. The water-absorbed silica may also be added as a solid.

[0063] Method 4 In some in situ sMAO preparation cases, sMAO containing both supported MAO (e.g., siloxy-anchored MAO as shown in the C species of Formula 4, where C is a simplified structure introductory to a more complete understanding of the chemical) and unsupported MAO (unanchored free MAO as shown in the A species of Formula 4, where A is a simplified structure introductory to a more complete understanding of the chemical) may need to be heated to higher temperatures, e.g., 85°C, 92°C, 100°C, or 110°C, possibly to form MAO dimers and limit the soluble portion of MAO in the initiation solvent used in the slurry polymerization, avoiding leaching contamination of MAO due to the solubility of the A species in the solvent phase of the slurry polymerization medium. The heating step may cause the generation of free TMA, which is believed to occur via Formula 3. [ka] The free TMA generated by heating can be removed by adding an appropriate amount of the same water-absorbed silica used to prepare in situ sMAO, thereby reducing the overall charge TMA:water ratio. For example, under the conditions of Method 2, where the charge TMA:water is 1.42:1, adding an additional 5% water-absorbed silica to remove the free TMA released by heating can reduce the charge TMA:water ratio to, for example, 1.35:1, or even 1.31:1.

[0064] Method 5 Similar to Method 4, but instead of adding additional water-absorbed silica, calcined silica with controlled residual hydroxyls is added to remove any free TMA remaining in the supernatant after in situ sMAO formation, including any TMA generated by heating. Silica calcined at 150°C to 875°C may be used in controlled amounts to ensure that the amount of residual reactive hydroxyls on the silica matches the amount of free TMA. Raw silica can also be used, but the amount of absorbed water on the silica may be first quantified by Grignard titration or LOD (on dry material) to determine the compatibility of the active protons with TMA.

[0065] Polymerization process In at least one embodiment of the present disclosure, a method includes polymerizing an olefin to produce a polyolefin composition by contacting at least one olefin with a catalyst system of the present disclosure to obtain a polyolefin composition. The polymerization may be carried out at a temperature of from about 0° C. to about 300° C., at a pressure of from about 0.35 MPa to about 10 MPa, and / or for a time period of up to about 400 minutes. Embodiments of the present disclosure include a polymerization step in which a monomer (e.g., ethylene or propylene) and, optionally, a comonomer are contacted with a catalyst system comprising at least one catalyst compound and an activator, as described above. The at least one catalyst compound and activator may be combined in any order, and are typically combined before contact with the monomer. Slurry and gas phase polymerizations may be carried out in the presence of an aliphatic hydrocarbon solvent / diluent / condensing agent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic or alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably, aromatics are present in the solvent / diluent / condensing agent at less than 1 wt. %, preferably less than 0.5 wt. %, preferably 0 wt. %, based on the weight of the solvent / diluent / condensing agent). In a preferred embodiment, the solvent / diluent used in the polymerization is not aromatic, and preferably aromatics are present in the solvent / diluent at less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0% by weight, based on the weight of the solvent / diluent.

[0066] Monomers useful herein include substituted or unsubstituted C2-C 40 α-olefins, preferably C2 to C 20 α-olefins, preferably C2 to C 12 Alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. In a preferred embodiment, the olefin is a monomer that is propylene and one or more ethylene or C4-C6 40 Olefins, preferably C4-C 20 Olefins, or preferably C6-C 12 and one or more optional comonomers, including olefins. C4-C 40 The olefin monomers can be linear, branched, or cyclic. 40 The cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may contain one or more heteroatoms and / or one or more functional groups. In another preferred embodiment, the olefin is a monomer that is ethylene and a C3-C 40 Olefins, preferably C4-C 20 Olefins, or preferably C6-C 12 and an optional comonomer comprising one or more of the following olefins: C3 to C 40 The olefin monomers may be linear, branched, or cyclic. 40 Cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may contain heteroatoms and / or one or more functional groups. Example C2~C 40Olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentane, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentane, cyclopentane, dicyclopentadiene, norbornene, norbornadiene, and substituted derivatives thereof, preferably norbornene, norbornadiene, and dicyclopentadiene.

