Low cost process for in situ MAO loading and derived finished polyolefin catalyst

Abstract

The present disclosure provides a process for preparing a catalyst system, comprising contacting at least one water-absorbing support material with trimethylaluminum (TMA) in an organic solvent at a temperature of less than-6 DEG C to-60 DEG C to form a supported MAO (catalyst precursor) in situ and contacting the supported MAO with at least one catalyst precursor compound having Group (3) to (12) metal atoms or lanthanide series metal atoms, wherein the ratio of TMA to water and the in situ sMAO formation temperature are controlled such that after in situ supported MAO formation and optionally heating or after finished catalyst formation, the supernatant does not contain NMR detectable TMA or contains no more than 500 ppm TMA.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 355,250, filed June 24, 2022, the disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to methods of producing polyolefin catalyst systems that improve catalyst operability in slurry or gas phase polyolefin reactors and reduce the production cost of the catalyst system. Background Art

[0004] Polyolefins are widely used commercially due to their robust physical properties. For example, various types of polyethylene, including high density, low density and linear low density polyethylene are some of the most useful commercially. Polyolefins are typically prepared using a catalyst (mixed with one or more other components to form a catalyst system) that promotes polymerization of olefin monomers in a reactor (e.g., a gas phase reactor).

[0005] Methylaluminoxane, or MAO, is the most popular activator supported on silica for activating single site catalyst precursors (eg, metallocenes) to form active solid catalysts for the production of single site polyolefin resins in commercial gas phase reactors.

[0006] Commercial MAO is usually sold as a toluene solution because aromatic solvents can dissolve MAO to form a homogeneous solution without causing any of the problems observed when using other solvents, such as solvents containing donors (e.g., ethers or THF) deactivating MAO, solvents containing active protons (e.g., alcohols) reacting with MAO and destroying it, and aliphatic solvents (e.g., hexane) precipitating MAO. However, MAO toluene solutions are thermally unstable and need to be stored in a cold environment (e.g., -20°C to -30°C) to reduce the gelation process usually observed for this kinetic product in order to provide a more homogeneous (i.e., less gelled) MAO solution within a given period of time (e.g., about 3 months). Even under cooling, MAO molecules will begin to dimerize / oligomerize immediately after preparation to eventually form an insoluble gel. MAO products with different storage ages (e.g., 1 month vs. 3 months stored at -20°C) may therefore have significantly different molecular compositions, with the fresher one having a greater number of MAO molecules and smaller sizes, and the longer storage one having a smaller number of MAO molecules and larger sizes due to the gelation process. It is highly desirable to obtain MAO molecules with a lower gel content and thus more uniformly distributed in the pores of the catalyst support material (e.g., silica) to obtain a catalyst with good properties including good productivity and good operability. In addition, polyolefin products are often used as plastic packaging for sensitive products, and the amount of non-polyolefin compounds (e.g., toluene) present in the polyolefin product should be minimized.

[0007] US11,161,922 shows that MAO can be prepared in situ on a support (e.g., silica) by adding water-treated silica to a cold trimethylaluminum (TMA) solution. It has been found that once the MAO molecules are loaded (fixed on the pore surface), their gelation process is almost completely blocked because the MAO molecules cannot move to contact and dimerize. In situ loaded MAO (sMAO) therefore does not need to be stored at a cold temperature and the sMAO produced can maintain the ratio of macromolecules to small molecules and the total number of MAO molecules to provide more consistent performance during the storage period. The formation of in situ sMAO does not require aromatic solvents.

[0008] It has been experimentally demonstrated that active MAO compositions freshly prepared from the reaction of TMA under cooling contain coordinated TMA (TMA c ), for example, (Al 4 O 3 Me 6 ) 4 (TMA c ) n(n=1 or 2) (Sinn et al., "Formation, Structure, and Mechanism of Oligomeric Methylaluminoxane", in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, p. 105). TMA in MAO c It has been confirmed that it plays the role of AlMe in MAO 2 + The main active site of the precursor, the AlMe 2 + is the actual active substance (Luo, Jain, and Harlan, ACS Annual Meeting, Conference Abstracts PMSE 126 and INOR 1169, April 2-6, 2017). Related references include: U.S. Patent Nos. 8,354,485; 9,090,720; 7,910,764; 8,575,284; 8,575,284; 5,006,500; 4,937,217; U.S. Patent Publication No. 2016 / 0355618; and WO 2016 / 170017. In order to maximize the TMA on sMAO in situ c , using the MAO formula (Al 4 O 3 Me 6 ) 4 (TMA c ) 2 The ratio of TMA to water is at least 1.5:1 with an Al:O ratio (US 11,161,922). f With TMA c 1), such a ratio generally yields free TMA remaining in the supernatant (TMA f ).

[0009]

[0010] The remaining TMA in the supernatant f Need to be removed by filtration and washed with solution to avoid fouling of the polymerization reactor, which is presumably due to TMA f A neutral catalyst precursor (such as a neutral metallocene present in an equilibrium activation process) reacts with sMAO to form an unsupported, soluble, low activity species (Equation 2):

[0011] Summary of the invention

[0012] The 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 at a controlled ratio of TMA to water in an organic solvent at a temperature of -6°C to -60°C. Thus, a supernatant containing no free TMA or a low free TMA content is obtained. This eliminates the need for filtering and washing steps to simplify the finished catalyst production equipment / facility and the solid finished catalyst separation and drying process (e.g., using simple heating and / or vacuum drying). This also allows the solvent to be either directly reused in a continuous catalyst production process or disposed of normally without further treatment. The resulting finished catalyst also exhibits excellent reactor operability under both gas phase and slurry phase polymerization conditions.

[0013] Exemplary embodiments described herein relate to a method of preparing a catalyst system, comprising contacting at least one support material having absorbed water with TMA at a controlled ratio of TMA to water in an organic solvent at a temperature of -6°C to -60°C to form supported MAO 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. The supported MAO may be heated prior to contacting with the catalyst compound.

[0014] Exemplary embodiments described herein are directed to catalyst systems comprising a catalyst compound having a metal atom of Group 3 to Group 12 or a lanthanide series metal atom. The catalyst system further comprises an in-situ supported MAO and has no detectable amount of aromatic solvent when only aliphatic solvents are used. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The accompanying figure provides a graph comparing the TMA content in Examples 3 and 4. DETAILED DESCRIPTION

[0016] For catalyst preparation facilities without filtering and washing capabilities, free TMA cannot be removed; and even with filtering and washing capabilities, the remaining free TMA in the supernatant complicates waste solvent disposal, for example, requiring procedures to deactivate the free TMA prior to normal disposal processes.

[0017] Therefore, it is desirable to obtain a supported finished catalyst without free TMA in the supernatant, or at least in a concentration so low as not to cause any significant polymerization reactor operating problems and to allow direct reuse of the solvent as is.

[0018] The present disclosure relates to a method for preparing a catalyst system to obtain a supernatant free of TMA or low in TMA, to enable a simple catalyst preparation facility without filtering and washing capabilities to produce a dry finished catalyst system with good polymerization reactor operability and directly reuse the solvent used for in-situ supported MAO formation and / or its derived finished catalyst formation. An embodiment of the present disclosure includes a method for preparing an in-situ supported MAO, which includes 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 at a controlled feed Al:water ratio to obtain a supernatant free of free TMA or low in free TMA. The supported MAO is formed in situ when TMA reacts with absorbed water on silica, wherein based on the absorbed water content, TMA and absorbed water on the support are controlled at different ratios and the in-situ supported MAO formation temperature is controlled in different ranges, provided that:

[0019] a. For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0020] b. For a carrier containing 5.0 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0021] c. For supports containing 7.0-10.0 (mmol / g support) of absorbed water, the feed TMA:water ratio was controlled in the range of 1.20:1 to 1.15:1 and the in situ sMAO formation temperature was controlled in the range of -12°C to -60°C.

[0022] Alternatively, to obtain a supernatant free of free TMA or with a low free TMA content, the feed TMA to water ratio is controlled at 1.80:1 to 1.42:1 and the in-situ supported MAO formation temperature is controlled at -6°C to -60°C, and then after the in-situ supported MAO is formed or after the finished catalyst is formed, free TMA is removed from the supernatant by adding a second support containing hydroxyl groups to the supernatant, wherein the support containing hydroxyl groups can be a support containing absorbed water or a support containing pore surface hydroxyl groups, such as silica calcined at 150°C, 200°C, 400°C or higher.

[0023] The present disclosure also includes a method for preparing a catalyst system, including a heating step of the in-situ loaded MAO before contacting the in-situ loaded MAO with a catalyst precursor compound. The catalyst precursor compound has a metal atom from Group 3 to Group 12 or a lanthanide metal atom. The catalyst precursor compound can be a metallocene catalyst compound containing a Group 4 metal. Any organic solvent can be used, including aliphatic solvents to obtain a finished catalyst system that does not contain (cannot detect) aromatic compounds.

[0024] In at least one embodiment, the present disclosure is directed to a continuous process 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 to produce in situ supported MAO and a supported MAO derived finished catalyst, wherein the absorbed water and TMA on the support are controlled to have:

[0025] a. For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0026] b. For a carrier containing 5.0 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0027] c. For a carrier containing 7.0-10.0 (mmol / g carrier) of absorbed water, the feed TMA: water ratio is in the range of 1.20:1 to 1.15:1 and the in situ sMAO formation temperature is controlled at -12°C to -60°C; and

[0028] The in situ supported MAO or the derived finished catalyst is separated from the organic solvent (ie, supernatant) which can be reused as a solvent without further treatment.

[0029] The present disclosure also relates to a process for polymerizing olefins to produce a polyolefin composition comprising contacting at least one olefin with a catalyst system prepared as described herein and obtaining a polyolefin containing no detectable aromatic hydrocarbon solvents by using one or more aliphatic solvents (e.g., pentane, isohexane and / or heptane) in an in situ supported MAO formation and derivatization finished catalyst preparation process.

[0030] The present disclosure also relates to a method of preparing a catalyst system comprising 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 to form supported MAO, wherein the absorbed water and TMA on the support are controlled to have:

[0031] a. For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0032] b. For a carrier containing 5.0 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0033] c. For a carrier containing 7.0-10.0 (mmol / g carrier) of absorbed water, the feed TMA: water ratio is in the range of 1.20:1 to 1.15:1 and the in situ sMAO formation temperature is controlled at -12°C to -60°C; and

[0034] The supported MAO is heated to at least 50°C and up to 140°C and then contacted with at least one catalyst precursor compound to form a finished catalyst comprising Group 3 to Group 12 metal atoms or lanthanide metal atoms.

[0035] The present disclosure also relates to a method of preparing a catalyst system comprising 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 to form an in-situ supported MAO, wherein the absorbed water and TMA on the support are controlled to have:

[0036] a. For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0037] b. For a carrier containing 5.0 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0038] c. For a carrier containing 7.0-10.0 (mmol / g carrier) of absorbed water, the feed TMA: water ratio is in the range of 1.20:1 to 1.15:1 and the in situ sMAO formation temperature is controlled at -12°C to -60°C; and

[0039] The supported MAO is contacted with at least one catalyst precursor compound comprising a Group 3 to Group 12 metal atom or a lanthanide metal atom to form a supported catalyst system and the supported catalyst system is heated to at least 50°C and up to 100°C.

[0040] The present disclosure also relates to a method for preparing in situ supported MAO in at least one organic solvent, comprising adding at least one support material having absorbed water as a solid or in the form of a slurry to a TMA organic solvent solution at a temperature in the range of -8°C to -60°C, wherein the absorbed water and TMA on the support are controlled to have:

[0041] a. For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0042] b. For a carrier containing 5.0 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0043] c. For supports containing 7.0-10.0 (mmol / g support) of absorbed water, the feed TMA:water ratio was in the range of 1.20:1 to 1.15:1 and the in situ sMAO formation temperature was controlled at -12°C to -60°C.

[0044] The present disclosure also relates to a method of preparing an in situ supported MAO and a derived finished catalyst free of aromatic solvents, comprising adding at least one support material having absorbed water, as a solid or as an aliphatic solvent slurry, to a TMA aliphatic solvent solution at a temperature in the range of -8°C to -60°C, wherein the absorbed water on the support and the TMA are controlled to have:

[0045] a. For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0046] b. For a carrier containing 5.0 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C; or

[0047] c. For supports containing 7.0-10.0 (mmol / g support) of absorbed water, the feed TMA:water ratio was in the range of 1.20:1 to 1.15:1 and the in situ sMAO formation temperature was controlled at -12°C to -60°C.

[0048] The present disclosure also relates to a method for preparing in situ supported MAO and a derived finished catalyst free of aromatic solvents, comprising adding at least one support material having absorbed water, as a solid or as an aliphatic solvent slurry, to a TMA aliphatic solvent solution at a temperature in the range of -6°C to -60°C, wherein the ratio of feed TMA to water is controlled at 1.80:1 to 1.42:1, and then removing free TMA from the supernatant after the in situ supported MAO is formed or after the finished catalyst is formed, by adding a second support containing hydroxyl groups to the supernatant, wherein the support containing hydroxyl groups can be a support containing absorbed water or a support containing pore surface hydroxyl groups, such as silica calcined at a temperature of 150°C, 200°C, 400°C or higher.

[0049] The present disclosure also relates to any of the methods described herein, wherein the TMA solution concentration is from 0.1 wt % to 40 wt %, preferably from 1.0 wt % to 20 wt %.

[0050] The present disclosure also relates to such processes wherein the process is continuous and includes separation of solid supported MAO or derived finished catalyst product and recycling of organic solvent without additional treatment.

[0051] The present disclosure also relates to any of the methods described herein, wherein the supported MAO composition formed in situ is additionally heat treated at a temperature selected from 50°C to 140°C for 0.5 to 24 hours prior to contacting with the catalyst precursor compound.

[0052]

[0013] Embodiments of the present disclosure also include catalyst systems comprising a Group 4 metal catalyst compound selected from a metallocene catalyst precursor compound, a mono-metallocene catalyst precursor compound, or a post-metallocene catalyst precursor compound.

[0053] The use of an aliphatic solvent such as isohexane rather than an aromatic solvent such as toluene provides a catalyst system (and polyolefin product) that contains no detectable amount of aromatic hydrocarbon solvent content while maintaining activity similar to that of a catalyst system prepared using preformed MAO in the desired aromatic solvent (such as Grace's commercially available MAO product, e.g., a 30% MAO solution in toluene).

[0054] Eliminating aromatic hydrocarbon solvents in the catalyst system provides a polyolefin product that does not contain detectable aromatic hydrocarbon solvents (preferably does not contain detectable toluene), as determined by gas chromatography described in the experimental section below. The polyolefin product can be used as a plastic material for toluene-free materials, such as packaging for food products, automotive interior materials, and medical devices. In addition, many saturated hydrocarbons have lower boiling points than aromatic hydrocarbons, such as pentane (36.1°C) to toluene (110°C), which makes it easier to remove saturated hydrocarbons from the polyolefin product to reduce energy consumption. The in-situ MAO loading technology also eliminates the solution MAO production facilities required to store and transport MAO products between MAO facility locations and user locations under cooling conditions 24 / 7 before use, which further reduces energy consumption. MAO gel cleaning facilities for removing gels in both MAO formation reactors and storage containers are also eliminated to avoid wastewater entering rivers or land.

