Toluene-free supported methylaluminoxane precursors

Abstract

The present disclosure relates to a precursor for preparing an activator in a catalyst system for olefin polymerization and a process for producing the precursor, the catalyst system, and a polyolefin. In at least one embodiment, the aluminoxane precursor comprises (i) a reaction product of at least one non-hydrolyzable oxygen-containing compound and at least one hydrocarbyl aluminum; and (ii) an aliphatic hydrocarbon fluid. The reaction product can be formed by reacting the non-hydrolyzable oxygen-containing compound and the hydrocarbyl aluminum in the presence of the aliphatic hydrocarbon fluid. 1 The first set of signals in the region from about 4.5 ppm to about 5.1 ppm and the second set of signals in the region from about 5.1 ppm to about 6.5 ppm in the H NMR spectrum are confirmed. The ratio of the first set of signals to the second set of signals is greater than or equal to about 2.8. The aluminoxane precursor is susceptible to storage and transportation compared to MAO, which is an intermediate product in a conventional process for forming supported aluminoxanes.

Description

[0001] Inventor : Francis C. Rix, Ky KALe, Charles J. Harlan

[0002] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 117,312, filed November 23, 2020, the disclosure of which is incorporated herein by reference. Technical Field

[0003] This disclosure relates to a precursor for preparing an activator in a catalyst system for olefin polymerization and a method for producing the precursor, the catalyst system, and the polyolefin formed from the catalyst system. Background Technology

[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 examples of commercially available polyolefins. Polyolefins are typically prepared using catalysts (mixed with one or more other components to form a catalyst system) that promote the polymerization of olefin monomers in reactors such as gas-phase reactors.

[0005] Methylaluminoxane (MAO) is a commonly used activator that can be supported on silica to activate single-point catalyst precursors, such as metallocenes, to form active solid catalysts for the production of single-point polyolefin resins in commercial gas-phase reactors. Commercial MAO is typically sold as a toluene solution because aromatic solvents can dissolve MAO without causing any of the problems observed with other solvents. However, polyolefin products are commonly used as plastic packaging for food, and the amount of non-polyolefin compounds such as toluene present in polyolefin products should be minimized.

[0006] Furthermore, the preparation of MAO is challenging. MAO is typically formed by the low-temperature reaction of trimethylaluminum (TMA) and water in toluene. This reaction is highly exothermic and requires extremely careful control. Commercially available MAO has a short shelf life, typically less than one week under ambient conditions and less than twelve months under refrigeration, and even under refrigeration, MAO undergoes compositional changes, such as gelation.

[0007] Therefore, a more stable MAO activator is needed. Methods for forming such a MAO activator and a catalyst system including the MAO activator are also required.

[0008] References cited in the Disclosure Statement (37 CFR 1.97(h)): US 5,777,143, US 5,831,109, US 6,013,820, US 7,910,764, US 8,404,880, US 9,505,788, US 10,323,047, US2002 / 0177685; US 2003 / 0191254; US 2009 / 0088541; US ​​2012 / 0071679; US 2013 / 0029834; US 2013 / 0345376; US 2015 / 0315308; US 2016 / 0340496; US 2019 / 0127497, US 2019 / 0127499, US 2019 / 0330139; US 2019 / 0330246; US 2019 / 0330392; WO 2016 / 170017; Hlatky, G. (2000) “Heterogeneous Single-Site Catalysts for Olefin Polymerization,” Chem. Rev., Vol. 100, pp. 1347-1376; Fink, G. et al. (2000) “Propene Polymerization with Silica-Supported Metallocene / MAO Catalysts for propylene polymerization using silica-supported metallocene / MAO catalysts,” Chem. Rev., Vol. 100(4), pp. 1377-1390; Severn, JR et al. (2005) “Bound but Not Gagged”-Immobilizing Single-Site α-Olefin Polymerization Catalysts,” Chem. Rev., Vol. 105, pp. 4073-4147; Zjilstra, HS et al. (2015) “Methylalumoxane – History, Production, Properties, and Applications,” Eur. J. Inorg. Chem., Vol. 2015(1), pp. 19-43; Imhoff, DWGhiotto et al. (1998) “Characterization of Methylaluminoxanes and Determination of Trimethylaluminum Using Proton NMR,” Organometallics, Vol. 17(10), pp. 1941-1945; Ghiotto, F. et al. (2013) “Probing the Structure of Methylalumoxane (MAO) by a Combined Chemical, Spectroscopic, Neutron Scattering, and Computational Approach,” Organometallics, Vol. 32(11), pp. 3354-3362; Collins, S. et al. (2017) “Activation of Cp2ZrX2(X=Me,Cl) by Methylaluminoxane As Studied by Electrospray Ionization Mass Spectrometry: Relationship to Polymerization Catalysis, “Electrospray Ionization Mass Spectrometry: Relationship to Polymerization Catalysis of Cp2ZrX2 (X = Me, Cl) Activated by Methylaluminoxanes,” Macromolecules, Vol. 50(22), pp. 8871-8884; Dalet, T. et al. (2004) “Non-Hydrolytic Route to Aluminoxane-Type Derivative for Metallocene Activation towards Olefin Polymerization,” Macromol. Chem. and Phys., Vol. 205(10), pp. 1394-1401; Meisters, A. and Mole, T.(1974) "Exhaustive C-methylation of carboxylic acids by trimethylaluminium: A new route to t-butyl compounds," *Aust. J. Chem.*, Vol. 27(8), pp. 1665-1672; Kilpatrick, AFR et al. (2016) "Synthesis and Characterization of Solid Polymethylaluminoxane: A Bifunctional Activator and Support for Slurry-Phase Ethylene Polymerization," *Chem. Mater.*, Vol. 28, pp. 7444-7450. Summary of the Invention

[0009] This disclosure relates to methods and compositions for preparing activators in catalyst systems for olefin polymerization, as well as methods for producing precursors, the catalyst system, and polyolefins formed from the catalyst system.

[0010] In at least one embodiment, the composition comprises (i) at least one compound containing non-hydrolyzable oxygen and at least one hydrocarbon-based aluminum reaction product; and (ii) an aliphatic hydrocarbon fluid, wherein the molar ratio of aluminum to non-hydrolyzable oxygen in the composition is greater than or equal to 1.5, wherein the composition has a... 1 The first group of signals in the H NMR spectrum in the region from about 4.5 ppm to about 5.1 ppm and in 1 The composition contains a second group of signals in the region from about 5.1 ppm to about 6.5 ppm in the H NMR spectrum, wherein the ratio of the first group of signals to the second group of signals is greater than or equal to about 2.8, and wherein the composition comprises an aliphatic hydrocarbon fluid from about 1 wt% to about 50 wt% based on the total weight of the composition. Attached Figure Description

[0011] Figure 1 It is the catalyst precursor prepared in Comparison 1 1 Vinyl region of H NMR (C6D6) spectrum.

[0012] Figure 2 The concentrated precursor prepared in Example 6a is described. 1 Vinyl region of H NMR (C6D6) spectrum.

[0013] Figure 3 The concentrated precursor prepared in Example 6a is described. 1 H NMR (C6D6) spectrum.

[0014] Figure 4 The concentrated precursors prepared in Example 6a before and after the addition of the semi-alkoxide Me2Al(μ-Me)(μ-OCMe2CMe=CH2)AlMe2 are depicted. 1 Vinyl region of H NMR (C6D6) spectrum.

[0015] Figure 5 The X-ray crystallographic spectrum (Oak Ridge Thermal Ellipsoid Plot) of [Me2Al(μ-O2CCMe=CH2)]2 prepared in Example 16a is depicted.