[0067] In at least one embodiment, the one or more dienes are present in the polymers produced herein at up to about 10 wt.%, e.g., from about 0.00001 wt.% to about 1.0 wt.%, e.g., from about 0.002 wt.% to about 0.5 wt.%, e.g., from about 0.003 wt.% to about 0.2 wt.%, based on the total weight of the composition. In at least one embodiment, not more than about 500 ppm, e.g., not more than about 400 ppm, e.g., not more than about 300 ppm, of diene is added to the polymerization. In at least one embodiment, at least about 50 ppm, or not less than about 100 ppm, or not less than 150 ppm of diene is added to the polymerization. Diolefin monomers include any hydrocarbon structure, preferably C4-C6, having at least two unsaturated bonds, where at least two of the unsaturated bonds are readily incorporated into a polymer by either stereospecific or non-stereospecific catalysis. 30and the like. More preferably, the diolefin monomer is selected from α,ω-diene monomers (i.e., di-vinyl monomers). In at least one embodiment, the diolefin monomer is a linear divinyl monomer, e.g., one containing from 4 to 30 carbon atoms. Non-limiting examples of dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacodiene, and the like. Particularly preferred dienes include 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 (Mw less than 1000 g / mol). Non-limiting examples of cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene, or higher molecular weight ring-containing diolefins with or without substituents at various ring positions. In at least one embodiment, butene is a comonomer, and the butene source may be a mixed butene stream containing various isomers of butene. 1-butene monomer is expected to be preferentially consumed in the polymerization process compared to other butene monomers. The use of such mixed butene streams may provide economic benefits, as they are often waste streams from refinery processes, e.g., C4 raffinate streams, and therefore may be substantially cheaper than pure 1-butene.

[0068] The polymerization process of the present disclosure can be carried out in any suitable manner. Suitable slurry or gas phase polymerization processes can be used. Such processes can be carried out in batch, semi-batch, or continuous modes. The preferred polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polyolefin. Typical temperatures and / or pressures include temperatures of about 0°C to about 300°C, e.g., about 20°C to about 200°C, e.g., about 35°C to about 150°C, e.g., about 40°C to about 120°C, e.g., about 65°C to about 95°C; and pressures of about 0.35 MPa to about 10 MPa, e.g., about 0.45 MPa to about 6 MPa, or preferably about 0.5 MPa to about 4 MPa. In a typical polymerization, the reaction run time is up to about 400 minutes, such as from about 5 minutes to about 250 minutes, for example, from about 10 minutes to about 120 minutes. Hydrogen may be added to the reactor to control the molecular weight of the polyolefin. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to 50 psig (0.007 kPa to 345 kPa), for example, about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), for example, about 0.1 psig to 10 psig (0.7 kPa to 70 kPa). In one embodiment, 600 ppm or less of hydrogen is added, or 500 ppm or less of hydrogen, or 400 ppm or less, or 300 ppm or less of hydrogen is added. In other embodiments, at least 50 ppm, or 100 ppm or more, or 150 ppm or more of hydrogen is added.

[0069] In an alternative embodiment, the catalyst activity is at least about 50 g / mmol / hr, such as about 500 g / mmol / hr or more, for example about 5,000 g / mmol / hr or more, such as about 750,000 g / mmol / hr or more, based on the amount of metallocene catalyst. In an alternative embodiment, the olefin monomer conversion is at least about 10%, such as about 20% or more, for example about 30% or more, such as about 50% or more, for example about 80% or more, based on the polymer yield (by weight) and the weight of monomer entering the reaction zone. Preferably, the alumoxane is present in a catalyst compound such that the molar ratio of aluminum to transition metal is less than about 500:1, such as less than about 300:1, such as less than about 100:1, such as less than about 1:1. In a preferred embodiment, little or no scavenger is used in the process for producing the polyolefin composition. Preferably, the scavenger (e.g., trialkylaluminum) is present at 0 mole %. Alternatively, the scavenger is present at a molar ratio of scavenger metal to catalyst transition metal of less than about 100:1, e.g., less than about 50:1, e.g., less than about 15:1, e.g., less than about 10:1. In a preferred embodiment, the polymerization is: 1) carried out at a temperature of 0°C to 300°C (preferably 25°C to 150°C, preferably 40°C to 120°C, preferably 45°C to 80°C); 2) carried out at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 MPa to 10 MPa, preferably 0.45 MPa to 6 MPa, preferably 0.5 MPa to 4 MPa); 3) the catalyst system used in the polymerization is a catalyst in which the alumoxane is reacted with a hydroxy group having a molar ratio of aluminum to transition metal of the catalyst compound of less than 200:1, preferably 75:1 to 160:1, preferably 90:1 to 150:1. , for example, 95:1 to 125:1; 4) the polymerization preferably occurs in one reaction zone; 5) the productivity of the catalyst compound is at least 80,000 g / mmol / h (preferably at least 150,000 g / mmol / h, preferably at least 200,000 g / mmol / h, preferably at least 250,000 g / mmol / h, preferably at least 300,000 g / mmol / h); 6) optionally, a scavenger (e.g., a trialkylaluminum compound) is not present (e.g., present at 0 mol%). Alternatively, the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1; and 8) optionally, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), preferably 0.01 psig to 25 psig (0.07 kPa to 172 kPa), more preferably 0.1 psig to 10 psig (0.7 kPa to 70 kPa). In a preferred embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone," also referred to as a "polymerization zone," is the vessel in which the polymerization occurs, e.g., a batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerizations, both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. Polymerization can occur in one or more reaction zones.