[0055] For the purposes of this disclosure, "supernatant" means the inert organic solvent used to dilute the starting materials and after the relevant reaction is complete, it is the same solvent with either in-situ supported MAO or insoluble products of the catalyst system derived in the reactor, including some soluble inert by-product materials formed from the reaction of water or support material with TMA, for example, CH from the reaction of TMA with water. 4 , siloxanes from the reaction of TMA with silicon and oxygen-containing materials on the support surface, or materials dissolved from the reactor equipment, such as oil or grease. "TMA-free supernatant" means that no TMA is detected in the supernatant by NMR. "Supernatant low in hydrocarbyl aluminum compounds" means that the supernatant contains 600 ppm or less TMA as determined by NMR. For the purposes of this disclosure, "detectable aromatic hydrocarbon solvent" means 0.1 mg / m 2 For the purpose of this disclosure, "detectable toluene" means 0.1 mg / m 2 or more.

[0056] 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 Metallocenes, single site catalysts, or transition metal compounds are all catalyst precursor compounds, meaning that they require an activator to become activated before they can polymerize olefins, and can be used interchangeably.

[0057] As used herein, the term "saturated hydrocarbon" includes hydrocarbons containing zero carbon-carbon double bonds. Saturated hydrocarbons can be linear or cyclic hydrocarbons. Saturated hydrocarbons can be C 3 -C 40Hydrocarbons, such as C 3 -C 7 In at least one embodiment, C 3 -C 40 The hydrocarbon is propane, isobutane, isopentane, cyclohexane, isohexane, hexane, heptane, octane, or a mixture thereof.

[0058] In at least one embodiment, the method of polymerizing olefins to produce a polyolefin composition comprises contacting at least one olefin with a catalyst system of the present disclosure and obtaining a polyolefin that does not contain detectable aromatic hydrocarbon solvents. The polymerization can be carried out at a temperature of about 0° C. to about 200° C., at a pressure of about 0.35 MPa to about 10 MPa, and for a period of up to about 300 minutes. At least one olefin can be C 2 -C 40 Olefins, preferably C 2 -C 20 The α-olefin is preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or a mixture thereof.

[0059] For purposes of this disclosure, the numbering of the Periodic Table Groups is used as described in Chemical and Engineering News, v. 63(5), page 27 (1985). Thus, a "Group 4 metal" is an element from Group 4 of the Periodic Table, for example, Hf, Ti or Zr.

[0060] "Catalyst productivity" is a measure of how many grams of polymer (P) are produced over a period of T hours using a polymerization catalyst containing W grams of catalyst (cat); and can be represented by the formula: P / (T x W) and expressed as gPgcat -1 hr -1 The conversion rate is expressed in units of mole % and is the amount of the monomer converted into a polymer, and is reported in units of mole % and is calculated based on polymer yield (weight) and the amount of the monomer fed into the reactor. Catalyst activity is a measure of the activity level of the catalyst and is reported as the mass (gP / g loaded catalyst) of the product polymer (P) produced by the catalyst (cat) per mass load. In at least one embodiment, the activity of the catalyst is at least 800 grams of polymer / gram loaded catalyst / hour, such as about 1000 or more grams of polymer / gram loaded catalyst / hour, such as about 2000 or more grams of polymer / gram loaded catalyst / hour, such as about 3000 or more grams of polymer / gram loaded catalyst / hour, such as about 4000 or more grams of polymer / gram loaded catalyst / hour, such as about 5000 or more grams of polymer / gram loaded catalyst / hour.

[0061] "Olefins", alternatively referred to as "alkenes", are linear, branched or cyclic compounds of carbon and hydrogen with at least one double bond. When a polymer or copolymer is referred to as comprising olefins, the olefins present in such polymers or copolymers are in the form of polymerization of olefins. For example, when a copolymer is said to have an ethylene content of 35% to 55% by weight, it is understood that the monomer ("mer") unit in the copolymer is derived from the ethylene in the polymerization reaction and the derived unit is present at 35% to 55% by weight, based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer with the same monomer units. A "copolymer" is a polymer with two or more monomer units that are different from each other. A "terpolymer" is a polymer with three monomer units that are different from each other. The use of "different" to refer to a monomer unit indicates that at least one atom of a monomer unit is different from each other or isomerically different. Therefore, as used herein, the definition of "copolymer" includes terpolymers, etc. An oligomer is typically a polymer with a low molecular weight, e.g., less than 25,000 g / mol, or an Mn of less than 2,500 g / mol, or a polymer with a low number of monomer units, e.g., 75 monomer units or less, or 50 monomer units or less. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mole % ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mole % propylene-derived units, and so forth.

[0062] 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 neutral stable forms of components, it is readily understood that the ionic forms of the components are the forms that react with the monomers to produce the polymer. For purposes of this disclosure, a "catalyst system" includes both neutral and ionic forms of the components of the catalyst system.

[0063] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z average molecular weight, wt% is the weight percent, and mol% is the mole percent. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol.

[0064] In the present disclosure, catalysts may be described as catalyst precursors, precatalyst compounds, catalyst compounds or transition metal compounds, and these terms may be used interchangeably. An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "neutral donor ligand" is an uncharged ligand that donates one or more pairs of electrons to a metal ion.

[0065] For the purposes of this disclosure, with respect to catalyst compounds, the term "substituted" means that a hydrogen group has been replaced with a hydrocarbon group, a heteroatom or a heteroatom-containing group. For example, methylcyclopentadiene (MeCp) is a Cp group substituted with a methyl group.

[0066] The present disclosure describes transition metal complexes. The term complex is used to describe molecules in which an auxiliary ligand is coordinated to a central transition metal atom. The ligand is firmly bonded to the transition metal to maintain its influence during the use of the catalyst (e.g., polymerization). The ligand can be coordinated to the transition metal by covalent bonds and / or electron-donating coordination or intermediate bonds. Transition metal complexes are generally activated using activators to exhibit their polymerization function, and transition metal complexes are believed to produce cations as a result of removing anionic groups, which are often referred to as leaving groups from transition metals.

[0067] As used in the present disclosure, the following abbreviations mean: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri-n-octylaluminum, MAO is methylaluminoxane, sMAO is supported methylaluminoxane, Bn is benzyl (i.e., CH 2 Ph), THF (also referred to as thf) is tetrahydrofuran, RT is room temperature (and is 23° C. unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

[0068] The terms "hydrocarbyl radical," "hydrocarbyl," "hydrocarbyl group," "alkyl group," and "alkyl" are used interchangeably throughout this disclosure. Likewise, the terms "radical," "group," and "substituent" are used interchangeably throughout this disclosure. For the purposes of this disclosure, a "hydrocarbyl radical" is defined as a C 1 -C 100A substituted hydrocarbyl group is a group in which at least one hydrogen atom of the hydrocarbyl group has been replaced by at least one non-hydrogen group such as a halogen (e.g., Br, Cl, F, or I) or at least one functional group (e.g., NR * 2 , OR * , SeR * ,TeR * , P.R. * 2 , AsR * 2 , SbR * 2 , SR * , B.R. * 2 ,SiR * 3 ,GeR * 3 , SnR * 3 , PbR * 3 or wherein at least one heteroatom is inserted into the hydrocarbon ring.

[0069] The term "alkenyl" means a straight chain, branched or cyclic hydrocarbon group having one or more carbon-carbon double bonds. These alkenyl groups may be substituted. Examples of suitable alkenyl groups include, but are not limited to, vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, etc., including their substituted analogs.

[0070] The term "aryl" or "aryl group" means an aromatic ring containing carbon and substituted variants thereof, including but not limited to phenyl, 2-methylphenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom (preferably N, O or S). As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles, which are heterocyclic substituents having similar properties and structure (close to planar) to aromatic heterocyclic ligands, but which are not aromatic by definition.

[0071] "Aromatic" means a hydrocarbon compound containing a planar unsaturated ring of atoms that is 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 pseudoaromatic compounds, which are compounds that have similar properties and structure (close to planar) to aromatic compounds, but are not aromatic by definition; likewise, the term aromatic also refers to substituted aromatic compounds.

[0072] When isomers of a given alkyl, alkenyl, alkoxy or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl and tert-butyl), reference to one member of the group (e.g., n-butyl) will explicitly disclose the remaining isomers in the group (e.g., isobutyl, sec-butyl and tert-butyl). Likewise, reference to an alkyl, alkenyl, alkoxy or aryl group (e.g., butyl) without specifying a particular isomer explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl and tert-butyl).

[0073] The term "ring atom" means an atom that is part of a cyclic ring structure. According to this definition, a phenyl group has six ring atoms and tetrahydrofuran has five ring atoms. A heterocycle is a ring with heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which hydrogens on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle and 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring.

[0074] As used herein, "complex" also often refers to a catalyst precursor, a precatalyst, a catalyst, a catalyst compound, a transition metal compound or a transition metal complex. These terms can be used interchangeably. Activator and cocatalyst can also be used interchangeably.

[0075] Scavengers are compounds that can be added to a catalyst system to promote polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as co-activators. Co-activators that are not scavengers can also be used 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.

[0076] In this disclosure, a catalyst may be described as a catalyst precursor, a precatalyst compound, a catalyst compound, or a transition metal compound, and these terms may be used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers.

[0077] The term "continuous" means a system that operates for a sustained period of time without interruption or stopping. For example, a continuous process to produce a polymer can be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0078] "Bulk polymerization" means a polymerization process in which the monomers and / or comonomers in the polymerization are used as solvents or diluents, with little or no inert solvents or diluents used. A small portion of an inert solvent may be used as a carrier for catalysts and scavengers. Bulk polymerization systems contain less than about 25% by weight of an inert solvent or diluent, such as less than about 10% by weight, such as less than about 1% by weight, such as 0% by weight.

[0079] The term "sigma bonding" means that two atoms form a single bond containing two electrons, where each atom donates one electron. The term "coordinate bond" means that two atoms form a single bond containing two electrons, where one of the atoms donates both electrons, or an electron pair donating bond.

[0080] Carrier material

[0081] In at least one embodiment, the catalyst system comprises a support material capable of absorbing water in an amount of at least 0.5 mmol of water per gram of support material. The support material can be a porous support material, for example, silica or other inorganic oxides such as alumina, zeolites, talc, clays, organoclays or any other organic or inorganic support material containing functional groups including Bronsted sites (e.g., OH groups), Lewis base sites (e.g., electron donor groups such as amine or phosphine groups) or Lewis acid sites (e.g., unsaturated metal centers such as 3-coordinate aluminum sites), etc., or mixtures thereof.

[0082] In at least one embodiment, the support material is an inorganic oxide in finely divided form. Inorganic oxide materials suitable for use in the catalyst systems herein include Group 2, 4, 13 and 14 metal oxides, such as silica, alumina and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with silica or alumina are magnesium oxide, titanium dioxide, zirconium oxide and the like. However, other suitable support materials may be employed, such as finely divided functionalized polyolefins, such as finely divided polyethylene, polypropylene and polystyrene, having functional groups capable of absorbing water, such as oxygen- or nitrogen-containing groups such as -OH, -RC=O, -OR and -NR 2 Particularly useful supports include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, layered silicates, zeolites, talc, clays, silica clays, silicon oxide clays, and the like. In addition, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. In at least one embodiment, the support material is selected from Al 2 O 3 , ZrO 2 , SiO 2 , SiO 2 / Al 2O 2 , silica clay, silicon oxide / clay or mixtures thereof. The support material may be fluorinated.

[0083] As used herein, the phrases "fluorinated support" and "fluorinated support composition" mean a support, desirably particulate and porous, that is treated with at least one inorganic fluorine-containing compound. For example, the fluorinated support composition can be a silica support in which a portion of the silica hydroxyl groups are 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.

[0084] The fluorine compound suitable for providing fluorine to the support may be an organic or inorganic fluorine compound and is desirably an inorganic fluorine-containing compound. Such an inorganic fluorine-containing compound may be any compound containing fluorine atoms as long as it does not contain carbon atoms. Particularly desirable is an inorganic fluorine-containing compound selected from the following: NH 4 BF 4 , (NH 4 ) 2 SiF 6 , NH 4 PF 6 , NH 4 F, (NH 4 ) 2 Tf 7 , NH 4 FWf 4 , (NH 4 ) 2 F 6 , (NH 4 ) 2 SmF 6 , (NH 4 ) 2 TiF 6 , (NH 4 ) 2 ZF 6 , MoF 6 ,ReF 6 , GaF 3 , SO 2 ClF,F 2 , SiF 4 , SF 6 , ClF 3 , ClF 5 ,BrF 5 , IF 7 , NF 3 , HF, BF 3 , NHF 2 , NH 4 HF 2In at least one embodiment, ammonium hexafluorosilicate and ammonium tetrafluoroborate are used.

[0085] In at least one embodiment, the support material comprises a support material treated with an electron-withdrawing anion. The support material can be silica, alumina, silica-alumina, silica-zirconia, alumina-zirconia, aluminum phosphate, heteropolytungstate, titania, magnesium oxide, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and the electron-withdrawing anion is selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof.

[0086] The support material may be treated with an electron-withdrawing component. The electron-withdrawing component may be any component that increases the Lewis or Bronsted acidity of the support material when treated (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 (e.g., a volatile organic compound) that serves as a source or precursor for the anion. The electron-withdrawing anion may be sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, phosphotungstate, or a mixture thereof, or a combination thereof. The electron-withdrawing anion may be fluoride, chloride, bromide, phosphate, trifluoromethanesulfonate, bisulfate, or sulfate, etc., or any combination thereof, at least one embodiment of the present disclosure. In at least one embodiment, the electron-withdrawing anion is sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or a combination thereof.

[0087] Thus, for example, a support material suitable for use in the catalyst systems of the present disclosure can be one or more of the following: fluorinated alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated 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 can comprise 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 other embodiments, the support material comprises alumina treated with hexafluorotitanic acid, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, fluorinated boria-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, or a combination thereof. Additionally, any of these activator-supports may optionally be treated with a metal ion.

[0088] Non-limiting examples of cations suitable for use in salts of electron-withdrawing anions in the present disclosure include ammonium, trialkylammonium, tetraalkylammonium, tetraalkyl H+, [H(OEt 2 ) 2 ]+,[HNR 3 ]+(R=C 1 -C 20 hydrocarbyl groups, which may be the same or different) or combinations thereof.

[0089] In addition, one or more different electron-withdrawing anions can be used in combination with different ratios to adjust the specific acidity of the support material to the required level. The combination of electron-withdrawing components can be contacted with the support material simultaneously or individually and in any order to provide the support material acidity of the required chemical treatment. For example, in at least one embodiment, two or more electron-withdrawing anion source compounds are in two or more separate contact steps.