[0016] Figure 6 The [Me2Al(μ-O2CCMe=CH2)]2 prepared in Example 16a is described. 1 H NMR (C6D6) spectrum.

[0017] Figure 7 The precursor stability test corresponding to the sample AC performed in Example 17 is described. 1 H NMR (C6D6) spectrum.

[0018] Figure 8 The precursor stability test corresponding to the sample DF performed in Example 17 is described. 1 H NMR (C6D6) spectrum.

[0019] Figure 9 The precursor stability test corresponding to the sample GI performed in Example 17 is described. 1 H NMR (C6D6) spectrum. Detailed Implementation

[0020] This disclosure relates to methods and compositions (e.g., precursors) for preparing activators in catalyst systems for olefin polymerization, as well as methods for producing precursors, the catalyst system, and polyolefins formed from the catalyst system.

[0021] For the purposes of this disclosure, the periodic table group numbering scheme as described below is used: Chemical and Engineering News, Vol. 63(5), p. 27 (1985). Thus, “Group 4 metals” are elements from Group 4 of the periodic table, such as Hf, Ti, or Zr.

[0022] As used herein, "composition" may include components of the composition and / or one or more reaction products of those components.

[0023] "Catalyst productivity" is a measure of how many grams of polymer (P) are produced over a time period T hours using a polymerization catalyst containing W g of catalyst (cat); and can be expressed by the following formula: P / (T×W), where gPgcat. -1 hr -1 The units are expressed as follows: "Conversion" is the amount of monomer converted into the polymer product and is reported as a mole percentage (mol%), calculated based on the polymer yield (by weight) and the amount of monomer fed into the reactor. "Catalyst activity" is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat h). To calculate catalyst activity (also known as catalyst productivity), only the weight of the transition metal component of the catalyst is used.

[0024] "Olefin," or alternatively "alkene," is a straight-chain, branched, or cyclic compound having at least one double bond between carbon and hydrogen. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is a polymeric form of an olefin. For example, when a copolymer is said to have a "ethylene" content of 35 wt% to 55 wt%, it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and said derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. Thus, as used herein, the definition of a copolymer includes terpolymers, etc. The term "different" used to refer to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene-derived units, "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene-derived units, and so on.

[0025] As used herein, and unless otherwise stated, the term "C" n "This refers to a hydrocarbon with n carbon atoms per molecule, where n is a positive integer."

[0026] The term "hydrocarbon" refers to a class of compounds containing hydrogen atoms bonded to carbon, and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds with different n values. Similarly, a "Cm-Cy" group or compound refers to a group or compound containing a total number of carbon atoms ranging from m to y. Therefore, C1-C 50 Alkyl groups are alkyl groups that contain a total number of carbon atoms ranging from 1 to 50.

[0027] The terms "group", "radical", and "substituent" are used interchangeably.

[0028] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined as meaning a group consisting only of hydrogen and carbon atoms. Preferred hydrocarbyl groups are C1-C. 100 A functional group, which can be straight-chain, branched, or cyclic, and when cyclic, is aromatic or non-aromatic. Examples of such functional groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., and aryl groups such as phenyl, benzyl, naphthyl, etc.

[0029] Unless otherwise specified (e.g., the definition of "substituted hydrocarbon group"), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, heteroatom, or heteroatom-containing group, such as a halogen (such as Br, Cl, F, or I); or at least one functional group, such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2)q-SiR*3, etc., where q is 1 to 10, and each R* is independently hydrogen, hydrocarbon, or halocarbyl, and two or more R* may be linked together to form a fully saturated, partially unsaturated, or aromatic cyclic (or polycyclic) structure, substituted or unsubstituted, or where at least one heteroatom has been inserted into the hydrocarbon ring.

[0030] The term "substituted hydrocarbon group" means a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group has been replaced by at least one heteroatom (such as a halogen, e.g., Br, Cl, F or I) or a heteroatom-containing group (such as a functional group, e.g. -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2)q-SiR*3, etc.), where q is 1 to 10, and each R* is independently hydrogen, hydrocarbon group or halohydrocarbon group, and two or more R* may be linked together to form a fully saturated, partially unsaturated, or aromatic cyclic (or polycyclic) structure, substituted or unsubstituted, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0031] The terms "alkyl radical" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl" is defined as a C1-C group that can be straight-chain, branched, or cyclic. 100 Alkyl groups. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and their substituted analogs. A substituted alkyl group is a group in which at least one hydrogen atom of the alkyl group has been substituted by: at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom, or a heteroatom-containing group, such as a halogen (such as Br, Cl, F, or I); or at least one functional group, such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2)q-SiR*3, etc., wherein q is 1 to 10 and each R* is independently hydrogen, a hydrocarbon group, or a haloalkyl group, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic (or polycyclic) structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0032] The term "alkoxy" or "aryloxy" refers to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group (group / radical) attached to an oxygen atom, and may include groups in which the alkyl group is C1 to C2. 10 Those with hydrocarbon groups. Alkyl groups can be straight-chain, branched, or cyclic. Hydrocarbon groups can be saturated or unsaturated. Suitable examples of alkoxy and aryloxy groups can include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, etc.

[0033] The term "aryl" or "aryl group" refers to an aromatic ring (typically composed of 6 carbon atoms) and its substituted variants, such as phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which one of the ring carbon atoms (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O, or S. As used herein, the term "aromatic" also refers to a pseudoaromatic heterocycle, which is a heterocyclic substituent with similar properties and structure (nearly planar) to aromatic heterocyclic ligands, but is not aromatic by definition.

[0034] When isomers of a named alkyl, alkenyl, alkoxy, or aryl group (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are present, reference to one member of that group (e.g., n-butyl) should explicitly disclose the remaining isomers in the family (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, reference to an alkyl, alkenyl, alkoxy, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0035] Metallocene catalysts are transition metal catalysts having one, two, or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands bound to a transition metal. Typically, metallocene catalysts are organometallic compounds containing at least one π-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety). Substituted or unsubstituted cyclopentadienyl ligands include substituted or unsubstituted indole, fluorenyl, tetrahydro-s-indal, tetrahydro-as-indal, benzo[f]indole, benzo[e]indole, tetrahydrocyclopentadieno[b]naphthalene, tetrahydrocyclopentadieno[a]naphthalene, etc.

[0036] 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 percentage, and mol% is the molar percentage. Molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol (g mol) -1 ).

[0037] The following abbreviations may be used in this article: Me is methyl, MAA is methacrylic acid, TMA is trimethylaluminum, MAO is methylaluminoxane, TIBAL (also known as TIBA) is triisobutylaluminum, THF (also known as thf) is tetrahydrofuran, and RT is room temperature (and 23 degrees Celsius unless otherwise stated).

[0038] A “catalyst system” is a combination of at least one catalyst compound, at least one activator, optional co-activator, and optional support material. When used to describe such a pairing prior to activation, “catalyst system” means the unactivated catalyst complex (pre-catalyst) together with the activator and optional co-activator. When used to describe such a pairing after activation, it means the activated complex and the activator or other charge-balancing component. Transition metal compounds can be neutral, as in pre-catalysts, or charged with counterions, as in activated catalyst systems. For the purposes of this document, when a catalyst system is described as comprising a neutral, stable form of a component, those skilled in the art will fully understand that the ionic form of the component is the form in which it reacts with the monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers.

[0039] In the description herein, a catalyst may be described as a catalyst, catalyst precursor, precatalyst compound, catalyst compound, or transition metal compound, and these terms are used interchangeably.