[0070] Other additives, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes, may also be used in the polymerization, if desired. The chain transfer agent may be an alkylalumoxane, a compound represented by the formula AlR3, ZnR2 (wherein each R is independently a C1-C8 aliphatic radical, preferably methyl, ethyl, propyl, butyl, penyl, hexyl, heptyl, octyl, or an isomer thereof), or a combination thereof, such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

[0071] Gas Phase Polymerization Gas-phase polymerization processes may also be used herein. Generally, in fluidized gas bed processes used to produce polymers, a gas stream containing one or more monomers is continuously cycled through a fluidized bed under reactive conditions in the presence of a catalyst. The gas stream is removed from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product is removed from the reactor and fresh monomer is added to replace the polymerized monomer. (See, e.g., U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661, and 5,668,228, all of which are incorporated herein by reference in their entireties).

[0072] Slurry Phase PolymerizationA slurry phase polymerization process may be used herein. Slurry polymerization processes are generally operated at pressures ranging from 1 to about 50 atmospheres (15 psi to 735 psi (103 kPa to 5068 kPa)) or higher, and at temperatures ranging from 0°C to about 120°C. In slurry polymerization, a suspension of solid particulate polymer is formed in a liquid polymerization diluent medium, to which monomer and comonomer are added along with a catalyst. This suspension, including the diluent, is intermittently or continuously removed from the reactor, where volatile components are separated from the polymer and recycled to the reactor, optionally after distillation. The liquid diluent used in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under the polymerization conditions. When a propane medium is used, the process should be operated above the critical temperature and pressure of the reaction diluent. Preferably, a hexane or isobutane medium is used. In another embodiment, the diluent is not aromatic, and preferably aromatics are present in the diluent at less than 1 wt. %, preferably less than 0.5 wt. %, preferably less than 0 wt. %, based on the weight of the diluent used.

[0073] Polyolefin Products The present disclosure also relates to polyolefin compositions, such as resins, made by the catalyst systems of the present disclosure. The polyolefins of the present disclosure can be free of detectable aromatic solvents. In at least one embodiment, the process utilizes the catalyst system of the present disclosure to produce propylene homopolymers or propylene copolymers, such as propylene-ethylene and / or propylene-α-olefins (preferably C3-C6), having a Mw / Mn of greater than about 1, e.g., greater than about 2, e.g., greater than about 3, e.g., greater than about 4. 20 ) copolymers (e.g., propylene-hexene copolymers or propylene-octene copolymers). In at least one embodiment, a process involves utilizing the catalyst system of the present disclosure to produce olefin polymers, preferably homopolymers and copolymers of polyethylene and polypropylene. In at least one embodiment, the polymers produced herein are homopolymers of ethylene or copolymers of ethylene, preferably containing from about 0 mol % to 25 mol % of one or more C3-C6 olefins. 20 The olefin comonomer (e.g., about 0.5 mol % to 20 mol %, e.g., about 1 mol % to about 15 mol %, e.g., about 3 mol % to about 10 mol %) is C3 to C6 12 The olefin monomer may be one or more of an α-olefin, such as propylene, butene, hexene, octene, decene, or dodecene, preferably propylene, butene, hexene, or octene. The olefin monomer may be ethylene or a C4-C6 12 It may be one or more of an α-olefin, preferably ethylene, butene, hexene, octene, decene, or dodecene, preferably ethylene, butene, hexene, or octene. The polymers produced herein may have a Mw of about 5,000 g / mol to about 1,000,000 g / mol (e.g., about 25,000 g / mol to about 750,000 g / mol, e.g., about 50,000 g / mol to about 500,000 g / mol), and / or a Mw / Mn of about 1 to about 40 (e.g., about 1.2 to about 20, e.g., about 1.3 to about 10, e.g., about 1.4 to about 5, e.g., about 1.5 to about 4, e.g., about 1.5 to about 3), as measured by GPC-4D as described in the Experimental Section below. The polyolefins produced herein contain 0 ppm aromatic hydrocarbons. Preferably, the polyolefins produced herein contain 0 ppm toluene.