[0090] An example of a method by which a chemically treated support material is prepared is as follows: a selected support material, or a combination of support materials, can be contacted with a first electron-withdrawing anion source compound to form a first mixture; such a 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 method, the first and second electron-withdrawing anion source compounds can be the same or different compounds.

[0091] The method by which the oxide is contacted with an electron-withdrawing component (typically a salt or acid of an electron-withdrawing anion) may include, but is not limited to, gelation, co-gelation, impregnation of one compound onto another, or the like, or a combination thereof. After the contacting method, the contacted mixture of the support material, the electron-withdrawing anion, and the optional metal ion may be calcined.

[0092] According to another embodiment of the present disclosure, the support material can be treated by a method comprising: (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 calcined first mixture; (iii) contacting the calcined first 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.

[0093] Preferably, the support material, most preferably an inorganic oxide, has about 10 m 2 / g to about 800m 2 / g(optional 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 500m 2 / g, a pore volume of about 0.5cc / g to about 3.5cc / g and an average particle size of about 10μm to about 200μm. The surface area of ​​the support material can be about 100m 2 / g to about 400m 2 / g, a pore volume of about 0.8cc / g to about 3.0cc / g and an average particle size of about 5μm to about 100μm. The average pore size of the support material can be about to about For example, about to about For example, about to about In at least one embodiment, the support material is a material having a molecular weight of 300 to 400 m 2 / gm surface area and 0.9 to 1.8cm3 In at least one embodiment, the supported material may optionally be a silica containing subparticles having an average subparticle size of 0.05 to 5 microns, for example, from spray drying of small particles having an average particle size of 0.05 to 5 microns to form large primary particles having an average particle size of 5 to 200 microns. In at least one embodiment of the supported material, at least 20% of the total pore volume (defined by the BET method) has pore diameters of 100 angstroms or greater. Non-limiting example silicas 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 Chemical (AGC); P-10 / 20 or P-10 / 40 from Fuji, and the like.

[0094] The terms "silica" and "support" are used in this application to describe the support material interchangeably, that is, if silica is used in the description, this is not meant to limit the support to silica. Other support materials may also be used.

[0095] Having a carrier material that absorbs water

[0096] In an embodiment of the present disclosure, the support material will contain 0.5 mmol of absorbed water per gram of support material to 10 mmol of absorbed water per gram of support material. The amount of absorbed water is determined by adding a known amount of water to a hydrocarbon slurry of a support that has been heat treated (e.g., 150°C, 200°C, 400°C, 600°C, or 875°C) to remove pre-absorbed water and allowing to stir in a closed container to evenly distribute the added water in the pores of the support. The amount of water loaded on the support can be quantified / confirmed by standard thermogravimetric analysis methods (e.g., LOD (loss on drying) at 300°C for 4 hours). Most commercially available support materials will contain some absorbed water and the amount of absorbed water may be sufficient in some cases. Additional water may be required in other cases; for example, the amount of pre-absorbed water may be determined first using the mentioned LOD method, and then additional water may be added to obtain the total amount of water absorbed on the desired support.

[0097] In an embodiment of the present disclosure, a support material containing 0.5 mmol of absorbed water per gram of support material to 10 mmol of absorbed water per gram of support material can be prepared as above in a closed container, except that no solvent is used. The solid in the closed container can then be placed in an environment to allow the container to be heated uniformly, i.e., there are no cold spots on which water condenses. The heating temperature can be 30° C. to 100° C., preferably 45° C. to 65° C. The heating time is at least 30 minutes, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or longer.

[0098] Preferably, the support material is silica, alumina, alumina-silica or a derivative thereof.

[0099] 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 2 / g of surface area.

[0100] Preferably, the support material has been treated with one or more of a Bronsted acid, a Lewis acid, a salt and a Lewis base.

[0101] Preferably, the support material comprises a silanizing agent.

[0102] Preferably, the support material comprises a hydrocarbyl aluminum compound.

[0103] Preferably, one or more of the support materials comprises an electron-withdrawing anion.

[0104] Organic solvents

[0105] Suitable organic solvents are materials in which all reactants used herein, such as the carrier and TMA, may or may not be dissolved and which are liquid at the reaction temperature. Non-limiting example solvents are those having the formula C n H (n+2) Acyclic alkanes, wherein n=3-30, such as propane, isobutylene, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and having the formula C n H n Cycloalkanes, wherein n=5-30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc. Aromatic solvents such as 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 can result in MAO dissolving in the supernatant, which needs to be removed (e.g., by a filtration step) to avoid reactor fouling and to reuse the solvent.

[0106] TMA

[0107] Although TMA is specifically used for in situ supported MAO formation. A portion of other alkyl aluminum compounds such as trialkyl aluminum compounds or heteroatom substituted alkyl aluminum compounds may also be present, for example, 50 mol% or less based on total Al. Alkyl substituents are alkyl groups with up to 10 carbon atoms, such as octyl, isobutyl, ethyl or methyl groups may be present as minor components. Thus, suitable trialkyl aluminum compounds include trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri(2-methylpentyl) aluminum, trihexyl aluminum, tri-n-octylaluminum, tri-n-decyl aluminum, and any mixed alkyl aluminum compounds, such as AlH i Bu 2 ,AlEt 2 i Bu,AlMe 2 Oct, etc. Preferred hydrocarbyl aluminum compounds are trimethyl aluminum and tri-n-octyl aluminum. Therefore, suitable heteroatom-substituted alkyl aluminum compounds include, but are not limited to, AlR 2 F,AlRF 2 , AlR 2 (OC 6 F 5 ), AlR 2 (OC 6 F 5 )wait.

[0108] In the method of the present disclosure, in one embodiment, for the in-situ supported MAO formation temperature in the range of -6°C to -60°C, the ratio of absorbed water to the amount of hydrocarbyl aluminum compound in the support material can be 1:1.25 to 1:1.42 to obtain a supernatant containing no free TMA or a low free TMA content, provided that: when the in-situ supported MAO is formed at a higher cooling temperature (e.g., -6°C to -12°C), the water:TMA ratio is controlled at 1:1.25 to 1:1.31, and when it is formed at a lower cooling temperature (e.g., -12°C or lower), the water:TMA ratio is controlled at 1:31 to 1:1.42. It should be understood that when the first drop of absorbed water support is added to the TMA solution, the water:TMA ratio is close to 1:∞; therefore, in theory, the water:TMA ratio can be 1:1.5 (active MAO formula (Al 4 O 3 Me 6 ) 4 (AlMe 3 ) 2 The O:Al ratio in the mixture can be 1:3, 1:5, 1:10, 1:100, 1:1000, 1:10000 or higher to form an active in situ supported MAO composition. However, the final supernatant will contain a large amount of free TMA, for example, >600 ppm, >1 wt %, >5 wt % or higher.

[0109] In some embodiments of the process, TMA and other optional alane compounds are present in an amount of about 1.5 to 30 wt % aluminum, based on the weight of the separated solid product, excluding Al in the support material (e.g., alumina). Preferably, the amount of aluminum is 4 to 25 wt %, more preferably 6 to 15 wt %, based on the total weight of the separated solid product. More preferably, the optional alane compound is such that the modified supported MAO is less soluble to obtain a product containing less or no soluble alane species (e.g., AlR 2 F, for example, AlMe 2 F,AlEtF 2 , such as Al(C 6 F 5 ) 3 , AlMe(C 6 F 5 ) 2 etc.) in the supernatant.

[0110] In situ loaded MAO

[0111] The supported MAO of the present disclosure is prepared in situ by contacting a water-saturated support (e.g., silica) as a slurry in an organic solvent or as a solid without any solvent with TMA as a solution in an organic solvent. A preferred method for forming an in situ sMAO is to slowly add the support slurry to the TMA solution at a temperature in the range of -6°C to -60°C, preferably -10°C to -50°C, such as -12°C to -40°C, or below -15°C, -20°C or -30°C, so that the internal temperature of the reactor is maintained within the desired range, e.g., within 4°C, e.g., -10°C ± 1°C, -15°C ± 2°C, or -25°C ± 2°C; e.g., not higher than -6°C.

[0112] In at least one embodiment of the present disclosure, a high viscosity hydrocarbon solvent (eg, mineral oil) is used, at least in part, to form the support slurry in order to produce a viscous slurry to reduce or avoid rapid support settling.

[0113] In at least one embodiment of the present disclosure, a mixture of the hydrocarbyl aluminum and the water-saturated silica is stirred.

[0114] Control of the ratio of active MAO to inactive MAO gel

[0115] Active MAO formula (Al 4 O 3 Me 6 ) 4 (TMA c ) 1-2 The target MAO composition is theoretically derived from 17-18 equivalents of TMA and 12 equivalents of H 2O to provide 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", in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, p. 105). Experimental evidence strongly suggests that coordinated TMA serves as the primary active site to provide AlMe for ionization of the catalyst precursor compound. 2 + , and free TMA acts as an alkylating agent (see Luo, Jain, and Harlan, ACS Annual Meeting, Conference Abstracts PMSE 126 and INOR 1169, April 2-6, 2017; Luo, Wu, & Diefenbach, U.S. Patent 9,090,720 (2015)).

[0116] It has been found that the formation of active MAO as the major product requires two major key conditions: 1) cold temperatures, e.g., -8°C or lower; and 2) an environment of excess TMA around water molecules, e.g., to match the active MAO formula with at least one coordinated TMA (i.e., (Al 4 O 3 Me 6 ) 4 (TMA c ) 1 ) with a TMA:water ratio of at least 1.42:1. If either of the two conditions is not met, the inactive MAO gel molecules (AlOMe) n It can be formed as the main product, because the active MAO molecules are the kinetic products that tend to form more stable MAO gel molecules, as shown in the energy curve below (Scheme 1):

[0117] Solution 1

[0118]

[0119] The experimental results are consistent with the above energy curves, indicating that active MAO molecules in solution form are unstable under ambient conditions, for example, for a 30 wt % MAO toluene solution, a MAO gel of >30 wt % can be formed after 3-4 days under ambient conditions. The MAO solution therefore needs to be stored at cold temperatures, for example, at temperatures within the practical cooling range of -20°C to -30°C, to reduce the gelation process so as to maintain performance over a more practical storage period (e.g., several months), with a limited gel content, e.g., <5 wt % of the total MAO content. Based on experimental observations of a gradual increase in free TMA content, the gelation process is believed to undergo a continuous dimerization process of MAO molecules, i.e., two monomers dimerize to form a dimer, a monomer and a dimer dimerize to form a trimer, two dimers dimerize to form a tetramer, etc., and the elimination of coordinated TMA to produce larger and larger MAO molecules (and therefore fewer and fewer total MAO molecules).

[0120] On the other hand, once the MAO molecules are loaded, the gelation process is almost completely blocked, most likely due to the difficulty of the MAO molecules to move to contact and dimerize. The loaded MAO thus has a longer shelf life, even under ambient conditions, such as maintaining 90% or higher activation efficiency for 3 years under an inert environment.

[0121] Theoretically, the lower the reaction temperature, the more energy barriers (E in Scheme 1) * ) to form more stable MAO gel molecules. However, it is not practical to reach very low temperatures (e.g., below -60°C) in commercial reactors. Therefore, for the design of commercial production conditions, there is a compromise between the practical cooling temperature and the MAO gel molecular weight allowed in the system.

[0122] The supported MAO can also be heated to change the properties of the supported MAO, for example due to the solubility of the non-supported small MAO molecules, to dimerize the non-supported small MAO molecules and the supported MAO molecules to reduce the amount of non-supported MAO molecules for better operability in a slurry polymerization process, for example when the supported MAO is used to activate more positively charged stabilizing centers and / or more open ligand frameworks of catalyst precursor compounds, to increase the size of weaker ion-pairing MAO molecules, or to control the ratio of supported MAO molecules to non-supported large MAO molecules, for example for a desired comonomer distribution.

[0123] In at least one embodiment of the present disclosure, a supported catalyst system that still has suitable activity is obtained by allowing a portion of the gel molecules to form under more realistic reaction conditions, for example, at a reaction temperature of -8°C, -10°C, or -12°C to allow the formation of less than about 40 wt%, less than about 30 wt%, or less than about 20 wt% gel, based on the total MAO loaded on the support. Because the gel MAO molecules have a TMA:water uptake ratio close to 1:1, a supported MAO system containing a small portion of MAO gel can exhibit an overall TMA:water uptake ratio that is less than the Al:O ratio in the active MAO formula, i.e., <1.5:1 for active MAO with 2 coordinated TMAs, or <1.42:1 for active MAO with 1 coordinated TMA, e.g., about 1.25:1, about 1.30:1, or about 1.35:1. For example, a mixture of 3 equivalents of loaded active MAO molecules (1 coordinated TMA) and 1 equivalent of loaded gelled MAO molecules provides 3 / 4 1.42:1+ 1 / 4 1:1 = final TMA:water uptake ratio of 1.32:1.

[0124] 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 so that the reaction temperature can be maintained at a low temperature, such as -10°C ± 1°C, -20°C ± 2°C, -30°C ± 4°C, or -60°C ± 6°C, so that a major portion of the total water-absorbed silica, such as 60 wt%, 70 wt% or 80 wt%, can have a large excess of TMA around the water molecules, such as a TMA:water ratio of about 100:1, 80:1, 60:1, 40:1, 20:1 or 10:1, to maximize the formation of coordinated TMA.

[0125] In at least one embodiment of the present disclosure, the feed TMA:water ratio is controlled so that at the end of the in situ sMAO formation reaction, the feed TMA:water ratio is controlled so that ... 1 NMR spectroscopy determined that there was no detectable TMA in the supernatant or that TMA did not exceed 600 ppm. In at least one embodiment of the present disclosure, the feed TMA:water ratio is no higher than the Al:O ratio in the composition containing both the loaded active MAO and the loaded inactive MAO gel molecules, i.e., the feed TMA:water ratio is no higher than the TMA:water uptake ratio determined, for example, by the ratio of active MAO to inactive MAO gel.

[0126] Optional thermal treatment of supported aluminoxane

[0127] The supported aluminoxanes of the present disclosure, after being prepared in situ, can be further treated at a higher temperature for a period of time, either as an organic solvent slurry or as a solid. In at least one embodiment, the high temperature treatment can be in the range of 60°C-140°C, preferably 70°C-120°C, and more preferably 85°C-110°C. The heating time can be 30 minutes up to 12 hours, preferably 2-8 hours, and more preferably 3-6 hours. After such heat treatment, some finished catalyst systems can have significant activity improvements, for example, hafnocene and other structurally open zirconocene catalyst precursor compounds such as dimethylsilyl bridged zirconocenes, while some do not have this activity improvement, for example, structurally closed zirconocenes such as non-bridged zirconocenes. After such heat treatment, soluble MAO is limited thereby improving the operability of the catalyst, especially in a slurry polymerization process, presumably due to dimerization of soluble small unimmobilized MAO molecules to become large insoluble MAO molecules, and / or unimmobilized MAO molecules become immobilized by dimerization with immobilized MAO molecules, as indicated by the observation of less THF-extractable MAO on the finished catalyst system after heat treatment. Heat treatment also reduces hydroxyl groups in the finished catalyst system as indicated by IR spectroscopy; unreacted hydroxyl groups are believed to be a deactivating factor for the finished catalyst system.