[0040] For the purposes of this paper, particle size (PS) or diameter and its distribution were determined by laser diffraction using a MASTERSIZER 3000 (range 1 to 3500 μm) from Malvern Instruments, Ltd., Worcestershire, England, or an LS 13 320MW (range 0.4 to 2000 μm) with a microfluidic module from Beckman Coulter, Inc., Brea, California. Average PS refers to the distribution of particle volume relative to particle size.

[0041] For the purposes of this paper, the surface area (SA, also known as specific surface area or BET surface area), pore volume (PV), and pore size (PD) of the catalyst support material were determined by adsorption-desorption of nitrogen (liquid nitrogen temperature: 77 K) using the Brunauer-Emmett-Teller (BET) method and / or the Barrett-Joyner-Halenda (BJH) method, with a MICROMERITICS TRISTAR II 3020 instrument or a MICROMERITICS ASAP 2420 instrument, after degassing the raw material / calcined silica powder at 100°C to 300°C for 4 to 8 hours or degassing the silica-supported aluminoxane at 40°C to 100°C for 4 hours to overnight. More information about this method can be found, for example, in the following: “Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density,” S. Lowell et al., Springer, 2004. PV refers to total PV, including both internal and external PV.

[0042] One way to determine the spatial distribution of the aluminoxane or aluminoxane precursor disclosed herein within the pores of the support material composition is to determine the Al / Si ratio in the unground material versus the ground material, wherein the support material is a supported aluminoxane precursor, aluminoxane, or catalyst on silica. For example, when the support material composition is SiO2, the composition may have an unground (Al / Si) / ground (Al / Si) value from about 1 to about 4, such as from about 1 to about 3, such as from about 1 to about 2, such as about 1, as determined by X-ray photoelectron spectroscopy. As used herein, the term "ground" is defined as support material that has been ground into fine particles using a mortar and pestle. As used herein, the term "unground" is defined as material that has not been ground into fine particles using a mortar and pestle. To measure the unground (Al / Si) / ground (Al / Si) value, X-ray photoelectron spectra of the support material are obtained. The metal content of the outer surface of the support material is determined as wt% of the outer surface using the spectra. The catalyst system is then ground into fine particles using a mortar and pestle. Subsequent X-ray photoelectron spectroscopy (XPS) of the fine particles was obtained, and the metal content on the surface of the fine particles was determined as wt% using XPS. The determined wt% value of the uncrushed support material was divided by the wt% value of the pulverized supported aluminoxane precursor (i.e., fine particles) to provide an uncrushed / pulverized value. A value of 1 indicates a completely uniform metal distribution on the outer surface and within the void spaces of the catalyst system. A value greater than 1 indicates that the amount of metal on the outer surface of the support material composition is greater than the amount in the voids of the support material composition. A value less than 1 indicates that the amount of metal on the surface of the support material composition within the voids is greater than the amount of metal on the outer surface of the support material composition.

[0043] Aluminoxane precursor

[0044] In at least one embodiment, the aluminoxane precursor can be formed by combining at least one compound containing non-hydrolyzable oxygen with at least one hydrocarbon aluminum in an aliphatic hydrocarbon fluid acting as a solvent at a temperature of less than about 70 degrees Celsius.

[0045] In at least one embodiment, the at least one non-hydrolyzable oxygen-containing compound may comprise a compound represented by formula (I):

[0046]

[0047] Where R 1 and R 2 It is independently hydrogen or hydrocarbon group (preferably C1 to C2). 20 Alkyl, alkenyl, or C5 to C5 20 aryl, such as those selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), R 3It is a hydrocarbon group, optionally R 1 R 2 、or R 3 They can be connected together to form a loop, and R 4 It is -OH (hydroxyl group), -OC(O)CR 3 =CR 1 R 2 OCR 3 3. -F, or -Cl. In at least one embodiment, the at least one non-hydrolyzable oxygen-containing compound comprises an alkyl acrylic acid represented by the formula R*-C(=CH2)COOH, wherein each R* is C1 to C2. 20 Alkyl groups (such as those selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl). In at least one embodiment, the at least one non-hydrolyzable oxygen-containing compound comprises methacrylic acid. In at least one embodiment, the at least one non-hydrolyzable oxygen-containing compound comprises benzoic acid.

[0048] In at least one embodiment, the at least one non-hydrolyzable oxygen-containing compound may comprise a compound represented by formula (II):

[0049]

[0050] Where R 1 R 2 R 9 and R 10 It is either a hydrogen or hydrocarbon group; R 3 and R 8 It is a hydrocarbon group; optionally, R 1 R 2 、or R 3 They can be connected together to form a loop; optionally, R 8 R 9 、or R 10 They can be connected together to form a loop; and R 4 R 5 R 6 and R 7 Each of them is independently C2-C 20 Hydrocarbon group, methyl group, hydrogen group, or group containing heteroatoms. Typically, R... 4 R 5 R 6 and R 7 Each of them is a methyl group. Alternatively, it can be represented by R. 4 R 5 R 6 and R 7 At least three members of the group are methyl groups, such as R 4 R 5 and R6 or R 4 R 5 and R 7 Typically, compounds containing non-hydrolyzable oxygen comprise a variety of compounds represented by formula (II). In this regard, based on R in these various compounds... 4 R 5 R 6 and R 7 The total number of moles, R 4 R 5 R 6 and R 7 It contains at least about 85% methyl groups and up to about 15% C2-C groups. 20 The compound contains a hydrocarbon group or a heteroatom-containing group and up to about 10 mol% hydrogen. Preferably, the compound represented by formula (II) comprises the reaction product of trimethylaluminum (TMA) and an unsaturated carboxylic acid. In at least one embodiment, the compound is represented by formula (III).

[0051]

[0052] In some respects, stable compositions may be formed from compounds represented by formula (II). In such respects, based on the total weight of the composition, the composition may contain compounds represented by formula (II) in amounts greater than about 1 wt%, such as greater than about 50 wt%, or greater than about 75 wt%, or greater than about 90 wt%.

[0053] In at least one embodiment, the at least one hydrocarbon-based aluminum comprises that of formula R 1 R 2 R 3 Al represents the compound, where R 1 R 2 and R 3 Each of them is independently C1 to C2. 20 Alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl). Typically, this at least one alkyl aluminum group comprises a plurality of compounds of the aforementioned formula R. 1 R 2 R 3 Compounds represented by Al. In this regard, based on R in these various compounds. 1 R 2 and R 3 The total number of moles, R 1 R 2 and R 3 It contains at least about 85% methyl groups and up to about 15 mol% C1-C. 20The aluminum group consists of a hydrocarbon group or a heteroatom-containing group and hydrogen from 0 to 10 mol%. In at least one embodiment, the at least one hydrocarbon aluminum group comprises trimethylaluminum.