[0074] Experimental materials Chemicals: Trimethylaluminum was purchased from Sigma Aldrich (St. Louis, MO) or AkzoNobel (now Nouryon) and used as received unless otherwise noted. Spray-dried silica ES70™ was purchased from PQ Corporation (now Ecovyst), and non-spray-dried silica DM-L403 was purchased from AGC Chemicals. ES70X and ES70 are ES70™ silicas calcined at either 200°C, 400°C, or 875°C for 4 hours. DM-L 403 silica is calcined at 200°C for 4 hours. Silica parameters provided by the suppliers are summarized below: [Table 1]

[0075] Isohexane (in-house plant-grade solvent) and heptane (purchased from Sigma-Aldrich, anhydrous grade) were sparged with dry N2 and then stored with activated 3 Å molecular sieves in a container containing 5% to 10% by weight of molecular sieves at least overnight before use. Water used was lab deionized water. All reactions were performed under an inert nitrogen atmosphere unless otherwise noted. All deuterated solvents were obtained from Cambridge Isotopes (Cambridge, MA) and dried over 3 Å molecular sieves before use. Apparatus: Ace Glass 600 mL and 4 L jacketed filter reactors fitted with Lauda chillers using Kryo 20 coolant capable of controlling the temperature range from -30° C. to 150° C. The water-absorbed silica slurry was charged to the well-sealed 600 mL reactor and metered into the 4 L reactor through Teflon tubing, with the addition rate controlled by positive pressure N2 via a needle valve. TMA residues in the supernatant were investigated using in situ supported MAO silica calcined at 200°C, 400°C, or 875°C with water loadings ranging from 4.3 to 9.1 mmol / g and charge TMA:water ratios ranging from 12.7:1 to 1.31:1 (Table 2). Three metallocene catalyst precursor compounds representing different ligand structures and different metal centers were used to prepare finished catalysts for activity comparison: unbridged zirconocene bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (M1); bridged zirconocene dimethylsilyl-bis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl (M2); and unbridged hafnocene bis(propylcyclopentadienyl)hafnium dimethyl (M3). M1 exhibits excellent solubility in aliphatic solvents, whereas the M2 and M3 dichloride forms are significantly less soluble. These methylated forms are used because of their high solubility in the preferred aliphatic solvents. [Table 2] JPEG2025525402000020.jpg72163 1 The reference catalysts were M1, M2, and M3 metallocenes supported on the same silica-derived supported MAO standard (WR Grace, 30% MAO solution in toluene) with an MAO loading of 6.2 mmol Al / g silica, giving activities of 2,912, 3,389, and 6,294 g / gcat / hr, respectively; 2 Before heating, heat is applied to a solid.

[0076] Example 1 (M3, ES70 silica calcined at 400°C, in situ sMAO solid heated at 92°C) 1. In a drybox, three bottles (1 L volume) were each charged with 100 g of silica ES70 (400°C), 360 g of isohexane, and 11.7 g of water. The three bottles, containing a total of 300 g of silica, 1080 g of isohexane, and 35.1 g (1.95 mol) of water, were capped and tightly sealed with electrical tape. The three bottles were removed from the drybox and placed on a roller set at 80 rpm for two hours. After two hours, the three bottles were returned to the drybox. 2.760 g of dry isohexane (3A molecular sieves, overnight) was charged to a 4 L reactor equipped with an anchor impeller. The Lauda chiller temperature controller was set to -30°C and turned on. The agitator was turned on and set to 170 rpm. 3. After the isohexane had cooled to -1°C, the filter cap at the bottom of the reactor was checked to ensure there were no leaks, and 184.2g (2.55 moles) of neat TMA was added to the reactor. The TMA:water ratio was 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, one of the three bottles of water-absorbed silica slurry was transferred to a 600 mL reactor, cooled to approximately -5°C, and stirred to ensure good mixing. 5. After the TMA solution temperature reached -15°C, the addition of water-absorbed silica was started at 250 rpm at a rate that maintained the reaction temperature between -9°C and -12°C. 6. After addition of the silica slurry, the agitation was adjusted to 170 rpm and the jacket temperature was increased to 1° C. and held for 30 minutes before being allowed to reach ambient conditions. 7. The stirring was stopped and the solvent was removed under vacuum through the bottom filter of the reactor. 1 H-NMR spectra obtained in THF-d8 (deuterated tetrahydrofuran) showed no MAO or TMA. 8. The wet solids were dried in a 4 L jacketed filter reactor at ambient conditions for 2 hours, then heated to 100° C. for 4 hours at a solid temperature of 92° C. Yield: 441.5 g. 9. 1.0 g of the sMAO obtained above was slurried with 4 g of isohexane in a 20 mL vial, and then 19.0 mg of M3 metallocene was added. 10. The slurry was placed in a shaker, shaken for 1 hour, filtered through a frit, and then vacuum dried for 1 hour. Yield: 1.0 g. The catalyst was tested for gas-phase ethylene polymerization in a 2 L autoclave salt bed reactor using the procedure described in Example 22.