[0128] The reaction mixture after contacting the support material with absorbed water and TMA in an organic solvent at low temperature can also be spray dried at a higher temperature in a spray drying reactor to evaporate the solvent / volatiles and form a solid product with a desired average particle size and particle size distribution. The preferred temperature range is 60°C-200°C, more preferably 80°C-190°C, and most preferably 90°C-160°C.

[0129] Catalyst precursor compound

[0130] In at least one embodiment, the present disclosure provides a catalyst system comprising a catalyst precursor with a metal atom. The catalyst precursor compound can be a metallocene, a single metallocene, or a post-metallocene single-site catalyst precursor compound. The metal can be a 3rd to 12th family metal atom, such as a 3rd to 10th family metal atom, or a lanthanide atom. The catalyst compound with a 3rd to 12th family metal atom can be monodentate or polydentate, such as bidentate, tridentate, or tetradentate, wherein the heteroatoms of the catalyst, such as phosphorus, oxygen, nitrogen or sulfur are chelated to the metal atom of the catalyst. Non-limiting examples include bis(phenolates). In at least one embodiment, the 3rd to 12th family metal atom is selected from the 5th family, the 6th family, the 8th family, or the 10th family metal atom. In at least one embodiment, the 3rd to 10th family metal atom is 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 atom is selected from Group 4, 5, and 6 metal atoms. In at least one embodiment, the metal atom is a Group 4 metal atom selected from Ti, Zr, or Hf. The oxidation state of the metal atom ranges from 0 to +7, such as +1, +2, +3, +4, or +5, such as +2, +3 or +4.

[0131] The catalyst compound of the present disclosure may be chromium or a chromium-based catalyst. Chromium-based catalysts include chromium oxide (CrO 3 ) and silylchromate catalysts. In the field of continuous fluidized bed gas phase polymerization for producing polyethylene polymers, chromium catalysts have been the subject of many developments. Such catalysts and polymerization methods have been described, for example, in U.S. Publication No. 2011 / 0010938 and U.S. Pat. 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.

[0132] The metallocene catalyst compounds used herein include metallocenes comprising a Group 3 to Group 12 metal complex, preferably a Group 4 to Group 6 metal complex, such as a Group 4 metal complex. The metallocene catalyst compound of the catalyst system of the present disclosure may be a non-bridged metallocene catalyst compound represented by the formula:

[0133] Cp A Cp B M'X' n ,

[0134] Where Cp A and Cp BEach independently selected from a cyclopentadienyl ligand and a ligand isolobal to the cyclopentadienyl group, Cp A and Cp B One or both of them may contain heteroatoms, and Cp A and Cp B One or two of the groups may be substituted with one or more R" groups. M' is selected from atoms of Groups 3 to 12 and lanthanide atoms. X' is an anion 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, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphino, phosphine, amino, amine, ether and thioether.

[0135] In at least one embodiment, Cp A and Cp B Each is independently selected from cyclopentadienyl, indenyl, fluorenyl, cyclopentaphenanthreneyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthroindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thienoindenyl, thienofluorenyl, and hydrogenated variants thereof.

[0136] Non-limiting examples of non-bridged metallocenes are:

[0137] Bis(n-propylcyclopentadienyl)hafnium dichloride,

[0138] Bis(n-propylcyclopentadienyl)hafnium dimethyl,

[0139] Bis(n-propylcyclopentadienyl)zirconium dichloride,

[0140] Bis(n-propylcyclopentadienyl)zirconium dimethyl,

[0141] Bis(n-propylcyclopentadienyl)titanium dichloride,

[0142] Bis(n-propylcyclopentadienyl)dimethyltitanium,

[0143] (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,

[0144] (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dimethyl,

[0145] (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dichloride,

[0146] (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)hafnium dimethyl,

[0147] (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)titanium dichloride,

[0148] (n-propylcyclopentadienyl)(pentamethylcyclopentadienyl)titanium dimethyl,

[0149] (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,

[0150] (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dimethyl,

[0151] (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)hafnium dichloride,

[0152] (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)hafnium dimethyl,

[0153] (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)titanium dichloride,

[0154] (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)titanium dimethyl,

[0155] Bis(cyclopentadienyl)hafnium dimethyl,

[0156] Bis(n-butylcyclopentadienyl)hafnium dichloride,

[0157] Bis(n-butylcyclopentadienyl)hafnium dimethyl,

[0158] Bis(n-butylcyclopentadienyl)zirconium dichloride,

[0159] Bis(n-butylcyclopentadienyl)zirconium dimethyl,

[0160] Bis(n-butylcyclopentadienyl)titanium dichloride,

[0161] Bis(n-butylcyclopentadienyl)dimethyltitanium,

[0162] Bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,

[0163] Bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dimethyl,

[0164] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,

[0165] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

[0166] Bis(1-methyl-3-n-butylcyclopentadienyl)titanium dichloride, and

[0167] Bis(1-methyl-3-n-butylcyclopentadienyl)dimethyltitanium.

[0168] The metallocene catalyst compound may be a bridged metallocene catalyst compound represented by the following formula:

[0169] Cp A (A)Cp B M'X' n ,

[0170] Where Cp A and Cp B Each is independently selected from a cyclopentadienyl ligand and a ligand isolobal to a cyclopentadienyl group. A and Cp B One or both of them may contain heteroatoms, and Cp A and Cp BOne or two of the groups may be substituted with one or more R" groups. M' is selected from atoms of Groups 3 to 12 and lanthanide atoms. X' is an anion leaving group. n is 0 or an integer from 1 to 4. (A) is selected from 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, divalent heteroalkynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylsulfide, divalent lower alkylsulfide, divalent arylsulfide, 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 A group containing a heteroatom, a divalent hydrocarbon group, a divalent lower hydrocarbon group, a divalent substituted hydrocarbon group, a divalent heterohydrocarbon group, a divalent silyl group, a divalent boryl group, a divalent phosphine group, a divalent phosphine group, a divalent amino group, a divalent amine group, a divalent ether group, and a divalent sulfide group. R" is selected from the group consisting of 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, a group containing a heteroatom, a hydrocarbon group, a lower hydrocarbon group, substituted hydrocarbon group, heterohydrocarbon group, a silyl group, a boryl group, a phosphine group, a phosphine group, an amino group, an amine, germanium, an ether, and a sulfide group.

[0171] In at least one embodiment, Cp A and Cp B Each is independently selected from cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl.

[0172] (A) can be O, S, NR', or SiR' 2 , wherein R' is each independently hydrogen or C 1 -C 20 Hydrocarbon.

[0173] Non-limiting examples of bridged metallocenes are:

[0174] Ethylene-bis(indenyl)zirconium dichloride or ethylene-bis(indenyl)zirconium dimethyl;

[0175] Dimethylsilanediylbis(4,5,6,7-indenyl)zirconium dichloride or dimethylsilanediylbis(4,5,6,7-indenyl)zirconium dimethyl;

[0176] Dimethylsilanediylbis(4,5,6,7-tetrahydroindenyl)zirconium dichloride or dimethylsilanediylbis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl;

[0177] Dimethylsilanediyl(2-methyl-(4-(3',5'-di-tert-butyl-4'-methoxy-phenyl)indenyl)(2-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-(4-(3',5'-di-tert-butyl-4'-methoxy-phenyl)indenyl)(2-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0178] Dimethylsilanediyl(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0179] Dimethylsilanediyl(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0180] Dimethylsilanediyl(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0181] Dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0182] Dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium(CH 3 ) 2 ;

[0183] Dimethylsilanediyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0184] Dimethylsilanediyl(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0185] Dimethylsilanediyl(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0186] Dimethylsilanediyl(2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0187] Dimethylsilanediyl(2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0188] Dimethylsilanediyl(2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0189] Dimethylsilanediyl(2-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0190] Dimethylsilanediyl(2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0191] Dimethylsilanediyl(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl; dimethylsilanediyl(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or Dimethylsilanediyl(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl; and dimethylsilanediyl(2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0192] Dimethylsilanediyl(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0193] 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)zirconium dichloride or 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)zirconium dimethyl;

[0194] Dimethylsilanediyl(2-methyl-4-phenyl-(1,5,6,7-tetrahydro-s-indacenyl))(2-isopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-phenyl-(1,5,6,7-tetrahydro-s-indacenyl))(2-isopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0195] Dimethylsilanediyl(2-methyl-4(4'-tert-butylphenyl)indenyl)(2-isopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4(4'-tert-butylphenyl)indenyl)(2-isopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0196] Dimethylsilanediyl(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0197] Dimethylsilanediyl(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0198] Dimethylsilanediyl(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0199] Dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0200] Dimethylsilanediyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0201] Dimethylsilanediyl(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0202] Dimethylsilanediyl(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0203] Dimethylsilanediyl(2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0204] Dimethylsilanediyl(2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0205] Dimethylsilanediyl(2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0206] Dimethylsilanediyl(2-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0207] Dimethylsilanediyl(2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0208] Dimethylsilanediyl(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0209] Dimethylsilanediyl(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0210] Dimethylsilanediyl(2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or dimethylsilanediyl(2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0211] Dimethylaminoborane (2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0212] Dimethylaminoborane (2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0213] Dimethylaminoborane (2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0214] Dimethylaminoborane (2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0215] Dimethylaminoborane (2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0216] Dimethylaminoborane (2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0217] Dimethylaminoborane (2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0218] Dimethylaminoborane (2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0219] Dimethylaminoborane (2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0220] Dimethylaminoborane (2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0221] Dimethylaminoborane (2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0222] Dimethylaminoborane (2-tert-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-tert-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0223] Dimethylaminoborane (2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0224] Dimethylaminoborane (2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0225] Dimethylaminoborane (2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0226] Dimethylaminoborane (2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or dimethylaminoborane (2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0227] Diisopropylaminoborane (2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0228] Diisopropylaminoborane (2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0229] Diisopropylaminoborane (2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0230] Diisopropylaminoborane (2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0231] Diisopropylaminoborane (2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0232] Diisopropylaminoborane (2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0233] Diisopropylaminoborane (2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0234] Diisopropylaminoborane (2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0235] Diisopropylaminoborane (2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0236] Diisopropylaminoborane (2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0237] Diisopropylaminoborane (2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0238] Diisopropylaminoborane (2-tert-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-tert-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0239] Diisopropylaminoborane (2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0240] Diisopropylaminoborane (2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0241] Diisopropylaminoborane (2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0242] Diisopropylaminoborane (2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dichloride or diisopropylaminoborane (2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl) indenyl) (2-n-hexyl-4-(o-biphenyl) indenyl) zirconium dimethyl;

[0243] Bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0244] Bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0245] Bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0246] Bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-di-tert-butyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0247] Bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0248] Bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0249] Bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0250] Bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-bistrifluoromethyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0251] Bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0252] Bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0253] Bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0254] Bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-diisopropyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0255] Bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-methyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0256] Bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-ethyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0257] Bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-propyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0258] Bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dichloride or bis(trimethylsilyl)aminoborane(2-butyl-4-(3',5'-diphenyl-4'-methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)zirconium dimethyl;

[0259] Dimethylsilanediylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride or dimethylsilanediylbis(2-methyl-4-phenyl-indenyl)zirconium dimethyl;

[0260] Dimethylsilanediylbis(2-methyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-methyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dimethyl;

[0261] Dimethylsilanediylbis(2-methyl-4-(3',5-di-tert-butyl-4-methoxyphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-methyl-4-(3',5-di-tert-butyl-4-methoxyphenyl)indenyl)zirconium dimethyl;

[0262] Dimethylsilanediylbis(2-methyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-methyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0263] Dimethylsilanediylbis(2-ethyl-4-phenyl-indenyl)zirconium dichloride or dimethylsilanediylbis(2-ethyl-4-phenyl-indenyl)zirconium dimethyl;

[0264] Dimethylsilanediylbis(2-ethyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-ethyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dimethyl;

[0265] Dimethylsilanediylbis(2-ethyl-4-(3',5-di-tert-butyl-4-methoxyphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-ethyl-4-(3',5-di-tert-butyl-4-methoxyphenyl)indenyl)zirconium dimethyl;

[0266] Dimethylsilanediylbis(2-ethyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-ethyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0267] Dimethylsilanediylbis(2-propyl-4-phenylindenyl)zirconium dichloride or dimethylsilanediylbis(2-propyl-4-phenylindenyl)zirconium dimethyl;

[0268] Dimethylsilanediylbis(2-propyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-propyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dimethyl;

[0269] Dimethylsilanediylbis(2-propyl-4-(3',5-di-tert-butyl-4-methoxyphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-propyl-4-(3',5-di-tert-butyl-4-methoxyphenyl)indenyl)zirconium dimethyl;

[0270] Dimethylsilanediylbis(2-propyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-propyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0271] Dimethylsilanediylbis(2-isopropyl-4-phenylindenyl)zirconium dichloride or dimethylsilanediylbis(2-isopropyl-4-phenylindenyl)zirconium dimethyl;

[0272] Dimethylsilanediylbis(2-isopropyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-isopropyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dimethyl;

[0273] Dimethylsilanediylbis(2-isopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-isopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0274] Dimethylsilanediylbis(2-cyclopropyl-4-phenylindenyl)zirconium dichloride or dimethylsilanediylbis(2-cyclopropyl-4-phenylindenyl)zirconium dimethyl;

[0275] Dimethylsilanediylbis(2-cyclopropyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-cyclopropyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dimethyl;

[0276] Dimethylsilanediylbis(2-cyclopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-cyclopropyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0277] Dimethylsilanediylbis(2-butyl-4-phenylindenyl)zirconium dichloride or dimethylsilanediylbis(2-butyl-4-phenylindenyl)zirconium dimethyl;

[0278] Dimethylsilanediylbis(2-butyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-butyl-4-(3',5-di-tert-butylphenyl)indenyl)zirconium dimethyl;

[0279] Dimethylsilanediylbis(2-butyl-4-(4'-tert-butylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-butyl-4-(4'-tert-butylphenyl)indenyl)zirconium dimethyl;

[0280] Dimethylsilanediylbis(2-methyl-4-(2'-methylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-methyl-4-(2'-methylphenyl)indenyl)zirconium dimethyl;

[0281] Dimethylsilanediylbis(2-isopropyl-4-(2'-methylphenyl)indenyl)zirconium dichloride or dimethylsilanediylbis(2-isopropyl-4-(2'-methylphenyl)indenyl)zirconium dimethyl;

[0282] Dimethylsilanediylbis(2-methyl-4-carbazolyl)zirconium dichloride or dimethylsilanediylbis(2-methyl-4-carbazolyl)zirconium dimethyl; and

[0283] Dimethylsilanediylbis(2-isopropyl-4-carbazolyl)zirconium dichloride or dimethylsilanediylbis(2-isopropyl-4-carbazolyl)zirconium dimethyl;