[0054] Typically, the at least one hydrocarbon-based aluminum is introduced in a concentration exceeding that of the at least one compound containing non-hydrolyzable oxygen. It is not intended to be theoretically constrained, but it is believed that adding a hydrocarbon-based aluminum in a concentration exceeding that of the compound containing non-hydrolyzable oxygen ensures that the surface of the support material particles described herein can be coated with both the aluminoxane precursor and the hydrocarbon-based aluminum to form a supported aluminoxane precursor. It is further believed that heating the supported aluminoxane precursor can cause the hydrocarbon-based aluminum to react with the aluminoxane precursor to form the supported aluminoxane described herein. Typically, the at least one hydrocarbon-based aluminum is introduced at a concentration such that the molar ratio of aluminum to non-hydrolyzable oxygen in solution is greater than or equal to 1.5. Typically, the at least one hydrocarbon-based aluminum can be introduced at a concentration greater than or equal to 3 molar equivalents of the at least one compound containing non-hydrolyzable oxygen. For example, the molar ratio of the at least one compound containing non-hydrolyzable oxygen to the at least one hydrocarbon-based aluminum can be from about 1:3 to about 1:9, such as from about 1:3 to about 1:5. Alternatively, in aspects where the at least one non-hydrolyzable oxygen-containing compound comprises a compound of formula (II) or (III), the at least one hydrocarbon aluminum is introduced at a concentration greater than or equal to 2 molar equivalents of the at least one non-hydrolyzable oxygen-containing compound. For example, in such aspects, the molar ratio of the at least one non-hydrolyzable oxygen-containing compound to the at least one hydrocarbon aluminum can be from about 1:2 to about 1:9, such as from about 1:2 to about 1:5. Typically, the molar ratio of the at least one hydrocarbon aluminum to the at least one non-hydrolyzable oxygen-containing compound is greater than or equal to [A*B+0.5(C*D)] / B, where A is 2 or 3; B is the number of moles of the non-hydrolyzable oxygen-containing compound; C is the number of moles of hydrocarbon aluminum per gram of carrier material chemisorbed onto the surface of the carrier material in the absence of the non-hydrolyzable oxygen-containing compound; and D is the number of grams of carrier material. In this respect, if the at least one non-hydrolyzable oxygen-containing compound comprises a compound represented by formula (II), then A is typically 2, and if the at least one non-hydrolyzable oxygen-containing compound comprises a compound represented by formula (I), then A is typically 3. Furthermore, in this respect, B / D is typically greater than or equal to about 1.5 mmol / g.

[0055] Typically, suitable aliphatic hydrocarbon fluids include those having a boiling point less than about 70 degrees Celsius, such as from about 20 degrees Celsius to about 70 degrees Celsius. The boiling point of the aliphatic hydrocarbon fluid may be lower than that of the hydrocarbon-based aluminum. In at least one embodiment, the boiling point of the aliphatic solvent is at least 40 degrees Celsius lower than that of the hydrocarbon-based aluminum, such as at least 50 degrees Celsius or at least 60 degrees Celsius lower. Suitable aliphatic hydrocarbon fluids include, but are not limited to, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred aliphatic hydrocarbon fluids may include n-alkanes (such as those available from ExxonMobil Chemical Company, Houston, Texas). Hydrocarbon fluids), isoparaffins (such as those available from ExxonMobil Chemical Company in Houston, Texas). Hydrocarbon fluids and combinations thereof. For example, aliphatic hydrocarbon fluids can be selected from C3 to C4. 12 Straight-chain, branched, or cyclic alkanes. In some embodiments, the aliphatic hydrocarbon fluid is substantially free of aromatic hydrocarbons. Preferably, the aliphatic hydrocarbon fluid is substantially free of toluene. Available aliphatic hydrocarbon fluids are ethane, propane, n-butane, 2-methylpropane, n-pentane, cyclopentane, 2-methylbutane, 2-methylpentane, n-hexane, cyclohexane, methylcyclopentane, 2,4-dimethylpentane, n-heptane, 2,2,4-trimethylpentane, methylcyclohexane, octane, nonane, decane, or dodecane, and mixtures thereof. In at least one embodiment, based on the weight of the hydrocarbon fluid, the aromatic compound is present in the aliphatic hydrocarbon fluid in amounts less than 1 wt%, such as less than 0.5 wt%, such as 0 wt%. In at least one embodiment, the aliphatic hydrocarbon fluid is n-pentane and / or 2-methylpentane.

[0056] The combination of the at least one hydrocarbon-based aluminum with the at least one compound containing non-hydrolyzable oxygen and a support material is typically carried out at a temperature below about 70 degrees Celsius. Typically, the combination can be carried out at the reflux temperature of the aliphatic hydrocarbon fluid. The reflux temperature is based on the boiling point of the aliphatic hydrocarbon fluid, such as from about 20 degrees Celsius to about 70 degrees Celsius or from about 25 degrees Celsius to about 70 degrees Celsius.

[0057] Typically, the at least one non-hydrolyzable oxygen-containing compound is combined with the at least one hydrocarbon-based aluminum before being combined with a support material. Generally, the at least one non-hydrolyzable oxygen-containing compound can be dissolved in an aliphatic hydrocarbon fluid before being combined with the at least one hydrocarbon-based aluminum, which can also be dissolved in an aliphatic hydrocarbon fluid. In this respect, the aliphatic hydrocarbon fluid in which the at least one non-hydrolyzable oxygen-containing compound and the at least one hydrocarbon-based aluminum are dissolved can be the same or different. In at least one embodiment, the aluminoxane precursor in solution can be prepared by adding a solution of methacrylic acid (MAA) in pentane to a solution of trimethylaluminum (TMA) in pentane at a rate sufficient to maintain controlled reflux (i.e., maintaining the reaction temperature at about 36.1 degrees Celsius, which is the boiling point of pentane). In this respect, MAA can be introduced into TMA at a molar ratio from about 1:3 to about 1:5. Generally, the effectiveness of the aluminoxane precursor as a catalyst activator and the activity of the resulting supported catalyst both increase with increasing TMA / MAA ratio.

[0058] Both concentrated and solution forms of aluminoxane precursors can be obtained through... 1 Characteristic spectral patterns in H NMR (C6D6) are used for identification. Typically, in 1 In the H NMR spectrum, a first set of signals exists in the region from approximately 4.5 ppm to approximately 5.1 ppm, and a second set of signals exists in the region from approximately 5.1 ppm to approximately 6.5 ppm. To avoid being bound by theory, it is assumed that the signal from 5.1 to 6.5 ppm represents bridging carboxylates (such as in...). Figure 5 The vinyl group in the dimer Me2Al(μ-O2CCMe=CH2)2AlMe2 shown is 4.5 to 5.1 ppm, while the signal indicates a bridged alkoxide such as Figure 4 The vinyl group of Me2Al(μ-Me)(μ-OCMe2CMe=CH2)AlMe2 shown is CH. Typically, very few bridging carboxylates are present in the precursor. For example, typically, the ratio of the first group signal to the second group signal is greater than or equal to about 2.8. It is not desirable to be bound by theory, but it is considered that the presence of carboxylates in the precursor is detrimental to the formation of MAO on the support.

[0059] carrier material

[0060] In the embodiments described herein, a carrier material may be used. In at least one embodiment, the carrier material is a porous carrier material, such as talc or an inorganic oxide. Other carrier materials include zeolite, clay, organoclay, or any other suitable organic or inorganic carrier material, or mixtures thereof.

[0061] In at least one embodiment, the support material is an inorganic oxide. Suitable inorganic oxide materials for the catalyst systems used herein include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina are magnesium oxide, titanium dioxide, zirconium oxide, etc. However, other suitable support materials can be used, for example, functionalized polyolefins, such as polypropylene. Support materials may include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, shale silicates, zeolites, talc, clay, etc. Additionally, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium dioxide, etc. Support materials may include Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica-clay, silica / clay, or mixtures thereof. However, other suitable support materials can be used, such as finely chopped functionalized polyolefins, such as finely chopped polyethylene, polypropylene, and polystyrene, which have water-absorbing functional groups, such as oxygen- or nitrogen-containing groups, such as -OH, -RC=O, -OR, and -NR2. Particularly useful supports include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, shale silicates, zeolite, talc, clay, silica clay, silica clay, etc. Additionally, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium dioxide, etc. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O2, silica clay, silica / clay, or mixtures thereof. The support material may be fluorinated.