[0077] Example 2 (M3, 200°C calcined ES70 silica, in situ sMAO slurry heated at 92°C) 1. In a drybox, three bottles (1 L volume) were each charged with 100 g of silica ES70 (200°C), 360 g of heptane, and 11.7 g of water. The three bottles, containing a total of 300 g of silica, 1080 g of heptane, and 35.1 g (1.95 mol) of water, were capped and tightly sealed with electrical tape. The three bottles were removed from the drybox and placed on a roller set at 80 rpm for two hours. After two hours, the three bottles were returned to the drybox. 2.760 g of dry heptane (3A molecular sieves, overnight) was charged to a 4 L reactor equipped with an anchor impeller. The Lauda chiller temperature controller was set to -30°C and turned on. The agitator was turned on and set to 170 rpm. 3. After the heptane was cooled to -1°C, the filter cap at the bottom of the reactor was checked to ensure there were no leaks, and 184.2g (2.55 moles) of neat TMA was added to the reactor. The TMA:water ratio was 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, one of the three bottles of water-absorbed silica slurry was transferred to a 600 mL reactor, cooled to approximately -5°C, and stirred to ensure good mixing. 5. After the TMA solution temperature reached -15°C, the addition of water-absorbed silica was started at 250 rpm at a rate that maintained the reaction temperature between -9°C and -12°C. 6. After addition of the silica slurry, the agitation was adjusted to 170 rpm and the jacket temperature was increased to 1° C. and held for 30 minutes before being allowed to reach ambient conditions. 7. Stop stirring and allow the solid to settle. 1 H-NMR spectra obtained in THF-d8 (deuterated tetrahydrofuran) showed no MAO or TMA. 8. The agitator was turned back on and set to 170 rpm, and then the heater was set to 96°C to heat the slurry to a reaction temperature of 92°C to 93°C, which was maintained for 4 hours. 9. After heating, the slurry was cooled to 25°C, the agitator was increased to 300 rpm, and 8.45g of M3 metallocene was added. 10. After adding M3, the stirrer was slowed down to 170 rpm and stirred for 2 hours. 11. The slurry was filtered, washed with 2 x 1 L isohexane and dried under vacuum at ambient temperature overnight. Yield: 445.5 g. The catalyst was tested for gas phase ethylene polymerization in a 2 L autoclave salt bed reactor using the procedure described in Example 22.

[0078] Example 3 (M3, ES70 silica calcined at 200°C, in situ sMAO slurry heated at 65°C) 1. In a drybox, three bottles (1 L volume) were each charged with 100 g of silica ES70 (200°C), 360 g of heptane, and 11.7 g of water. The three bottles, containing a total of 300 g of silica, 1080 g of heptane, and 35.1 g (1.95 mol) of water, were capped and tightly sealed with electrical tape. The three bottles were removed from the drybox and placed on a roller set at 80 rpm for two hours. After two hours, the three bottles were returned to the drybox. 2.715 g of dry heptane (3A molecular sieves, overnight) was charged to a 4 L reactor equipped with an anchor impeller. The Lauda chiller temperature controller was set to -30°C and turned on. The agitator was turned on and set to 200 rpm. 3. After the heptane was cooled to -1°C, the filter cap at the bottom of the reactor was checked to ensure there were no leaks, and 184.2g (2.55 moles) of neat TMA was added to the reactor. The TMA:water ratio was 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, one of the three bottles of water-absorbed silica slurry was transferred to a 600 mL reactor, cooled to approximately -5°C, and stirred to ensure good mixing. 5. After the TMA solution temperature reached -15°C, the addition of water-absorbed silica was started at 300 rpm at a rate that maintained the reaction temperature between -9°C and -12°C. 6. After addition of the silica slurry, the agitation was adjusted to 200 rpm and the jacket temperature was increased to 1° C. and held for 30 minutes before being allowed to reach ambient conditions. 7. The heater was set to 68°C to heat the slurry to a reaction temperature of approximately 65°C and maintained for 4 hours. 8. The temperature was then allowed to drop to ambient temperature (approximately 21°C). The agitator was turned off and the solids were allowed to settle. 1 H-NMR spectra obtained in THF-d8 (deuterated tetrahydrofuran) showed no MAO or TMA. 9. The agitator was turned on and set to 60 rpm and stirred overnight. 10. The agitator was increased to 300 rpm and 8.84 g of M3 metallocene was added. 11. After adding M3, the stirrer was slowed down to 200 rpm and stirred for 2 hours. 12. The slurry was filtered, washed with 2 x 1 L isohexane and dried under vacuum at ambient temperature overnight. Yield: 459 g. The catalyst was tested for gas phase ethylene polymerization in a 2 L autoclave salt bed reactor using the procedure described in Example 22.