[0284] In at least one embodiment, a number of C1 symmetric bis-Cp metallocene catalysts having high Tm PP and / or diene incorporation capabilities can be represented by formula (C1a) with bridged substituted cyclopentadienyl and substituted indenyl catalyst precursor compounds:

[0285]

[0286] in:

[0287] M is a transition metal atom;

[0288] T is a bridging group;

[0289] X 1 and X 2 Each is a monovalent anionic ligand, or X 1 and X 2 joining to form a metal annular ring;

[0290] R 1 is hydrogen, halogen, unsubstituted C 1 -C 40 Hydrocarbon, C 1 -C 40 Substituted hydrocarbon, unsubstituted C 4 -C 62 Aryl, substituted C 4 -C 62 Aryl, unsubstituted C 4 -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 C 1 -C 10 alkyl and R' are each hydrogen, halogen, C 1 -C 10 Alkyl, or C 6 -C 10 Aryl;

[0291] R 3 is unsubstituted C 4 -C 62 Cycloalkyl, substituted C 4 -C 62 Cycloalkyl, unsubstituted C 4 -C 62 Aryl, substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, or substituted C 4 -C 62 heteroaryl;

[0292] R 2 and R 4 are independently hydrogen, halogen, unsubstituted C 1 -C 40 Hydrocarbon, C 1 -C 40 Substituted hydrocarbon, unsubstituted C 4 -C 62 Aryl, substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 ,-PR' 2 or -R"-SiR' 3 , where R' is C 1 -C 10 alkyl and R' are each hydrogen, halogen, C 1 -C 10 Alkyl, or C 6 -C10 Aryl;

[0293] R 5 , R 6 , R 7 and R 8 are independently hydrogen, halogen, unsubstituted C 1 -C 40 Hydrocarbon, C 1 -C 40 Substituted hydrocarbon, unsubstituted C 4 -C 62 Aryl, substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 ,-PR' 2 or -R"-SiR' 3 , where R' is C 1 -C 10 alkyl and R' are each hydrogen, halogen, C 1 -C 10 Alkyl, or C 6 -C 10 Aryl, or R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 One or more pairs of C 4 -C 62 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof; and

[0294] J 1 and J 2 Each is combined to form a substituted or unsubstituted C 4 -C 62 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0295] In some embodiments of the present disclosure, M is a transition metal such as a transition metal of Group 3, 4, or 5 of the Periodic Table of Elements, such as a Group 4 metal, such as Zr, Hf, or Ti.

[0296] In some embodiments of the present disclosure, X 1 and X 2 Each independently is unsubstituted C1 -C 40 Hydrocarbyl (e.g. unsubstituted C 2 -C 20 Hydrocarbyl), substituted C 1 -C 40 Hydrocarbyl (e.g. substituted C 2 -C 20 Hydrocarbon), unsubstituted C 4 -C 62 Aryl, substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, hydride, amide, alkoxy, sulfide, phosphide, halide, diene, amine, phosphine, ether, and combinations thereof, such as X 1 and X 2 are each independently halogen or C 1 -C 5 In some embodiments, X 1 and X 2 Each is independently chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of the present disclosure, X 1 and X 2 Forming part of a fused ring or ring system.

[0297] In some embodiments, T is represented by the formula (R* 2 G) g represents, wherein G is C, Si or Ge, g is 1 or 2, and R* is independently hydrogen, halogen, unsubstituted C 1 -C 20 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), substituted C 1 -C 20 A hydrocarbon group, or two or more R* may be 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 bridging group and is formed by R' 2 C, R' 2 Si, R' 2 Ge, R' 2 CCR' 2 , R' 2 CCR' 2CR' 2 ,R' 2 CCR' 2 CR' 2 CR' 2 ,R'C=CR',R'C=CR'CR' 2 ,R' 2 CCR'=CR'CR' 2 ,R'C=CR'CR'=CR',R'C=CR'CR' 2 CR' 2 ,R' 2 CSiR' 2 ,R' 2 SiSiR' 2 ,R 2 CSiR' 2 CR' 2 ,R' 2 SiCR' 2 SiR' 2 ,R'C=CR'SiR' 2 ,R' 2 CGeR' 2 ,R' 2 GeGeR' 2 ,R' 2 CGeR' 2 CR' 2 ,R' 2 GeCR' 2 GeR' 2 ,R' 2 SiGeR' 2 ,R'C=CR'GeR' 2 ,R'B,R' 2 C–BR',R' 2 C–BR'–CR' 2 ,R' 2 C–O–CR' 2 ,R' 2 CR' 2 C–O–CR' 2 CR' 2 ,R' 2 C–O–CR' 2 CR' 2 ,R' 2 C–O–CR'=CR',R' 2 C–S–CR' 2 ,R' 2 CR' 2 C–S–CR' 2 CR' 2 ,R' 2C–S–CR' 2 CR' 2 , R' 2 C–S–CR'=CR', R' 2 C–Se–CR' 2 , R' 2 CR' 2 C–Se–CR' 2 CR' 2 , R' 2 C–Se–CR 2 CR' 2 , R' 2 C–Se–CR'=CR',R' 2 C–N=CR',R' 2 C–NR'–CR' 2 , R' 2 C–NR'–CR' 2 CR' 2 , R' 2 C–NR'–CR'=CR', R' 2 CR' 2 C–NR'–CR' 2 CR' 2 , R' 2 C–P = CR', or R' 2 C–PR'–CR' 2 represents, wherein R' is independently hydrogen or unsubstituted C 1 -C 20 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), substituted C 1 -C 20 Hydrocarbon, C 1 -C 20 Halogenated hydrocarbon (halocarbyl), C 1 -C 20 Silylcarbyl, or C 1 -C 20 A germylcarbyl substituent, or two or more adjacent R's 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 bridging group containing carbon or silicon, such as a dialkylsilyl group, for example, T is CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , (Ph) 2C, (p-(Et) 3 SiPh) 2 C,SiMe 2 ,SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , or Si(CH 2 ) 4 .

[0298] In some embodiments, R 1 is hydrogen, substituted C 1 -C 20 Hydrocarbon, or unsubstituted C 1 -C 20 Hydrocarbyl, such as substituted C 1 -C 12 Hydrocarbon or unsubstituted C 1 -C 12 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as hydrogen, substituted C 1 -C 6 Hydrocarbon, or unsubstituted C 1 -C 6 Hydrocarbon.

[0299] In some embodiments, R 2 and R 4 are independently hydrogen, substituted C 1 -C 20 Hydrocarbon, or unsubstituted C 1 -C 20 Hydrocarbyl, such as substituted C 1 -C 12 Hydrocarbon or unsubstituted C 1 -C 12 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as hydrogen, substituted C 1 -C 6 Hydrocarbon, or unsubstituted C 1 -C 6 Hydrocarbon.

[0300] In some embodiments, R 5 , R 6 , R 7 and R 8 are independently hydrogen, substituted C 1 -C 20 Hydrocarbon, or unsubstituted C 1 -C20 Hydrocarbyl, such as substituted C 1 -C 12 Hydrocarbon or unsubstituted C 1 -C 12 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as substituted C 1 -C 6 Hydrocarbon, or unsubstituted C 1 -C 6 A hydrocarbon group (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 One or more pairs of C 4 -C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0301] In some embodiments, R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 One or more pairs of C 5 -C 8 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0302] In some embodiments, R 3 is unsubstituted C 4 -C 20 Cycloalkyl (e.g., cyclohexane, cyclopentane, cyclooctane, adamantane), or substituted C 4 -C 20 Cycloalkyl.

[0303] In some embodiments, R 3 is a substituted or unsubstituted phenyl group, benzyl group, carbazolyl group, naphthyl group, or fluorenyl group.

[0304] In some embodiments, R 3 is a substituted or unsubstituted aryl group represented by the formula:

[0305]

[0306] Where R 9 , R 10 , R 11 , R 12and R 13 are independently hydrogen, unsubstituted C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 A hydrocarbon group, a heteroatom, a group containing a heteroatom, or R 9 , R 10 , R 11 , R 12 and R 13 Two or more of them join together to form C 4 -C 62 Cyclic or polycyclic ring structures, or combinations thereof.

[0307] In some embodiments of the present disclosure, R 9 , R 10 , R 11 , R 12 and R 13 are independently hydrogen, halogen, unsubstituted C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 Hydrocarbyl, unsubstituted C 4 -C 62 Aryl (e.g. unsubstituted C 4 -C 20 Aryl, such as phenyl), substituted C 4 -C 62 Aryl (e.g. substituted C 4 -C 20 Aryl), unsubstituted C 4 -C 62 Heteroaryl (e.g., unsubstituted C 4 -C 20 Heteroaryl), substituted C 4 -C 62 Heteroaryl (e.g. substituted C 4 -C 20 Heteroaryl), -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 ,-PR' 2 or -R"-SiR' 3 , where R' is C 1 -C 10 alkyl and R' is each hydrogen, halogen, C 1 -C 10 Alkyl, or C 6 -C 10 Aryl. For example, R 9 , R 10 , R11 , R 12 and R 13 are independently hydrogen, substituted C 1 -C 20 Hydrocarbon, or unsubstituted C 1 -C 20 Hydrocarbyl, such as substituted C 1 -C 12 Hydrocarbon or unsubstituted C 1 -C 12 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as substituted C 1 -C 6 Hydrocarbon, or unsubstituted C 1 -C 6 A hydrocarbon group (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 the 4 -C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0308] In some embodiments of the present disclosure, R 9 , R 10 , R 11 , R 12 and R 13 At least one of the groups is a phenyl group.

[0309] In some embodiments of the present disclosure, J 1 and J 2 Each is joined to form an unsubstituted C 4 -C 20 Cyclic or polycyclic rings, any of which may be saturated, partially saturated or unsaturated. In some embodiments, J each joins to form a substituted C 4 -C 20 Cyclic or polycyclic rings, any of which may be saturated or unsaturated. Examples include:

[0310]

[0311] In at least one embodiment, the C1 symmetric bis-Cp metallocene catalyst can also be represented by a bridged substituted cyclopentadienyl and substituted indenyl catalyst precursor compound as represented by formula (C1b):

[0312]

[0313] Among them, M, T, J 1 , J 2 , X 1 , X 2 , R 1 , R 2 and R 4 -R 13 Described above.

[0314] In at least one embodiment, the C1 symmetric bis-Cp metallocene catalyst can also be represented by a bridged substituted cyclopentadienyl and substituted indenyl catalyst precursor compound as represented by formula (C1c):

[0315]

[0316] in:

[0317] R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are independently hydrogen, unsubstituted C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 A hydrocarbon group, a heteroatom, a group containing a heteroatom, or R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Two or more of are joined together to form a cyclic or polycyclic ring structure, or a combination thereof; and

[0318] M, T, X 1 , X 2 , R 1 , R 2 and R 4 -R 13 Described above.

[0319] In some embodiments, R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are independently hydrogen, halogen, unsubstituted C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 Hydrocarbyl, unsubstituted C 4 -C62 Aryl, substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 ,-PR' 2 or -R"-SiR' 3 , where R' is C 1 -C 10 alkyl and R' are each hydrogen, halogen, C 1 -C 10 Alkyl, or C 6 -C 10 Aryl. For example, R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are independently hydrogen, substituted C 1 -C 20 Hydrocarbon, or unsubstituted C 1 -C 20 Hydrocarbyl, such as substituted C 1 -C 12 Hydrocarbon or unsubstituted C 1 -C 12 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as substituted C 1 -C 6 Hydrocarbon, or unsubstituted C 1 -C 6 A hydrocarbon group (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 the may be joined to form a substituted or unsubstituted C 4 -C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0320] In at least one embodiment, the C1 symmetric bis-Cp metallocene catalyst can also be represented by a bridged substituted cyclopentadienyl and substituted indenyl catalyst precursor compound as represented by formula (C1d):

[0321]

[0322] in:

[0323] R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 are independently hydrogen, unsubstituted C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 A hydrocarbon group, a heteroatom, a group containing a heteroatom, or R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 Two or more of are joined together to form a cyclic or polycyclic ring structure, or a combination thereof; and

[0324] M, T, X 1 , X 2 , R 1 , R 2 , and R 4 -R 13 Described above.

[0325] In some embodiments, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 are independently hydrogen, halogen, unsubstituted C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 Hydrocarbyl, unsubstituted C 4 -C 62 Aryl, substituted C 4 -C 62 Aryl, unsubstituted C 4 -C 62 Heteroaryl, substituted C 4 -C 62 Heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR'3 ,-PR' 2 , or -R'-SiR' 3 , where R' is C 1 -C 10 alkyl and R' are each hydrogen, halogen, C 1 -C 10 Alkyl, or C 6 -C 10 Aryl. For example, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 are independently hydrogen, substituted C 1 -C 20 Hydrocarbon, or unsubstituted C 1 -C 20 Hydrocarbyl, such as substituted C 1 -C 12 Hydrocarbon or unsubstituted C 1 -C 12 Hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as substituted C 1 -C 6 Hydrocarbon, or unsubstituted C 1 -C 6 A hydrocarbon group (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 the may be joined to form a substituted or unsubstituted C 4 -C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0326] Useful examples of bridged C1 metallocenes for polyolefin production, particularly for propylene and diene polymerization and copolymerization, include, but are not limited to:

[0327]

[0328]

[0329] In other embodiments, the metallocene catalyst compound is represented by the formula:

[0330] T y Cp m MG n X q ,

[0331] wherein Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or a substituted or unsubstituted ligand isolobal to cyclopentadienyl, such as indenyl, fluorenyl and indacenyl. M is a Group 4 transition metal, such as Hf, Ti or Zr. G is a ligand of the formula JR * z represents a heteroatom group, wherein J is N, P, O or S, and R * Is linear, branched or cyclic C 1 -C 20 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 is equal to the oxidation state of the transition metal, preferably 2, 3 or 4, preferably 4.

[0332] 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. Preferably JR * z Groups include tert-butylamino (amido) and cyclododecylamino.

[0333] Preferred examples of the bridging group T include CH 2 , CH 2 CH 2 ,SiMe 2 ,SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 ,O,S,NPh,PPh,NMe,PMe,NEt,NPr,NBu,PEt,PPr,Me 2 SiOSiMe 2 , and PBu. In a preferred embodiment of the invention, in any embodiment of any formula described herein, T is of the formula ER d 2 or (ER d 2 ) 2 where E is C, Si or Ge, and R d are independently hydrogen, halogen, C 1 -C 20a hydrocarbon group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C 1 -C 20 substituted hydrocarbon group, and both R d Ring structures including aromatic, partially saturated, or saturated cyclic or fused ring systems may be formed.

[0334] X is each independently selected from a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a hydrogen group, an amino group, an alkoxy group, a thio group, a phosphorus group, a halide group, a diene group, an amine, a phosphine group, an ether group and combinations thereof, (two X groups may form a part of a fused ring or a ring system), preferably X is each independently selected from a halide group, an aryl group and a C 1 -C 5 The alkyl groups, preferably X, are each phenyl, methyl, ethyl, propyl, butyl, pentyl or chloro groups.