[0062] As used herein, the phrases “fluorinated support” and “fluorinated support composition” refer to a support that has been treated with at least one inorganic fluorinated compound and is preferably particulate and porous. For example, a fluorinated support composition may be a silica support in which a portion of the hydroxyl groups in the silica has been replaced by fluorine or a fluorinated compound. Suitable fluorinated compounds include, but are not limited to, inorganic fluorinated compounds and / or organic fluorinated compounds.

[0063] Suitable fluorine compounds for providing fluorine to a support can be organic or inorganic fluorine compounds, and preferably inorganic fluorine-containing compounds. Such inorganic fluorine-containing compounds can be any compound containing fluorine atoms, provided they do not contain carbon atoms. Particularly desirable are inorganic fluorine-containing compounds selected from NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, NHF2, NH4HF2, and combinations thereof. In at least one embodiment, ammonium hexafluorosilicate and ammonium tetrafluoroborate are used.

[0064] In at least one embodiment, the carrier material comprises a carrier material treated with electron-withdrawing anions. The carrier material may be silica, alumina, silica-alumina, silica-zirconia, alumina-zirconia, aluminum phosphate, heteropolytungstate, titanium dioxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, or mixtures thereof; and the electron-withdrawing anion is selected from fluoride ions, chloride ions, bromide ions, phosphate ions, trifluoromethanesulfonate ions, bisulfate ions, sulfate ions, or any combination thereof.

[0065] Electron-withdrawing components can be used to treat carrier materials. The electron-withdrawing component can be any component that increases the Lewis or Brønsted acidity of the carrier material after treatment (e.g., compared to carrier materials 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 such as a volatile organic compound (which serves as a source or precursor of the anion). Electron-withdrawing anions can be sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, phosphotungstenate, or mixtures thereof, or combinations thereof. In at least one embodiment of this disclosure, the electron-withdrawing anion can be fluoride, chloride, bromide, phosphate, trifluoromethanesulfonate, bisulfate, or sulfate, or any combination thereof. In at least one embodiment, the electron-withdrawing anion is sulfate, hydrogen sulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, or a combination thereof.

[0066] Therefore, for example, a suitable support material for use in the catalyst system disclosed herein may be one or more of the following: fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titanium dioxide, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphoric silica-coated alumina, etc., or combinations thereof. In at least one embodiment, the activator-support may be or may comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphoric silica-coated alumina, or combinations thereof. In another embodiment, the carrier material includes alumina treated with hexafluorotitanic acid, alumina coated with silica treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, fluorinated boron oxide-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphate, or combinations thereof. Furthermore, any of these activator-carriers may optionally be treated with metal ions.

[0067] Non-limiting examples of cations suitable for use in salts containing electron-withdrawing anions in this disclosure include ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H+, [H(OEt2)2]+, [HNR3]+ (R=Cl-C 20 Hydrocarbon groups (which may be the same or different) or combinations thereof.

[0068] Furthermore, one or more different electron-withdrawing anions can be combined in varying proportions to adjust the specific acidity of the carrier material to a desired level. The combination of electron-withdrawing components can be contacted with the carrier material simultaneously or individually, and in any order to provide the desired acidity of the carrier material for chemical treatment. For example, in at least one embodiment, two or more electron-withdrawing anion source compounds are contacted in two or more separate steps.

[0069] In one embodiment of this disclosure, an example of a method for preparing a chemically treated carrier material is as follows: a selected carrier material or combination of carrier materials may be contacted with a first electron-withdrawing anion source compound to form a first mixture; this first mixture may be calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture may then be calcined to form the treated carrier material. In this method, the first and second electron-withdrawing anion source compounds may be the same or different compounds.

[0070] The methods by which an oxide is contacted with an electron-withdrawing component (typically a salt or acid of an electron-withdrawing anion) can include, but are not limited to, gelation, co-gelation, impregnation of one compound onto another, or combinations thereof. Following the contacting method, the contact mixture of the carrier material, the electron-withdrawing anion, and optionally the metal ion can be calcined.

[0071] According to another embodiment of this disclosure, the carrier material can be processed by a method comprising: (i) contacting the carrier 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 the processed carrier material.

[0072] Preferably, the carrier material, most preferably an inorganic oxide, has a thickness of approximately 10m. 2 / g and approximately 700m 2 The surface area is between approximately 0.1 cc / g and approximately 4.0 cc / g, the pore volume is between approximately 0.1 cc / g and approximately 4.0 cc / g, and the average particle size is between approximately 5 μm and approximately 500 μm. In at least one embodiment, the surface area of ​​the carrier material is approximately 50 m² / g. 2 / g and approximately 500m 2 The particle size distribution ranges from approximately 0.5 cc / g to approximately 3.5 cc / g, with average particle sizes ranging from approximately 10 μm to approximately 200 μm. The surface area of ​​the carrier material can be approximately 100 m². 2 / g and approximately 400m 2 The pore volume is between approximately 0.8 cc / g and approximately 3.0 cc / g, and the average particle size is between approximately 5 μm and approximately 100 μm. The average pore size of the support material can be approximately... With the agreement Between, such as in the period With the agreement Between, such as in the period With the agreement Between. In at least one embodiment, the carrier material has a surface area of ​​300-400 m². 2 / gm; 0.9-1.8cm 3Amorphous silica with a pore volume of / gm. In at least one embodiment, the supported material may optionally be silica-containing subparticles having an average subparticle size in the range of 0.05 to 5 micrometers, for example, formed by spray drying small particles with an average particle size in the range of 0.05 to 5 micrometers to form large master particles with an average particle size in the range of 5 to 200 micrometers. In at least one embodiment, the supported material may optionally have pores with a pore diameter of = or > 100 angstroms (at least 20% of the total pore volume as defined by the BET method). Non-limiting examples of silica include Grace Davison's 952, 955, and 948; PQ Corporation's ES70 series, PD 14024, PD16042, and PD16043; Asahi Glass Chemical (AGC)'s D70-120A, DM-H302, DM-M302, DM-M402, DM-L302, and DM-L402; and Fuji's P-10 / 20 or P-10 / 40; etc.

[0073] The carrier material, such as inorganic oxides, optionally has a thickness of 50m. 2 / g to 800m 2 The surface area per g, pore volume ranging from 0.5 cc / g to 5.0 cc / g, and average particle size ranging from 1 μm to 200 μm.

[0074] The support material should be dry, i.e., substantially free of absorbed water. Drying of the support material can be achieved by heating or calcining at 100°C to 1,000°C, such as at least about 600°C. When the support material is silica, it is heated to at least 200°C, such as 200°C to 900°C, such as at about 600°C; and for a duration of 1 minute to about 100 hours, from 12 hours to 72 hours, or from 24 hours to 60 hours. The calcined support material should have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system disclosed herein. The calcined support material is then contacted with at least one polymerization catalyst and an activator comprising at least one catalyst compound.