[0079] Example 4 (M3, 400°C calcined ES70 silica, in situ sMAO slurry heated at 92°C) 1. In a drybox, three bottles (1 L volume) were each charged with 100 g of silica ES70 (400°C), 360 g of heptane, and 11.7 g of water. The three bottles, containing a total of 300 g of silica, 1080 g of heptane, and 35.1 g (1.95 mol) of water, were capped and tightly sealed with electrical tape. The three bottles were removed from the drybox and placed on a roller set at 80 rpm for two hours. After two hours, the three bottles were returned to the drybox. 2.700 g of dry heptane (3A molecular sieves, overnight) was charged to a 4 L reactor equipped with an anchor impeller. The Lauda chiller temperature controller was set to -30°C and turned on. The agitator was turned on and set to 200 rpm. 3. After the heptane was cooled to -1°C, the filter cap at the bottom of the reactor was checked to ensure there were no leaks, and 184.2g (2.55 moles) of neat TMA was added to the reactor. The TMA:water ratio was 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, one of the three bottles of water-absorbed silica slurry was transferred to a 600 mL reactor, cooled to approximately -5°C, and stirred to ensure good mixing. 5. After the TMA solution temperature reached -15°C, the addition of water-absorbed silica was started at 300 rpm at a rate that maintained the reaction temperature between -9°C and -12°C. 6. After addition of the silica slurry, the agitation was adjusted to 200 rpm and the jacket temperature was increased to 1° C. and held for 30 minutes before being allowed to reach ambient conditions. 7. The heater was set to 96°C to heat the slurry to a reaction temperature of 92°C-93°C, which was maintained for 4 hours. 8. The temperature was then allowed to drop to ambient temperature (approximately 21°C). The agitator was turned off and the solids were allowed to settle. 1 A 1 H-NMR spectrum was acquired in THF-d8 (deuterated tetrahydrofuran) and showed TMA at 170 ppm. 9. The agitator was turned on and set to 60 rpm and stirred overnight. 10. The agitator was increased to 300 rpm and 8.45 g of M3 metallocene was added. 11. After adding M3, the stirrer was slowed down to 200 rpm and stirred for 2 hours. 12. The slurry was filtered, washed with 2 x 1 L isohexane and dried under vacuum at ambient temperature overnight. Yield: 458.8 g. The catalyst was tested for gas phase ethylene polymerization in a 2 L autoclave salt bed reactor using the procedure described in Example 21.

[0080] Example 5 (M3, 200°C calcined ES70X silica, in situ sMAO slurry heated at 92°C) 1. In a drybox, three bottles (1 L volume) were each charged with 100 g of silica ES70X (200°C), 360 g of heptane, and 11.7 g of water. The three bottles, containing a total of 300 g of silica, 1080 g of heptane, and 35.1 g (1.95 mol) of water, were capped and tightly sealed with electrical tape. The three bottles were removed from the drybox and placed on a roller set at 80 rpm for two hours. After two hours, the three bottles were returned to the drybox. 2.760 g of dry heptane (3A molecular sieves, overnight) was charged to a 4 L reactor equipped with an anchor impeller. The Lauda chiller temperature controller was set to -30°C and turned on. The agitator was turned on and set to 170 rpm. 3. After the isohexane had cooled to -1°C, the filter cap at the bottom of the reactor was checked to ensure there were no leaks, and 184.2g (2.55 moles) of neat TMA was added to the reactor. The TMA:water ratio was 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, one of the three bottles of water-absorbed silica slurry was transferred to a 600 mL reactor, cooled to approximately -5°C, and stirred to ensure good mixing. 5. After the TMA solution temperature reached -15°C, the addition of water-absorbed silica was started at 250 rpm at a rate that maintained the reaction temperature between -9°C and -12°C. 6. After addition of the silica slurry, the agitation was adjusted to 170 rpm and the jacket temperature was increased to 1° C. and held for 30 minutes before being allowed to reach ambient conditions. 7. The heater was set to 96°C to heat the slurry to a reaction temperature of 92°C-93°C, which was maintained for 5 hours. 8. The reaction temperature was allowed to drop to ambient temperature. Stirring was stopped and the solid was allowed to settle. 1 A 1 H-NMR spectrum was acquired in THF-d8 (deuterated tetrahydrofuran) and showed TMA at 270 ppm. 9. The agitator was turned back on and set to 170 rpm and 8.63 g of M3 catalyst precursor compound was added all at once and the slurry was stirred for 2 hours. 10. The slurry was then filtered, washed with 2 x 1 L isohexane and dried under vacuum at ambient temperature overnight. Yield: 471.5 g. The catalyst was tested for gas phase ethylene polymerization in a 2 L autoclave salt bed reactor using the procedure described in Example 21.