[0335] The single metallocene catalyst precursor compound may be selected from:

[0336] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)dimethyltitanium;

[0337] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride;

[0338] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium;

[0339] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride;

[0340] Dimethylsilyl(cyclopentadienyl)(l-adamantanylamino)M(R) 2 ;

[0341] Dimethylsilyl(3-tert-butylcyclopentadienyl)(l-adamantanylamino)M(R) 2 ;

[0342] Dimethylsilyl(tetramethylcyclopentadienyl)(l-adamantanylamino)M(R) 2 ;

[0343] Dimethylsilyl(tetramethylcyclopentadienyl)(l-adamantanylamino)M(R) 2 ;

[0344] μ-(CH 3 ) 2 C(Tetramethylcyclopentadienyl)(l-adamantanylamino)M(R) 2 ;

[0345] Dimethylsilyl(tetramethylcyclopentadienyl)(l-tert-butylamino)M(R) 2 ;

[0346] Dimethylsilyl(fluorenyl)(l-tert-butylamino)M(R) 2 ;

[0347] (Tetramethylcyclopentadienyl)(l-cyclododecylamino)M(R) 2 ;

[0348] μ-(C 6 H 5 ) 2 C(Tetramethylcyclopentadienyl)(l-cyclododecylamino)M(R) 2 ;and

[0349] Dimethylsilyl (η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamino)M(R) 2 ;

[0350] wherein M is selected from Ti, Zr and Hf; and R is each selected from halogen or C 1 To C 5 Alkyl (preferably chloro, bromo, methyl, ethyl, propyl, butyl, pentyl or an isomer thereof).

[0351] In at least one embodiment, the catalyst precursor compound can be a post-metallocene single site catalyst compound, such as a Group 3 to Group 12 transition metal directly bonded to at least two heteroatoms (e.g., O, N, P, S, CN, etc.) on at least one organic ligand via sigma and / or coordination bonds, optionally with a sigma bond between the carbon on the organic ligand and the transition metal center, such as:

[0352]

[0353] has a ligand with two nitrogen donors, forming an N-Hfσ bond and an N-Hf coordination bond, while It has a ligand having two nitrogen donors to form an N-Hfσ bond and an N-Hf coordination bond plus a C-Hfσ bond. Two of the at least two heteroatoms on the organic ligand can form a 4, 5, 6, 7, 8 or more membered ring with a transition metal center. For example, the two compounds above have a five-membered ring formed by two N and two C atoms on the ligand and the metal center; for example, the compound with the following formula has two six-membered rings formed by N, O, three C atoms and the metal center:

[0354]

[0355] (R 1 -R 5 are independently H or C 1 -C 20 An organic group, M is Ti, Zr or Hf, and X is a halide such as Cl or an alkyl such as Me); for example, the following two Hf compounds have two seven-membered rings plus one six-membered ring formed by two O and three or four C atoms on the ligand and the metal center:

[0356]

[0357] (Bz = benzyl); for example, the following three compounds have two eight-membered rings formed by the N, O and five C atoms on the ligand and the metal center:

[0358]

[0359] (M = Ti, Zr or Hf; X = halogen such as Cl or alkyl such as Bz, Me); etc.

[0360] It is also possible to use multiple catalyst precursors; for example, a bridged metallocene and an unbridged metallocene, a metallocene plus a monometallocene, a metallocene and a postmetallocene, or two postmetallocenes.

[0361] Catalyst system formation

[0362] Embodiments of the present disclosure include methods of preparing a catalyst system, comprising contacting an 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 may be a metallocene or post-metallocene catalyst precursor compound containing a Group 4 metal.

[0363] In at least one embodiment, the in situ supported MAO is heated prior to contacting with the catalyst precursor compound.

[0364] The in-situ loaded 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 separated as a solid-loaded MAO for subsequent use to prepare a finished catalyst. The catalyst precursor compound can also be added to the in-situ loaded MAO as a solid or as a slurry in an organic solvent. In at least one embodiment, the slurry of the in-situ loaded MAO is contacted with the catalyst precursor compound for a period of about 0.02 hours to about 24 hours, such as about 0.1 hours to 1 hours, 0.2 hours to 0.6 hours, 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0365] The mixture of the catalyst precursor compound and the in-situ supported MAO can be heated to about 30° C. to about 100° C., such as about 45° C. to about 70° C., or not heated, such as at room temperature. The contact time can be from about 0.02 hours to about 24 hours, such as from about 0.1 hours to 1 hour, 0.2 hours to 0.6 hours, 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

[0366] Useful organic solvents are materials in which all or part of the reactants used herein (e.g., in situ supported MAO and catalyst precursor compounds) are at least partially soluble (or suspended in the case of a solid support) and which are liquid at the reaction temperature. Non-limiting example solvents are those having the formula C n H (n+2) (wherein n is 3 to 30) non-cyclic alkanes such as propane, isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and having the formula C n H n (where n is 5 to 30) cycloalkanes, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc. Suitable organic solvents also include any mixture of the above. Although aromatic solvents such as benzene or toluene can also be used to prepare finished catalysts with good performance, they are not preferred because MAO that is not fixed on the support is more soluble in these solvents and can result in high levels of MAO residual in the supernatant, which needs to be removed before contacting the catalyst precursor compound to prepare the finished catalyst to avoid catalyst operability problems, and before the solvent can be used again.

[0367] If the in-situ loaded MAO is separated as a solid for subsequent use, to prepare a finished catalyst using the separated in-situ loaded MAO solid, a solvent can be loaded into the reactor, followed by the solid-loaded MAO. The catalyst precursor compound can then be loaded into the reactor, for example, as a solution in an organic solvent or as a solid. The mixture can be stirred at a certain temperature (e.g., room temperature). Additional solvent can be added to the mixture to form a slurry with a desired consistency, such as about 2cc / g of silica to about 20cc / g of silica, such as about 4cc / g. The solvent is then removed. The solvent is removed to dry the mixture and can be carried out under a vacuum atmosphere, purging with an inert atmosphere, heating the mixture, or a combination thereof. For heating the mixture, any suitable temperature for evaporating the organic solvent can be used. It should be understood that the reduced pressure under vacuum will reduce the boiling point of the organic solvent according to the pressure of the reactor. The solvent removal temperature can be from about 10°C to about 100°C, for example, from about 60°C to about 90°C, for example, from about 60°C to about 80°C, for example, about 75°C or lower, for example, about 65°C or lower. In at least one embodiment, removing the solvent comprises applying heat, applying a vacuum, and applying a nitrogen purge from the bottom of the container by bubbling nitrogen through the mixture. Drying the mixture.

[0368] Method for obtaining supernatant without TMA or with low TMA content

[0369] Embodiments of the present disclosure include methods of preparing an in situ supported MAO or derived finished catalyst system wherein the supernatant contains no free TMA or a low level of free TMA after forming the in situ supported MAO or derived finished catalyst, such that:

[0370] 1) Eliminate or reduce potential fouling factors caused by the reaction of free TMA in the supernatant with catalyst precursor compounds to form unsupported soluble low-activity species; and

[0371] 2) It enables direct reuse of the supernatant as a solvent without further treatment.

[0372] the term Feed TMA:water (or water:TMA) ratio Refers to the ratio of starting materials TMA and water charged into the in-situ sMAO formation reaction equipment. TMA: Water Uptake Ratio refers to an indirect measure of the ratio of TMA and feed water that react to form MAO molecules supported on silica, which is determined by the H of free TMA remaining in the supernatant after the in situ sMAO formation reaction. 1 The results were estimated by NMR quantification, since the water-reactive Al-Me units are more reactive than the OH units of the feed water (e.g., for a feed TMA:water ratio of 1.30:1, TMA (AlMe 3) is 1.30×3 equiv.=3.90 equiv. and the OH unit of water is 2 equiv.), by assuming that all water molecules are converted into MAO molecules, the TMA:water uptake ratio can be calculated as follows:

[0373] TMA:water uptake ratio = (feed TMA - residual TMA):feed water.

[0374] Method 1

[0375] For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, when the feed 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 at not higher than -8°C, such as -10±2°C, -12±4°C, -15±7°C, -20±12°C, or not higher than -8°C and not lower than -60°C, a TMA-free (H) can be obtained. 1 NMR) or having a TMA concentration of no greater than 600 ppm (using the H 1 NMR quantification) of in situ sMAO or derived supernatant of a finished catalyst slurry, as indicated in Table 2 entries 1-4. Although the data in Table 2 are generated from a catalyst prepared from a TMA concentration of about 20 wt % and a silica slurry of about 22 wt %, higher or lower concentrations of the two components may also be used, such as a TMA concentration of 30-80 wt % or 1-3 wt % and a silica slurry of 23-25 ​​wt % or 1-10 wt %. The silica slurry may also be added as a solid.

[0376] Method 2

[0377] For a carrier containing 5.0 (mmol / g carrier) or less absorbed water, when the feed 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 at not higher than -12°C, such as -14±2°C, -20±8°C, -30±18°C, or not higher than -12°C and not lower than -60°C, a TMA-free (H) can be obtained. 1 NMR) or having a TMA concentration of no greater than 600 ppm (using the H 1The supernatant of the finished catalyst slurry (quantitative by NMR) was prepared from a slurry of about 20 wt% TMA and about 22 wt% water-absorbed silica, as indicated in Table 2, entries 5-13. Although the data in Table 2 are generated from a catalyst prepared from a slurry of about 20 wt% TMA and about 22 wt% water-absorbed silica, higher or lower concentrations of the two components may also be used, such as 30 wt% to 80 wt% or 1 wt% to 3 wt% TMA concentration and 23 wt% to 25 wt% or 1 wt% to 10 wt% water-absorbed silica. The water-absorbed silica may also be added as a solid.

[0378] Method 3

[0379] For a carrier containing 7.0-10.0 (mmol / g carrier), such as 7.0, 7.5, 8.0, 9.0 or 10.0 (mmol / g silica) of absorbed water, when the feed TMA:water ratio is 1.20:1 or less, such as 1.15:1, and the in situ sMAO formation temperature is controlled to be no higher than -12°C or less, a TMA-free (not detectable by 1H NMR) or TMA concentration of no more than 600 ppm (using the H NMR method described in Example 22) can be obtained. 1 NMR quantification) of the supernatant of the finished catalyst slurry, provided that the higher the water content, the lower the cooling temperature required. For example, for 7.8 (mmol water / g carrier) loading, the sMAO formation temperature should be controlled at -12°C or lower, and for 9.0 (mmol water / g carrier) loading, the sMAO formation temperature should be controlled at -20°C or lower, as indicated in Table 2 entries 15-16. Although the Table 2 data are generated from a catalyst prepared from a TMA concentration of about 20 wt% and a silica slurry of about 22 wt% absorbed water, higher or lower concentrations of the two components may also be used, such as a TMA concentration of 30 wt% to 80 wt% or 1 wt% to 3 wt% and a silica slurry of 23 wt% to 25 wt% or 1 wt% to 10 wt% absorbed water. The silica absorbed water may also be added as a solid.

[0380] Method 4

[0381] In some in situ sMAO preparation cases, sMAO containing both supported MAO (e.g., siloxy-fixed MAO as summarized in Equation 4, Specimen C, which is the simplified structure C in the introductory section for the purpose of better chemical understanding) and unsupported MAO (unfixed free MAO, as summarized in Equation 4, Specimen A, which is the simplified structure A in the introductory section for the purpose of better chemical understanding) may need to be heated at higher temperatures (e.g., 85° C., 92° C., 100° C., or 110° C.), presumably to form MAO dimers to limit the soluble MAO portion of the derivatized catalyst used in the slurry polymerization to prevent MAO leaching fouling, presumably due to Specimen A becoming soluble in the solvent phase of the slurry polymerization medium. The heating step may result in the possible production of free TMA via Equation 3.

[0382]

[0383] Free TMA generated by heating can be removed by an additional matching amount of the same water-absorbed silica used to prepare the in situ sMAO and thus the overall feed TMA:water ratio reduced; for example, under the conditions of Method 2 (wherein the feed TMA:water is 1.42:1), adding an additional 5% water-absorbed silica to remove free TMA released by heating can reduce the feed TMA:water ratio, for example, to 1.35:1, or 1.31:1.

[0384] Method 5

[0385] Similar to method 4, but instead of adding additional absorbed water, silica with controlled hydroxyl residue calcined silica is added to remove free TMA remaining in the supernatant after in-situ sMAO formation, including TMA generated by heating. Silica calcined at 150°C-875°C can be used, and the amount is controlled so that the amount of reactive hydroxyl residue on the silica matches the amount of free TMA. Pristine silica can also be used but the amount of absorbed water on the silica can be quantified first, for example by Grignard titration or LOD (loss on drying) method to determine the active proton and TMA match.

[0386] Aggregation methods

[0387] In at least one embodiment of the present disclosure, the method includes polymerizing olefins to produce a polyolefin composition and obtaining a polyolefin composition by contacting at least one olefin with a catalyst system of the present disclosure. The polymerization can be carried out at a temperature of about 0° C. to about 300° C., at a pressure of about 0.35 MPa to about 10 MPa, and / or for a time of up to about 400 minutes.

[0388] Embodiments of the present disclosure include polymerization processes in which monomers (e.g., ethylene or propylene) and optional comonomers 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 the activator can be combined in any order, and are typically combined prior to contacting with the monomers.

[0389] Slurry polymerization and gas phase polymerization can be carried out in the presence of aliphatic hydrocarbon solvents / diluents / condensing agents (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably aromatic compounds 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).

[0390] In a preferred embodiment, the solvent / diluent used in the polymerization is not aromatic, preferably the aromatic compound is present in the solvent / diluent at less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0 wt % based on the weight of the solvent / diluent.

[0391] Monomers useful herein include substituted or unsubstituted C 2 -C 40 α-olefins, preferably C 2 -C 20 α-olefins, preferably C 2 -C 12 α-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and mixtures thereof. In a preferred embodiment, the olefin comprises a monomer which is propylene and one or more optional comonomers, the optional comonomers comprising one or more ethylene or C 4 -C 40 Olefins, preferably C 4 -C 20 Olefins, or preferably C 6 -C 12 Olefins. 4 -C 40 Olefin monomers can be linear, branched or cyclic. 4 -C 40 The cyclic olefins 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 comprises a monomer that is ethylene and an optional comonomer, the optional comonomer comprising C 3 -C 40Olefins, preferably C 4 -C 20 Olefins, or preferably C 6 -C 12 One or more of olefins. 3 -C 40 Olefin monomers can be linear, branched or cyclic. 3 -C 40 The cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may include heteroatoms and / or one or more functional groups.

[0392] Exemplary C 2 -C 40 Olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cyclohexene, 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-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and substituted derivatives thereof, preferably norbornene, norbornadiene and dicyclopentadiene.