[0075] Supported aluminoxane precursors

[0076] Supported aluminoxane precursors can be formed by coating a support material such as silica particles with the aluminoxane precursor. In one embodiment, the supported precursor can be formed by mixing the aluminoxane precursor and alkyl aluminum in an aliphatic hydrocarbon fluid, followed by distilling the solution at a pressure greater than about 0.5 atm to remove at least a portion of the aliphatic hydrocarbon fluid. Typically, the aliphatic hydrocarbon fluid is preferentially removed compared to unreacted alkyl aluminum present in the solution. For example, the concentration of unreacted alkyl aluminum present in the solution is typically maintained during distillation because the boiling point of alkyl aluminum is greater than that of the aliphatic hydrocarbon fluid. Typically, the supported aluminoxane precursor contains from about 1 wt% to about 50 wt% of the aliphatic hydrocarbon fluid based on the total weight of the supported aluminoxane precursor. For example, the supported aluminoxane precursor may include from about 1 wt% to about 40 wt% of the aliphatic hydrocarbon fluid, such as from about 1 wt% to about 30 wt%, or from about 1 wt% to about 20 wt% of the aliphatic hydrocarbon fluid, based on the total weight of the supported aluminoxane precursor.

[0077] The particles of the support material can be coated with both an aluminoxane precursor and an alkylaluminum. In at least one embodiment, the aluminoxane precursor is uniformly distributed on the support material and covers more than 50% of the surface area of ​​the support material. By introducing an alkylaluminum beyond the non-hydrolyzable oxygen compound as described herein, both the alkylaluminum and the aluminoxane precursor are typically present on the surface of the particles. Subsequent heating of the particles can cause the alkylaluminum to react with the aluminoxane precursor to form an alkylaluminoxane, such as MAO. In at least one embodiment, the total amount of the supported aluminoxane precursor comprises from about 1 wt% to about 90 wt% alkylaluminum. In at least one embodiment, the molar ratio of alkylaluminum to aluminoxane precursor in the supported aluminoxane precursor is in the range of from about 1:10 to about 10:1, such as about 4:1. The supported aluminoxane precursor is stable at ambient temperatures and low temperatures such as below about 25 degrees Celsius and is easy to store and transport.

[0078] Supported aluminum oxide

[0079] Supported aluminum oxanes can be formed by heating a supported aluminum oxane precursor to a temperature greater than the boiling point of an aliphatic hydrocarbon fluid and less than about 160 degrees Celsius, such as from about 70 degrees Celsius to about 120 degrees Celsius. In at least one example, the supported aluminum oxane is SMAO. Typically, heating the supported precursor produces volatile compounds. In this respect, the methods described herein may include removing at least a portion of the volatile compounds and optionally their derivatives. Thus, the methods described herein include forming an aluminum oxane precursor, forming a supported aluminum oxane precursor, and forming a supported aluminum oxane. Conventional methods for forming supported aluminum oxanes include forming the intermediate MAO, which is difficult to store and transport. The aluminum oxane precursors and supported aluminum oxane precursors disclosed herein have a shelf life longer than that of MAO. In addition, due to the stability of the aluminum oxane precursors and supported aluminum oxane precursors, transporting the aluminum oxane precursors and supported aluminum oxane precursors is easier than transporting MAO.

[0080] Catalyst compounds

[0081] In at least one embodiment, this disclosure provides a catalyst system comprising a catalyst compound having metal atoms. The catalyst compound may be a metallocene catalyst compound. The metal may be a group 3 to 12 metal atom, such as a group 3 to 10 metal atom, or a lanthanide group atom. The catalyst compound having group 3 to 12 metal atoms may be monodentate or multidentate, such as bidentate, tripentate, or tetradentate, wherein a heteroatom of the catalyst, such as phosphorus, oxygen, nitrogen, or sulfur, chelates with a metal atom of the catalyst. Non-limiting examples include bis(phenolic salts). In at least one embodiment, the group 3 to 12 metal atoms are selected from group 5, group 6, group 8, or group 10 metal atoms. In at least one embodiment, the group 3 to 10 metal atoms are selected from Cr, Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni. In at least one embodiment, the metal atoms are 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 can be in the range of 0 to +7, for example +1, +2, +3, +4, or +5, for example +2, +3, or +4.

[0082] The catalyst compounds disclosed herein may be chromium or chromium-based catalysts. Chromium-based catalysts include chromium oxide (CrO3) and silyl chromate catalysts. Chromium catalysts have been the subject of many developments in the field of continuous fluidized bed gas-phase polymerization for the production of polyethylene polymers. Such catalysts and polymerization methods have been described, for example, in U.S. Patent Application Publication No. 2011 / 0010938 and U.S. Patent Nos. 6,833,417, 6,841,630, 6,989,344, 7,202,313, 7,504,463, 7,563,851, 7,915,357, 8,101,691, 8,129,484, and 8,420,754.

[0083] The metallocene catalyst compounds used herein include metallocenes comprising group 3 to 12 metal complexes, preferably group 4 to 6 metal complexes, such as group 4 metal complexes. The metallocene catalyst compounds of the catalyst systems disclosed herein can be non-bridged metallocene catalyst compounds represented by the following formula: Cp A Cp B M'X' n Cp A and Cp B Each ligand is independently selected from cyclopentadienyl ligands and isolobal ligands of the cyclopentadienyl group, Cp A and Cp B One or two of them may contain heteroatoms, and Cp A and Cp B One or both of them may be replaced by one or more R” groups. M’ is selected from group 3 to 12 atoms 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, aryl, substituted aryl, heteroaryl, aryl, arylalkyl, arylenealkyl, alkylaryl, arylenealkyl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, group containing heteroatom, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphonyl, phosphine, amino, amine, ether and thioether.

[0084] In at least one embodiment, Cp A and Cp BEach is independently selected from cyclopentadienyl, indole, fluorenyl, cyclopentadienylphenanthrene, benzo[a]indole, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentadienylcyclododecene, phenanthrene, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopentadienyl[a]acenaphthenyl, 7-H-dibenzofluorenyl, indole[1,2-9]anthraene, thienenoyl, thienenoyl, and their hydrogenated forms.

[0085] Metallocene catalyst compounds can be bridged metallocene catalyst compounds represented by the following formula: Cp A (A)Cp B M'X' n Cp A and Cp B Each is independently selected from cyclopentadienyl ligands and ligands isovalent with cyclopentadienyl. Cp A and Cp B One or two of them may contain heteroatoms, and Cp A and Cp B One or both of them may be replaced by one or more R” groups. M’ is selected from group 3 to 12 atoms 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 lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent arylalkyl, divalent arylalkylene, divalent arylalkylene, divalent alkylene aryl, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, divalent Groups containing heteroatoms, divalent hydrocarbon groups, divalent lower hydrocarbon groups, divalent substituted hydrocarbon groups, divalent heterohydrocarbon groups, divalent silyl groups, divalent borosyl groups, divalent phosphin groups, divalent phosphine groups, divalent amino groups, divalent amine groups, divalent ether groups, and divalent thioether groups. "R" is selected from alkyl groups, lower alkyl groups, substituted alkyl groups, heteroalkyl groups, alkenyl groups, lower alkenyl groups, substituted alkenyl groups, heteroalkenyl groups, alkynyl groups, lower alkenylyl groups, arylylyl groups, alkylthioyl groups, lower alkylthioyl groups, arylyl groups, substituted aryl groups, heteroaryl groups, arylalkyl groups, arylene alkyl groups, alkylaryl groups, alkylene aryl groups, alkylene aryl groups, haloalkyl groups, haloalkenyl groups, haloalkynyl groups, heteroalkyl groups, heterocyclic groups, heteroaryl groups, groups containing heteroatoms, hydrocarbon groups, lower hydrocarbon groups, substituted hydrocarbon groups, heterohydrocarbon groups, silyl groups, borosyl groups, phosphin groups, phosphine groups, amino groups, amine groups, germanium groups, ethers, and thioethers.