[0081] Examples 6 to 21 Preparation of Finished Catalysts from Silica with Different Calcination Temperatures and Water Contents, and from M1 and M2 Metallocenes Finished catalysts were prepared in Examples 6 to 15 and 17 to 21 using the same procedure as in Example 5, and in Example 16 using the same procedure as in Example 1, with the modifications shown in Table 3. [Table 3] JPEG2025525402000022.jpg70164 1 The reference catalysts were M1, M2, and M3 metallocenes supported on the same silica-derived supported MAO standard (WR Grace, 30% MAO solution in toluene) with an MAO loading of 6.2 mmol Al / g silica, giving activities of 2,912, 3,389, and 6,294 g / gcat / hr, respectively; 2Silica and water were charged into a 2 L round-bottom flask and tightly sealed with a rubber septum and electrical tape; the round-bottom flask was placed on a balance and the weight was recorded, and then placed in an oven set at 55°C and heated for 5 hours; the flask was removed from the oven, cooled to ambient temperature, and reweighed to ensure no significant weight loss, after which the solvent was added and mixed well; the slurry was then divided into three equal portions and added to a 600 mL jacketed reactor.

[0082] Example 22 (Polymerization test) In a lab-scale 2 L salt-bed gas-phase polymerization reactor, a 2 L autoclave reactor was heated to 110 °C and purged with N2 for at least 30 minutes. Dry NaCl (350 g; Fisher, S271-10, dehydrated at 180 °C, passed through a pump / purge cycle, and finally passed through a 16-mesh screen before use) and TIBAL-treated silica (5 g at 105 °C) were charged and stirred for 30 minutes. The temperature was adjusted to 85 °C. Dry, degassed 1-hexene (C6 = (See Table 4 for different amounts of each catalyst) was added to the reactor via syringe and the reactor was charged with N2 to a pressure of 20 psig. A mixture of H2 and N2 was flowed through the reactor while stirring the bed (see Table 4 for precharge H2; 10% H2 in N2 as used). The catalysts shown in Table 4 below were used in a 220 psig pressure reactor for ethylene (C2 = ) was injected into the reactor. In order to maintain a constant pressure in the reactor, C2 = I always played it while driving. C6 = was fed to the reactor at the ratio to ethylene shown in Table 4. H2 was fed to the reactor at the ratio to C2 shown in Table 4. = The ratio of H2 and C2 = The ratio of was determined by online GC analysis. After 1 hour, the polymerization was stopped by venting the reactor, cooling it to about 23°C, and exposing it to air. The salts were removed by washing twice with water. The polymer was isolated by filtration, washed briefly with acetone, and dried in air for at least 2 days. The catalyst activity is reported in Table 2 above. [Table 4]

[0083] Example 23 (H for quantifying the TMA content in the supernatant 1 -NMR method) A 5 mm NMR tube is charged with approximately 0.5 inches of the supernatant of interest and approximately 1 inch of THF-d8. The mixture is mixed well. H is measured on a Brucker 400 MHz instrument using ns=8 and D1=1 s. 1 NMR spectra are taken. Solvent peaks including CH3, CH2, and CH1 signals (region from about 0.3 ppm to about 2.5 ppm, including the THF-d8 peak at 1.73 ppm (minimum, not subtracted)) and TMA (sharp singlet peak between -0.9 and -1.0 ppm) are integrated, and the solvent integral is set to 1400 (iC6, 14H) or 1600 (heptane, 16H). If the integral of TMA is x, the TMA concentration y is calculated as follows: For iC6 solvent, y = (72.1 * x / 9) / (72.1 * x / 9+86.2 * 100) For heptane solvent, y = (72.1 * x / 9) / (72.1 * x / 9+100.2 * 100) For example, no TMA was detected in Example 3, but an integral of 0.21 of TMA was detected in Example 4. Therefore, the concentration y in heptane is as follows: y=72.1 * 0.21 / 9 / (72.1 * 0.21 / 9+100.2 * 100) = 0.000168 or 168 ppm The figure shows the spectra of the TMA of Examples 3 and 4.