[0393] In at least one embodiment, one or more dienes are present in the polymer produced herein at up to about 10 wt %, such as from about 0.00001 wt % to about 1.0 wt %, such as from about 0.002 wt % to about 0.5 wt %, such as from about 0.003 wt % to about 0.2 wt %, based on the gross weight of the composition. In at least one embodiment, about 500 ppm or less of diene is added to the polymerization, such as about 400 ppm or less, such as about 300 ppm or less. In at least one embodiment, at least about 50 ppm of diene is added to the polymerization, or about 100 ppm or more, or 150 ppm or more.

[0394] Diolefin monomers include any hydrocarbon structure having at least two unsaturated bonds, preferably C 4 -C 30, wherein at least two of the unsaturated bonds are easily incorporated into the polymer by stereospecific or non-stereospecific catalysts (one or more). It is further preferred that the diene monomers are selected from α, ω-diene monomers (i.e., diene monomers). In at least one embodiment, the diene monomers are linear diene monomers, such as those containing 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, eicosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, 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 polybutadiene (Mw less than 1000 g / mol). Non-limiting example cyclic dienes include cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing dienes with or without substituents at various ring positions.

[0395] In at least one embodiment, where butene is a comonomer, the butene source may be a mixed butene stream containing various butene isomers. 1-Butene monomer is expected to be consumed preferentially by the polymerization process compared to other butene monomers. Since these mixed streams are often waste streams from refinery processes, for example, C 4 The raffinate stream may therefore be much cheaper than pure 1-butene, and thus the use of such a mixed butene stream would provide an economic benefit.

[0396] The polymerization process of the present disclosure can be carried out in any suitable manner. Any suitable slurry or gas phase polymerization process can be used. Such a process can be operated in batch, semi-batch or continuous mode.

[0397] Preferably, the polymerization can be run at any temperature and / or pressure suitable for obtaining the desired polyolefin. Common temperatures and / or pressures include temperatures from about 0°C to about 300°C, such as from about 20°C to about 200°C, such as from about 35°C to about 150°C, such as from about 40°C to about 120°C, such as from about 65°C to about 95°C; and from about 0.35MPa to about 10MPa, such as from about 0.45MPa to about 6MPa, or preferably from about 0.5MPa to about 4MPa.

[0398] In typical polymerizations, 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.

[0399] Hydrogen can be added to reactor to control the molecular weight of polyolefin.In at least one embodiment, hydrogen is with about 0.001psig to 50psig (0.007kPa to 345kPa), for example about 0.01psig to about 25psig (0.07kPa to 172kPa), for example about 0.1psig to 10psig (0.7kPa to 70kPa) partial pressure is present in polymerization reactor.In one embodiment, add 600ppm or hydrogen still less, or add 500ppm or hydrogen still less, or 400ppm or still less or 300ppm or still less.In other embodiments, add at least 50ppm hydrogen, or 100ppm or more, or 150ppm or more.

[0400] In alternative embodiments, the activity of the catalyst is at least about 50 g / mmol / hour, such as about 500 or more g / mmol / hour, such as about 5000 or more g / mmol / hour, such as about 750000 or more g / mmol / hour, wherein the amount of metallocene is in the denominator. In alternative embodiments, the conversion of the olefin monomer is at least about 10%, based on the polymer yield (weight) and the weight of the monomer entering the reaction zone, such as about 20% or more, such as about 30% or more, such as about 50% or more, such as about 80% or more.

[0401] Preferably, the aluminoxane is present in a molar ratio of aluminum to transition metal of the catalyst compound of 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.

[0402] In a preferred embodiment, little or no scavenger is used in the method for producing the polyolefin composition. Preferably, the scavenger (e.g., trialkylaluminum) is present at zero mole %. Alternatively, the scavenger is present at a molar ratio of less than about 100:1, such as less than about 50:1, such as less than about 15:1, such as less than about 10:1 of the scavenger metal to the transition metal of the catalyst.

[0403] In a preferred embodiment, the polymerization: 1) is 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) is 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) wherein the catalyst system used in the polymerization has a molar ratio of aluminum to the 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 comprises aluminoxane; 4) polymerization preferably occurs in one reaction zone; 5) the productivity of the catalyst compound is at least 80,000 g / mmol / hr (preferably at least 150,000 g / mmol / hr, preferably at least 200,000 g / mmol / hr, preferably at least 250,000 g / mmol / hr, preferably at least 300,000 g / mmol / hr); 6) there is optionally no (for example, present at zero mole %) scavenger (for example, a trialkylaluminum compound). Alternatively, the scavenger is present in 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 a container in which polymerization occurs, such as a batch reactor. When multiple reactors are used in either a series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerization in both batch reactors and continuous reactors, each polymerization stage is considered a separate polymerization zone. Polymerization can occur in one or more reaction zones.

[0404] Other additives may also be used in the polymerization as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, alkyl aluminum or silane.

[0405] The chain transfer agent may be an alkylaluminoxane having the formula AlR 3 ,ZnR 2 (wherein each R is independently C 1 -C 8An aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or isomers thereof), or a combination thereof, for example diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

[0406] Gas Phase Polymerization: Gas phase polymerization processes may be used herein. Generally, in a fluidized gas bed process for producing polymers, a gas stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. The gas stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn 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 fully incorporated herein by reference).

[0407] Slurry phase polymerization: Slurry phase polymerization methods can be used herein. Slurry polymerization methods are generally operated at a pressure range of 1 to about 50 atmospheres (15psi to 735psi, 103kPa to 5068kPa) or even greater and at a temperature of 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 monomers and comonomers are added together with a catalyst. The suspension containing the diluent is intermittently or continuously removed from the reactor, wherein the volatile components are separated from the polymer and the volatile components are optionally recycled to the reactor after distillation. The liquid diluent employed in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid and relatively inert under the conditions of polymerization. When a propane medium is used, the method should operate above the critical temperature and pressure of the reaction diluent. Preferably, a hexane or isobutane medium is employed. In other embodiments, the diluent is not aromatic, preferably aromatic compounds 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 employed.

[0408] Polyolefin products

[0409] The present disclosure also relates to polyolefin compositions, such as resins, produced by the catalyst systems of the present disclosure.The polyolefins of the present disclosure may contain no detectable aromatic solvents.

[0410] In at least one embodiment, the process comprises using a catalyst system of the present disclosure to produce a propylene homopolymer or propylene copolymer, such as propylene-ethylene and / or propylene-α-olefin (preferably C 3 -C 20 ) copolymers (e.g., propylene-hexene copolymers or propylene-octene copolymers).

[0411] In at least one embodiment, the process comprises using the catalyst system of the present disclosure to produce olefin polymers, preferably polyethylene and polypropylene homopolymers and copolymers. In at least one embodiment, the polymer produced herein is a homopolymer of ethylene or a copolymer of ethylene, which preferably has from about 0 mol % to 25 mol % of one or more C 3 -C 20 Olefin comonomer (e.g., about 0.5 mol % to 20 mol %, such as about 1 mol % to about 15 mol %, such as about 3 mol % to about 10 mol %). The olefin comonomer may be C 3 -C 12 α-olefins, such as propylene, butene, hexene, octene, decene or dodecene, preferably one or more of propylene, butene, hexene or octene. The olefin monomer can be ethylene or C 4 -C 12 The α-olefin is preferably ethylene, butene, hexene, octene, decene, or dodecene, preferably one or more of ethylene, butene, hexene, or octene.

[0412] The polymers produced herein can have a Mw of about 5000 g / mol to about 1000000 g / mol (e.g., about 25000 g / mol to about 750000 g / mol, for example, about 50000 g / mol to about 500000 g / mol), and a Mw / Mn of about 1 / or to about 40 (e.g., about 1.2 to about 20, for example, about 1.3 to about 10, for example, about 1.4 to about 5, for example, about 1.5 to about 4, for example, about 1.5 to about 3), as determined by GPC-4D as described in the Experimental section below.

[0413] The polyolefin produced herein contains 0 ppm aromatic hydrocarbons. Preferably, the polyolefin produced herein contains 0 ppm toluene.

[0414] Experimental Materials

[0415] Chemicals: Trimethylaluminum was purchased from Sigma Aldrich (St. Louis, MO) or AkzoNobel (now Nouryon) and used as received unless otherwise indicated. Spray-dried silica ES70 TMDM-L403, a non-spray dried silica, was purchased from PQ Corporation (now Ecovyst) and was purchased from AGC Chemicals. ES70X and ES70 are ES70 that has been calcined at either 200°C, 400°C, or 875°C for 4 hours. TM Silica. DM-L403 silica was calcined at 200°C for 4 hours. The silica parameters provided by the vendor are summarized below:

[0416] Table 1. Silica parameters

[0417]

[0418] Before use, dry with N 2 Isohexane (in-house factory grade solvent) and heptane (purchased from Sigma Aldrich, anhydrous grade) were bubbled and then stored in a container (containing 5 wt%-10 wt% molecular sieves) with activated 3 angstrom molecular sieves for at least overnight. The water used was laboratory deionized water. All reactions were carried out under an inert nitrogen atmosphere unless otherwise indicated. All deuterated solvents were obtained from Cambridge Isotopes (Cambridge, MA) and dried over 3 angstrom molecular sieves before use.

[0419] Equipment: Ace Glass 600 mL and 4 L jacketed filter reactor with Lauda cooler with Kryo 20 coolant (which can control the temperature in the range of -30°C to 150°C). The silica slurry absorbed with water was charged into a well-sealed 600 mL reactor and was cooled by Teflon tubing through a needle valve using positive N 2 An additional pressure controlled rate meter was added to the 4 L reactor.

[0420] In situ supported MAO silica calcined at 200°C, 400°C, or 875°C with water loadings ranging from 4.3-9.1 mmol / g and feed TMA:water ratios ranging from 12.7:1 to 1.31:1 were used to study TMA residual in the supernatant (Table 2). Three metallocene catalyst precursor compounds representing different ligand structures and different metal centers were used to prepare the finished catalysts to compare activity: non-bridged zirconocene, bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (M1); bridged zirconocene, dimethylsilyl-bis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl (M2), and non-bridged hafnocene, bis(propylcyclopentadienyl)hafnium dimethyl (M3). M1 has good solubility in aliphatic solvents, while the M2 and M3 dichloride variants are significantly more insoluble. Their methylated versions have higher solubility in the preferred aliphatic solvents and are therefore used.

[0421] Table 2. sMAO formation conditions, supernatant TMA content, and finished catalyst activity

[0422]

[0423]

[0424] 1 The standard catalysts were M1, M2 and M3 metallocenes supported on the same silica-derived supported conventional MAO (WR Grace 30% MAO in toluene) with a MAO loading of 6.2 mmol Al / g silica to provide activities of 2912, 3389 and 6294 g / gcat / hr, respectively; 2 Prior to heating, heat is applied to the solid.

[0425] Example 1 (M3, ES70 silica calcined at 400°C, in-situ sMAO solid heated at 92°C)

[0426] 1. In a dry box, each of 3 bottles (1 L capacity) was filled with 100 g of silica ES70 (400°C), 360 g of isohexane, and 11.7 g of water. The 3 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 sealed with electrical tape. The 3 bottles were removed from the dry box and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were returned to the dry box.

[0427] 2. Charge 760 g of dry isohexane (3A molecular sieve overnight) into a 4 L reactor equipped with an anchor stirrer. Turn on the Lauda cooler and set the temperature controller to -30°C. Turn on the stirrer and set it to 170 rpm.

[0428] 3. After cooling the isohexane to -1°C, check the filter cap at the bottom of the reactor to ensure there are no leaks, and add 184.2 g (2.55 mol) of pure TMA to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1.

[0429] 4. While waiting for the TMA solution to reach -15°C, transfer the water absorbed silica slurry from 1 of the 3 bottles to the 600 mL reactor and cool it to about -5°C and stir to ensure good mixing.

[0430] 5. After the TMA solution temperature reaches -15°C, start adding the water absorbed silica at 250 rpm at a rate to maintain the reaction temperature between -9°C and -12°C.

[0431] 6. After addition of the silica slurry, stirring was adjusted to 170 rpm, the jacket temperature was increased to 1 °C and maintained for 30 minutes and then increased to ambient temperature.

[0432] 7. Stop stirring and remove the solvent through the bottom filter of the reactor under vacuum. The filtrate in THF-d8 (deuterated tetrahydrofuran) is obtained. 1 H-NMR spectrum and the spectrum did not show MAO or TMA.

[0433] 8. Dry the wet solids in a 4L jacketed filter reactor at ambient for 2 hours, then set the heating temperature to 100°C to bring the solids temperature to 92°C for 4 hours. Yield: 441.5 g.

[0434] 9. Slurry 1.0 g of sMAO from above in 4 g of isohexane in a 20 mL vial and then add 19.0 mg of M3 metallocene to it.

[0435] 10. The slurry was placed on a shaker to shake for 1 hour, the slurry was 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.

[0436] Example 2 (M3, ES70 silica calcined at 200°C, in-situ sMAO slurry heated at 92°C)

[0437] 1. In a drying oven, each of 3 bottles (1 L capacity) was filled with 100 g of silica ES70 (200° C.), 360 g of heptane, and 11.7 g of water. The 3 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 sealed with electrical tape. The 3 bottles were taken out of the drying oven and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were returned to the drying oven.

[0438] 2. Charge 760 g of dry heptane (3A molecular sieve overnight) into a 4 L reactor equipped with an anchor stirring blade. Turn on the Lauda cooler and set the temperature controller to -30°C. Turn on the stirrer and set it to 170 rpm.

[0439] 3. After cooling the heptane to -1°C, check the filter cap at the bottom of the reactor to ensure there are no leaks, and add 184.2 g (2.55 mol) of pure TMA to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1.

[0440] 4. While waiting for the TMA solution to reach -15°C, transfer the water absorbed silica slurry from 1 of the 3 bottles to the 600 mL reactor and cool it to about -5°C and stir to ensure good mixing.

[0441] 5. After the TMA solution temperature reaches -15°C, start adding the water absorbed silica at 250 rpm at a rate to maintain the reaction temperature between -9°C and -12°C.

[0442] 6. After addition of the silica slurry, stirring was adjusted to 170 rpm, the jacket temperature was increased to 1 °C and maintained for 30 minutes and then increased to ambient temperature.

[0443] 7. Stop stirring to allow the solid to settle. Obtain the filtrate in THF-d8 (deuterated tetrahydrofuran) 1 H-NMR spectrum and the spectrum did not show MAO or TMA.

[0444] 8. Turn the agitator back on and set at 170 rpm then heat the slurry by setting the heater to 96°C so that the reaction temperature is 92-93°C and maintain for 4 hours.

[0445] 9. After heating, the slurry was cooled to 25°C and the stirrer was increased to 300 rpm and 8.45 g of M3 metallocene was added.

[0446] 10. After adding M3, reduce the stirrer to 170 rpm for 2 hours.

[0447] 11. The slurry was filtered, washed with 2 x 1 L isohexane and then dried overnight at ambient under vacuum. Yield: 445.5 g. The catalyst was tested for gas phase ethylene polymerization using the procedure described in Example 22 in a 2 L autoclave salt bed reactor.