[0086] In at least one embodiment, Cp A and Cp BEach is independently selected from cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl and n-butylcyclopentadienyl.

[0087] (A) can be O, S, NR', or SiR'2, where each R' is independently hydrogen or C1-C. 20 Hydrocarbon group.

[0088] In at least one embodiment, Cp A Cp B M'X' n The following are listed: (n-propylcyclopentadienyl)2HfMe2, (1,3-methyl, butylcyclopentadienyl)ZrCl2, (1,3-methyl, butylcyclopentadienyl)ZrCl2, (1,3-methyl, butylcyclopentadienyl)ZrMe2, Me2Si(tetrahydroindene)ZrCl2, Me2Si(tetrahydroindene)ZrMe2, Me2Si(CpCH2SiMe3)2HfCl2, and Me2Si(CpCH2SiMe3)2HfMe2.

[0089] In another embodiment, the metallocene may have structure (I):

[0090]

[0091] In the case of metallocenes with substituted cyclopentadienyl rings, they can be configured with racemic or meso geometry. R1 is hydrogen, a hydrocarbon group, or a substituted hydrocarbon group. R1 can be the same or different. Two or more R1s can be linked together to form a ring. R2 is a hydrocarbon group or a substituted hydrocarbon group. Two R2s can be linked together to form a ring. R1 and R2 can also be linked together to form a ring. R3 is an alkyl group. R4 is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. X is an anionic leaving group, such as fluoride, chloride, alkoxy, methyl, allyl, benzyl, trimethylsilylmethyl. Two Xs can also be linked together, such as in butadienyl ligands.

[0092] In another embodiment, the metallocene catalyst compound is represented by (II):

[0093]

[0094] In another embodiment, the metallocene catalyst compound is represented by (III):

[0095]

[0096] In another embodiment, the metallocene catalyst compound is represented by the following formula:

[0097] T y Cpm MG n X q

[0098] Where Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or a substituted or unsubstituted isovalenced ligand with cyclopentadienyl. M is a group 4 transition metal. G is formed by formula JR* z The heteroatomic group represented by J is N, P, O, or S, and R* is a straight-chain, branched, or cyclic C1-C group. 20 Hydrocarbon group. z is 1 or 2. T is a bridging group. y is 0 or 1. X is a leaving group. m = 1, n = 1, 2 or 3, q ​​= 0, 1, 2 or 3, and the sum of m + n + q equals the oxidation state of the transition metal.

[0099] 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.

[0100] Metallocene catalyst compounds can be selected from:

[0101] Bis(1-methyl,3-n-butylcyclopentadienyl)zirconium dichloride;

[0102] Dimethylsilylbis(tetrahydroindenyl)zirconium dichloride;

[0103] bis(n-propylcyclopentadienyl)dimethylhafnium;

[0104] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium;

[0105] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride;

[0106] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium;

[0107] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride;

[0108] μ-(CH3)2Si(cyclopentadienyl)(l-adamantylamino)M(R)2;

[0109] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0110] μ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0111] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0112] μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0113] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2;

[0114] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)M(R)2;

[0115] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0116] μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0117] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indargen-1-yl)(tert-butylamino)M(R)2;

[0118] M is selected from Ti, Zr and Hf; and R is selected from halogens or C1 to C5 alkyl groups.

[0119] In another embodiment, the catalyst compound is represented by (IV):

[0120]

[0121] R1 is hydrogen, a hydrocarbon group, or a substituted hydrocarbon group. R1 can be the same or different. Two or more R1s can be linked together to form a ring. R2 and R3 are hydrocarbon groups or substituted hydrocarbon groups. X is an anionic leaving group, such as fluoride, chloride, alkoxy, methyl, allyl, benzyl, or trimethylsilylmethyl. Two Xs can also be linked together, such as in butadienyl ligands.

[0122] In at least one embodiment, the catalyst compound is a bis(phenolate) catalyst compound represented by formula (V):

[0123]

[0124] M is a Group 4 metal. X 1 and X 2 Independently, the unit price is C1-C 20 Hydrocarbon group, C1-C 20 Substituted hydrocarbon group, heteroatom or heteroatom-containing group, or X 1 and X 2Connected together to form C4-C 62 Ring-like or multi-ringed structures. R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Independently, it is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, or R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 、or R 10 Two or more of them are connected together to form C4-C 62 A cyclic or polycyclic ring structure, or a combination thereof. Q is a neutral donor group. J is a heterocyclic, substituted, or unsubstituted C7-C ring. 60 A fused polycyclic group, wherein at least one ring is aromatic, and at least one of them (which may or may not be aromatic) has at least five ring atoms. G is as defined for J, or may be hydrogen, C2-C. 60 Hydrocarbon group, C1-C 60 Substituted hydrocarbon groups, or those that can independently react with R 6 R 7 、or R 8 or combinations thereof form C4-C 60 Ring-like or multi-ringed structures. Y is divalent C1-C. 20 Hydrocarbon group or divalent C1-C 20 The substituted hydrocarbon group or (-Q*-Y-) together form a heterocycle. The heterocycle can be aromatic and / or can have multiple fused rings.

[0125] In at least one embodiment, the catalyst compound represented by formula (V) is represented by formula (VI) or formula (VII):

[0126]

[0127] M is Hf, Zr, or Ti. X 1 X 2 R 1 R 2 R 3 R 4 R5 R 6 R 7 R 8 R 9 R 10 And Y is as defined for equation (V). R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 and R 28 Independently, it is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, functional groups containing elements from groups 13 to 17, or R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 and R 28 Two or more of them can be independently connected together to form C4-C 62 A ring structure, either cyclic or multi-ringed, or a combination thereof. R 11 and R 12They can be linked together to form five- to eight-membered heterocycles. Q* is an atom of group 15 or 16. z is 0 or 1. J* is CR" or N, and G* is CR" or N, where R" is C1-C. 20 Hydrocarbon group or C1-C containing carbonyl group 20 Hydrocarbon group. If Q* is a group 16 atom, then z = 0, and if Q* is a group 15 atom, then z = 1.

[0128] In at least one embodiment, the catalyst is an iron complex represented by formula (VIII):

[0129]

[0130] in:

[0131] A represents chlorine, bromine, iodine, -CF3, or -OR. 11 ,

[0132] R 1 and R 2 Each of them is a hydrogen atom, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or a five-, six-, or seven-membered heterocyclic group comprising at least one atom selected from the group consisting of N, P, O, and S;

[0133] Where R 1 and R 2 Each of them is optionally halogenated, -NR 11 2. -OR 11 or -SiR 12 3 Replacement;

[0134] Where R 1 Optional with R 3 Bonding, and R 2 Optional with R 5 Bonding, forming pentagonal, hexagramal, or heptagonal rings independently in each case;

[0135] R 7 It is C1-C 20 alkyl;

[0136] R 3 R 4 R 5 R 8 R 9 R 10 R 15 R 16 and R 17Each of them is a hydrogen atom, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, -NR 11 2, -OR 11 Halogen, -SiR 12 3. Or a five-, six-, or seven-membered heterocyclic group containing at least one atom selected from the group consisting of N, P, O, and S;

[0137] Where R 3 R 4 R 5 R 7 R 8 R 9 R 10 R 15 R 16 and R 17 Optional halogenated, -NR 11 2. -OR 11 or -SiR 12 3 Replacement;

[0138] Where R 3 Optional with R 4 Bonding, R 4 Optional with R 5 Bonding, R 7 Optional with R 10 Bonding, R 10 Optional with R 9 Bonding, R 9 Optional with R 8 Bonding, R 17 Optional with R 16 Bonding, and R 16 Optional with R 15 Bonding, in each case independently forming a five-, six-, or seven-membered carbon ring or heterocycle, the heterocycle containing at least one atom from the group consisting of N, P, O, and S;

[0139] R 13 It is a C1-C bonded to an aryl ring via a primary or secondary carbon atom. 20 -alkyl,

[0140] R 14 It is a chlorine, bromine, iodine, -CF3, or -OR bonded to an aryl ring. 11 or C1-C 20 -alkyl;

[0141] Each R 11 Independently, it is hydrogen, C1-C22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or -SiR 12 3, where R 11 Optionally replaced by halogen, or both R 11 The groups are optionally bonded to form five- or six-membered rings;

[0142] Each R 12 Independently, it is hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or two R groups. 12 The groups are optionally bonded to form five- or six-membered rings.