[0084] Example 24 (Standard catalyst preparation from standard supported MAO) 10.0 g of ES70X (calcined at 600°C) or ES70 (calcined at 875°C) silica was added to a 100 mL stirred cell reactor along with 40 g of toluene. To this slurry, 12.4 g (13.5 wt% or 62.0 mmol Al based on Al in the 5.0 mmol / g MAO solution) of W.R. Grace's 30% solution in toluene was slowly added. After MAO addition, the mixture was stirred at ambient conditions for 1 hour. The solid-supported MAO was isolated by filtration through a frit, washed with 2 x 40 g of iC6, and dried under vacuum for 2 hours. Yield: 13.9 g. M1 Finished Catalyst (sMAO on ES70X (600°C)): 2.0 g of sMAO obtained from the above procedure was charged to a 20 mL vial, followed by 8 g of toluene. 35 mg (40 μmol / g sMAO) of M1 was mixed with this slurry and shaken on a shaker for 1 h. The solid supported catalyst was isolated by filtration through a frit, washed with 2 × 10 g of iC6, and vacuum dried for 1 h. Yield: 2.0 g M2 Finished Catalyst (sMAO on ES70X (600°C)): 2.0 g of sMAO obtained from the above procedure was charged to a 20 mL vial, followed by 8 g of toluene. 33 mg (35 μmol / g sMAO) of M2 was mixed with this slurry and shaken on a shaker for 1 h. The solid supported catalyst was isolated by filtration through a frit, washed with 2 × 10 g of iC6, and vacuum dried for 1 h. Yield: 2.0 g M3 Finished Catalyst (sMAO on ES70 (875°C)): 2.0 g of sMAO obtained above was charged to a 20 mL vial, followed by 8 g of toluene. 38 mg (45 μmol / g sMAO) of M3 was mixed with this slurry and shaken for 1 h. The solid supported catalyst was isolated by filtration through a frit, washed with 2 x 10 g of iC6, and dried under vacuum for 1 hour. Yield: 2.0 g

[0085] All documents cited herein, including any priority documents and / or testing procedures, are incorporated herein by reference to the extent they do not contradict this document. While several embodiments have been illustrated and described, as is apparent from the foregoing general description and specific embodiments, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, no limitation of the present disclosure is intended. Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever a composition, element, or group of elements precedes the transitional phrase "comprising," it is understood that the inventors also contemplate the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" preceding the recitation of the composition, element, or group of elements, and vice versa.

Claims

1. 1. A method for preparing a catalyst system comprising: contacting at least one support material having absorbed water with trimethylaluminum (TMA) in an organic solvent to form a supported MAO (catalyst precursor) in situ; contacting the supported MAO with at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom; the charge TMA to water ratio and the in situ MAO formation temperature are controlled so that the supernatant after the in situ supported MAO formation, with optional heating, or after finished catalyst formation contains no detectable TMA or contains 600 ppm or less of TMA, with the proviso that: a. For supports containing less than 6.5 (mmol / g support) absorbed water, the charge TMA:water ratio is controlled in the range of 1.31:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; b. For supports containing less than 5.0 mmol / g of absorbed water, the charge TMA:water ratio is controlled in the range of 1.42:1 to 1.25:1, and the in situ supported MAO formation temperature is controlled between -8°C and -60°C; and c. For supports containing 7.0-10.0 (mmol / g support) of absorbed water, the charge TMA:water ratio is controlled in the range of 1.20:1 to 1.15:1, and the in situ supported MAO formation temperature is controlled between -12°C and -60°C; method.

2. 1. A method for preparing a catalyst system comprising: contacting at least one support material having absorbed water with trimethylaluminum (TMA) in an organic solvent to form a supported MAO (catalyst precursor) in situ; contacting the supported MAO with at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom. the TMA to water ratio is 1.80:1 to 1.42:1, and the in situ supported MAO formation temperature is -6°C to -60°C; The step of recovering free TMA from the supernatant after the in situ supported MAO formation or the finished catalyst formation is eliminated by adding a second support containing a hydroxy group to the supernatant to eliminate detectable TMA in the supernatant or reduce the TMA content to 600 ppm or less. method.

3. 3. The method of claim 2, wherein the second support containing hydroxy groups is the same or different water-absorbed silica as used in making the in situ sMAO or the derived finished catalyst.

4. 3. The method of claim 2, wherein the support containing hydroxy groups is silica calcined at 150°C to 875°C.

5. 5. The method of claim 1, wherein the at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom comprises at least one substituted or unsubstituted cyclopentadienyl ligand to form a bridged or unbridged half-metallocene or metallocene.

6. 5. The method of claim 1, wherein the at least one catalyst precursor compound having a Group 3 to Group 12 metal atom or a Lanthanide metal atom comprises at least one organic ligand having at least two heteroatom donors.

7. 7. The method of claim 6, wherein the at least one organic ligand having at least two heteroatom donors comprises an oxygen, nitrogen, or phosphorus donor.

8. A method for producing a polyolefin product, comprising the step of polymerizing an olefin by contacting said olefin with the catalyst system produced by the method of any one of claims 1 to 6.

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