[0448] Example 3 (M3, ES70 silica calcined at 200°C, in-situ sMAO slurry heated at 65°C)

[0449] 1. In a drying oven, each of 3 bottles (1 L capacity) was filled with 100 g of silica ES70 (200° C.), 360 g of heptane, and 11.7 g of water. The 3 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 sealed with electrical tape. The 3 bottles were taken out of the drying oven and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were returned to the drying oven.

[0450] 2. Charge 715 g of dry heptane (3A molecular sieve overnight) into a 4 L reactor equipped with an anchor stirring blade. Turn on the Lauda cooler and set the temperature controller to -30°C. Turn on the stirrer and set it to 200 rpm.

[0451] 3. After cooling the heptane to -1°C, check the filter cap at the bottom of the reactor to ensure there are no leaks, and add 184.2 g (2.55 mol) of pure TMA to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1.

[0452] 4. While waiting for the TMA solution to reach -15°C, transfer the water absorbed silica slurry from 1 of the 3 bottles to the 600 mL reactor and cool it to about -5°C and stir to ensure good mixing.

[0453] 5. After the TMA solution temperature reaches -15°C, start adding the water absorbed silica at 300 rpm at a rate to maintain the reaction temperature at -9°C to -12°C.

[0454] 6. After addition of the silica slurry, stirring was adjusted to 200 rpm, the jacket temperature was increased to 1 °C and maintained for 30 minutes and then increased to ambient temperature.

[0455] 7. The slurry was then heated by setting the heater to 68°C so that the reaction temperature was about 65°C and maintained for 4 hours.

[0456] 8. The temperature was then lowered to ambient temperature (~21°C). Stirring was turned off to allow the solid to settle. The supernatant in THF-d8 (deuterated tetrahydrofuran) was obtained. 1H-NMR spectrum and the spectrum did not show MAO or TMA.

[0457] 9. Turn on the stirrer and set at 60 rpm overnight.

[0458] 10. Increase the stirrer to 300 rpm and add 8.84 g of M3 metallocene.

[0459] 11. After adding M3, reduce the stirrer to 200 rpm for 2 hours.

[0460] 12. The slurry was filtered, washed with 2 x 1 L isohexane and dried overnight under ambient vacuum. Yield: 459 g. The catalyst was tested for gas phase ethylene polymerization using the procedure described in Example 22 in a 2 L autoclave salt bed reactor.

[0461] Example 4 (M3, ES70 silica calcined at 400°C, in-situ sMAO slurry heated at 92°C)

[0462] 1. In a drying oven, each of 3 bottles (1 L capacity) was filled with 100 g of silica ES70 (400° C.), 360 g of heptane, and 11.7 g of water. The 3 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 sealed with electrical tape. The 3 bottles were taken out of the drying oven and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were returned to the drying oven.

[0463] 2. Charge 700 g of dry heptane (3A molecular sieve overnight) into a 4 L reactor equipped with an anchor stirring paddle. Turn on the Lauda cooler and set the temperature controller to -30°C. Turn on the stirrer and set it to 200 rpm.

[0464] 3. After cooling the heptane to -1°C, check the filter cap at the bottom of the reactor to ensure there are no leaks, and add 184.2 g (2.55 mol) of pure TMA to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1.

[0465] 4. While waiting for the TMA solution to reach -15°C, transfer the water absorbed silica slurry from 1 of the 3 bottles to the 600 mL reactor and cool it to about -5°C and stir to ensure good mixing.

[0466] 5. After the TMA solution temperature reaches -15°C, start adding the water absorbed silica at 300 rpm at a rate to maintain the reaction temperature at -9°C to -12°C.

[0467] 6. After addition of the silica slurry, stirring was adjusted to 200 rpm, the jacket temperature was increased to 1 °C and maintained for 30 minutes and then increased to ambient temperature.

[0468] 7. The slurry was then heated by setting the heater to 96°C so that the reaction temperature was 92°C-93°C and maintained for 4 hours.

[0469] 8. The temperature was then lowered to ambient temperature (~21°C). Stirring was turned off to allow the solid to settle. The supernatant in THF-d8 (deuterated tetrahydrofuran) was obtained. 1 H-NMR spectrum and the spectrum showed 170 ppm TMA.

[0470] 9. Turn on the stirrer and set at 60 rpm overnight.

[0471] 10. Increase the stirrer to 300 rpm and add 8.45 g of M3 metallocene.

[0472] 11. After adding M3, reduce the stirrer to 200 rpm for 2 hours.

[0473] 12. The slurry was filtered, washed with 2 x 1 L isohexane and dried overnight under ambient vacuum. Yield: 458.8 g. The catalyst was tested for gas phase ethylene polymerization using the procedure described in Example 21 in a 2 L autoclave salt bed reactor.

[0474] Example 5 (M3, ES70X silica calcined at 200°C, in-situ sMAO slurry heated at 92°C)

[0475] 1. In a drying oven, each of 3 bottles (1 L capacity) was filled with 100 g of silica ES70X (200° C.), 360 g of heptane, and 11.7 g of water. The 3 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 sealed with electrical tape. The 3 bottles were taken out of the drying oven and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were returned to the drying oven.

[0476] 2. Charge 760 g of dry heptane (3A molecular sieve overnight) into a 4 L reactor equipped with an anchor stirring blade. Turn on the Lauda cooler and set the temperature controller to -30°C. Turn on the stirrer and set it to 170 rpm.

[0477] 3. After cooling the heptane to -1°C, check the filter cap at the bottom of the reactor to ensure there are no leaks, and add 184.2 g (2.55 mol) of pure TMA to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1.

[0478] 4. While waiting for the TMA solution to reach -15°C, transfer the water absorbed silica slurry from 1 of the 3 bottles to the 600 mL reactor and cool it to about -5°C and stir to ensure good mixing.

[0479] 5. After the TMA solution temperature reaches -15°C, start adding the water absorbed silica at 250 rpm at a rate to maintain the reaction temperature between -9°C and -12°C.

[0480] 6. After addition of the silica slurry, stirring was adjusted to 170 rpm, the jacket temperature was increased to 1 °C and maintained for 30 minutes and then increased to ambient temperature.

[0481] 7. The slurry was then heated by setting the heater to 96°C so that the reaction temperature was 92°C-93°C and maintained for 5 hours.

[0482] 8. The temperature was then lowered to ambient temperature (~21°C). Stirring was turned off to allow the solid to settle. The supernatant in THF-d8 (deuterated tetrahydrofuran) was obtained. 1 H-NMR spectrum and the spectrum showed 270 ppm TMA.

[0483] 9. Turn the agitator back on and set at 170 rpm, add 8.63 g of the M3 catalyst precursor compound in one portion and stir the slurry for 2 hours.

[0484] 10. The slurry was then filtered, washed with 2 x 1 L isohexane and dried overnight at ambient vacuum. Yield: 471.5 g. The catalyst was tested for gas phase ethylene polymerization using the procedure described in Example 21 in a 2 L autoclave salt bed reactor.

[0485] Examples 6-21 (Preparation of finished catalysts from silica with different calcination temperatures and water contents and from M1 and M2 metallocenes)

[0486] The finished catalysts of Examples 6-15, 17-21 were prepared using a procedure similar to Example 5, and Example 16 was prepared using a procedure similar to Example 1, using the changes in Table 3:

[0487] Table 3. Preparation of finished catalysts of Examples 6-21

[0488]

[0489]

[0490] 1The standard catalysts were M1, M2, and M3 metallocenes supported on the same silica-derived supported conventional MAO (WR Grace 30% MAO in toluene) with a MAO loading of 6.2 mmol Al / g silica to provide activities of 2912, 3389, and 6294 g / gcat / hr, respectively; 2 Silica and water were charged to a 2L round bottom flask and sealed with a rubber septum and electrical tape; the round bottom flask was placed in a balance to record its weight, then placed in an oven set to 55°C to heat for 5 hr; the flask was removed from the oven and cooled to ambient temperature and weighed again to ensure there was no significant weight loss, then the solvent was added and mixed thoroughly; the slurry was then added to a 600 mL jacketed reactor in 3 equal portions.

[0491] Example 22 (Polymerization Test)

[0492] Laboratory scale 2 L salt bed gas phase polymerization reactor, where a 2 L autoclave reactor was heated to 110 °C and N 2 The purge was continued for at least 30 minutes. The reactor was charged with dry NaCl (350 g; Fisher, S271-10, dehydrated at 180°C before use and subjected to a pump / purge cycle and finally passed through a 16 mesh screen) and TIBAL treated silica (5 g at 105°C) and stirred for 30 minutes. The temperature was adjusted to 85°C. At 2 psig N 2 Dry and degassed 1-hexane (C6 ＝ , different volumes of different catalysts (see Table 4) were added to the reactor and then N 2 The reactor was charged to a pressure of 20 psig. While the bed was stirred, H 2 and N 2 The mixture flows into the reactor (pre-feed H 2 See Table 4; use N 2 10% H 2 The catalysts indicated in Table 4 below were reacted with ethylene (C2 ＝ ) are injected into the reactor together. ＝ flow to maintain a constant pressure in the reactor during the entire run. ＝ The ratio of H to ethylene is given in Table 4. 2 The same as C2 indicated in Table 4 ＝ The ratio of H to NH is sent to the reactor. H is measured by online GC analysis. 2 With C2 ＝Ratio. The polymerization was stopped after 1 hour by draining the reactor, cooling to about 23°C and exposing the reactor 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 two days. The catalyst activity is reported in Table 2 above.

[0493] Table 4. For gas phase ethylene (C2 ＝ )-Hexene(C6 ＝ ) 2L salt bed reactor for copolymerization

[0494]

[0495] Example 23 (H for quantification of TMA content in supernatant) 1 -NMR method)

[0496] A 5 mm NMR tube was charged with approximately 0.5 inch of the supernatant of interest and approximately 1 inch of THF-d8. The mixture was mixed thoroughly. H was obtained on a Brucker 400 MHz instrument using ns = 8 and D1 = 1 s. 1 NMR spectrum. 3 , CH 2 and CH 1 The solvent peaks of the signals (the -0.3 ppm to -2.5 ppm region including the THF-d8 1.73 ppm peak (too small to not subtract)) and TMA (a sharp singlet at -0.9 to -1.0 ppm) were integrated and the solvent integral was set to 1400 (for iC6, 14H) or 1600 (for heptane, 16H). If the integral of TMA is x, the TMA concentration y can be calculated as follows:

[0497] y = (72.1*x / 9) / (72.1*x / 9+86.2*100) for iC6 as solvent

[0498] y = (72.1*x / 9) / (72.1*x / 9+100.2*100) for heptane as solvent.

[0499] For example, Example 3 shows no TMA detected, while Example 4 shows TMA detected with an integral of 0.21; the concentration y in heptane is therefore:

[0500] y = 72.1*0.21 / 9 / (72.1*0.21 / 9+100.2*100) = 0.000168 or 168 ppm.

[0501] The Figure provides spectra showing TMA of Examples 3 and 4.

[0502] Example 24 (Preparation from Standard Catalyst of Supported Conventional MAO)

[0503] 10.0 g of ES70X (calcined at 600° C.) or ES70 (calcined at 875° C.) silica was added to a 100 mL cel-stir reactor along with 40 g of toluene. MAO (30% toluene solution from WR Grace) 12.4 g (62.0 mmol Al, 13.5 wt % or 5.0 mmol / g based on Al in the MAO solution) was slowly added to the slurry at ambient temperature. After adding MAO, the mixture was stirred at ambient temperature for 1 hour.

[0504] Solid supported MAO was isolated by filtering through a cartridge, washing with 2 x 40 g iC6, and drying under vacuum for 2 hours. Yield: 13.9 g.

[0505] M1 finished catalyst (sMAO on ES70X (600°C)): 2.0 g sMAO from the above procedure was charged into a 20 mL vial, followed by 8 g toluene. 35 mg (40 μmol / g sMAO) M1 was mixed with the slurry and then shaken on a shaker for 1 hour. The solid supported catalyst was separated by filtration through a cartridge, washed with 2×10 g iC6, and dried under vacuum for 1 hour. Yield: 2.0 g.

[0506] M2 finished catalyst (sMAO on ES70X (600°C)): 2.0 g sMAO from the above procedure was charged into a 20 mL vial, followed by 8 g toluene. 33 mg (35 μmol / g sMAO) M2 was mixed with the slurry and then shaken on a shaker for 1 hour. The solid supported catalyst was separated by filtration through a cartridge, washed with 2×10 g iC6, and dried under vacuum for 1 hour. Yield: 2.0 g.

[0507] M3 finished catalyst (sMAO on ES70 (875°C)): 2.0 g sMAO from the above procedure was charged into a 20 mL vial, followed by 8 g toluene. 38 mg (45 μmol / g sMAO) M3 was mixed with the slurry and then shaken on a shaker for 1 hour. The solid supported catalyst was separated by filtration through a cartridge, washed with 2×10 g iC6, and dried under vacuum for 1 hour. Yield: 2.0 g.

[0508] All documents described herein are incorporated herein by reference, including any priority documents and / or testing procedures, as long as they are not inconsistent with this document. As is apparent from the above general description and specific embodiments, although some embodiments have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not intended to limit the present disclosure thereby. Likewise, the term "comprising" is considered to be synonymous with the term "including". Likewise, whenever there is a transitional wording "comprising" before a composition, element or element group, it should be understood that we also consider the same composition or element group with a transitional wording "essentially consisting of...", "consisting of...", "selected from a group comprising...", or "is", and vice versa.

Claims

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 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 feed TMA to water ratio and the in situ sMAO formation temperature are controlled such that the supernatant after in situ supported MAO formation and optional heating or after finished catalyst formation contains no detectable TMA or no more than 600 ppm TMA, provided that, a. For a carrier containing 6.5 (mmol / g carrier) or less absorbed water, the feed 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 at -8°C to -60°C, b. For a support containing 5.0 (mmol / g support) or less absorbed water, the feed 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 in the range of -8°C to -60°C, and c. For supports containing 7.0-10.0 (mmol / g support) of absorbed water, the feed TMA:water ratio was controlled in the range of 1.20:1 to 1.15:1 and the in situ sMAO formation temperature was controlled in the range of -12°C to -60°C.

2. 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 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, wherein the ratio of TMA to water is from 1.80:1 to 1.42:1 and the in situ supported MAO formation temperature is from -6°C to -60°C; and Free TMA is recovered from the supernatant and removed by adding a second support containing hydroxyl groups to the supernatant after in situ supported MAO formation or after finished catalyst formation to result in no detectable TMA or no TMA above 600 ppm in the supernatant.

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

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

5. The process according to any one of claims 1 to 4, wherein at least one catalyst precursor compound having a metal atom of Group 3 to Group 12 or a lanthanide series metal atom comprises at least one substituted or unsubstituted cyclopentadienyl ligand to form a bridged or non-bridged monometallocene or metallocene.

6. The process according to any one of claims 1 to 4, wherein at least one catalyst precursor compound having a metal atom of Group 3 to Group 12 or a lanthanide series metal atom comprises at least one organic ligand having at least two heteroatom donors.

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

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

Images