[0143] E 1 E 2 and E 3 Each of them is independently carbon, nitrogen, or phosphorus;

[0144] If E 1 E 2 and E 3 If it is nitrogen or phosphorus, then each u is independently 0, and if E 1 E 2 and E 3 If it's carbon, then each u is 1.

[0145] Each X is independently fluorine, chlorine, bromine, iodine, hydrogen, C1-C 20 -alkyl, C2-C 10 -Alkenyl, C6-C 20 -aryl, wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, -NR 18 2. -OR 18 -SR 18 -SO3R 18 -OC(O)R 18 -CN, -SCN, β-diketone, -CO, -BF4 - -PF6 - Or large-volume uncoordinated anions, and the groups X can bond to each other;

[0146] Each R 18 Independently, it is hydrogen, C1-C 20 -alkyl, C2-C 20 -Alkenyl, C6-C 20-aryl, wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or -SiR 19 3, where R 18 It can be substituted with halogens or nitrogen- or oxygen-containing groups, and both R groups... 18 The groups are optionally bonded to form five- or six-membered rings;

[0147] Each R 19 Independently, it is hydrogen, C1-C 20 -alkyl, C2-C 20 -Alkenyl, C6-C 20 -aryl or wherein the alkyl group has from 1 to 10 carbon atoms and the aryl group has from 6 to 20 carbon atoms, wherein R 19 It can be substituted by halogens or nitrogen- or oxygen-containing groups, or both R groups. 19 The groups are optionally bonded to form five- or six-membered rings;

[0148] s is 1, 2, or 3.

[0149] D is a neutral donor, and

[0150] t is between 0 and 2.

[0151] In at least one embodiment, the catalyst is a quinolinyl diamino transition metal complex represented by formulas (IX) and (X):

[0152]

[0153] in:

[0154] M is a metal in Groups 3-12;

[0155] J is a three-atom-length bridge between quinoline and amino nitrogen;

[0156] E is selected from carbon, silicon, or germanium;

[0157] X is an anion leaving group;

[0158] L is a neutral Lewis base;

[0159] R 1 and R 13 The group consisting of free hydrocarbon groups, substituted hydrocarbon groups, and silyl groups is selected independently;

[0160] R 2 To R 12 It is independently selected from the group consisting of hydrogen, hydrocarbon group, alkoxy group, silyl group, amino group, aryloxy group, substituted hydrocarbon group, halogen group and phosphine group;

[0161] n is 1 or 2;

[0162] m is 0, 1, or 2

[0163] n+m is not greater than 4; and

[0164] Any two adjacent R groups (e.g., R...) 1 and R 2 R 2 and R 3 (etc.) can be linked to form substituted or unsubstituted hydrocarbon groups or heterocycles, wherein the ring has 5, 6, 7, or 8 ring atoms, and wherein the substituents on the ring can be linked to form additional rings;

[0165] Any two X groups can be linked together to form a dianionic group;

[0166] Any two L groups can be linked together to form a bidentate Lewis base;

[0167] The X group can be attached to the L group to form a monoanionic bidentate group.

[0168] In a preferred embodiment, M is a Group 4 metal, zirconium, or hafnium;

[0169] In a preferred embodiment, J is arylmethyl, dihydro-1H-indenyl, or tetrahydronaphthyl;

[0170] In a preferred embodiment, E is carbon;

[0171] In a preferred embodiment, X is an alkyl, aryl, hydrogen, alkylsilane, fluoride ion, chloride ion, bromide ion, iodide ion, trifluoromethanesulfonate ion, carboxylate ion, or alkylsulfonate ion.

[0172] In a preferred embodiment, L is an ether, amine, or thioether;

[0173] In a preferred embodiment, R 7 and R 8 Connect to form a six-membered aromatic ring, wherein the connected R 7 and R 8 The functional group is -CH=CHCH=CH-;

[0174] In a preferred embodiment, R 10 and R 11 Connect to form a quintuple, where the connected R 10 and R 11 The functional group is -CH2CH2-;

[0175] In a preferred embodiment, R 10 and R 11 Connect to form a six-membered ring, where the connected R 10 and R 11 The functional group is -CH2CH2CH2-;

[0176] In a preferred embodiment, R 1 and R 13 The phenyl group can be independently selected from those substituted with one to five different substituents, including F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl, and alkyl groups having one to ten carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and their isomers.

[0177] In another embodiment, the catalyst is a phenoxyimine compound represented by formula (XI):

[0178]

[0179] Where M represents a transition metal atom selected from Groups 3 to 11 of the periodic table; k is an integer from 1 to 6; m is an integer from 1 to 6; R a To R f They may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, wherein two or more groups may combine with each other to form a ring; when k is 2 or greater, R a Group, R b Group, R c Group, R d Group, R e Group, or R f The groups can be the same or different from each other, and the R contained in a ligand a To R f One of the groups and R contained in another ligand a To R f One of the groups can form a linking group or a single bond, and is contained in R a To R f The heteroatom in M ​​can coordinate or combine with M; m is the number of valences that satisfy M; Q represents a hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group; when m is 2 or greater, multiple groups represented by Q can be the same or different from each other, and multiple groups represented by Q can combine with each other to form a ring.

[0180] In another embodiment, the catalyst is a bis(imino)pyridyl group of formula (XII):

[0181]

[0182] in:

[0183] M is Co or Fe; each X is an anion; n is 1, 2 or 3, such that the total number of negative charges on the one or more anions is equal to the oxidation state of the Fe or Co atoms present in (XII);

[0184] R 1 R 2 and R 3 Each can be independently a hydrogen group, a hydrocarbon group, a substituted hydrocarbon group, or an inert functional group;

[0185] R 4 and R 5 Each is independently a hydrogen group, a hydrocarbon group, an inert functional group, or a substituted hydrocarbon group;

[0186] R 6 Equation (XIII):

[0187]

[0188] And R 7 This is formula (XIV):

[0189]

[0190] R 8 and R 13 Each is independently a hydrocarbon group, a substituted hydrocarbon group, or an inert functional group;

[0191] R 9 R 10 R 11 R 14 R 15 and R 16 Each can be independently a hydrogen group, a hydrocarbon group, a substituted hydrocarbon group, or an inert functional group;

[0192] R 12 and R 17 Each can be independently a hydrogen group, a hydrocarbon group, a substituted hydrocarbon group, or an inert functional group;

[0193] And the premise is that the R values ​​are adjacent to each other. 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 and R 17 Any two of them can form a ring together.

[0194] In at least one embodiment, the catalyst compound is represented by formula (XV):

[0195]

[0196] M 1 The alloy is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. In at least one embodiment, M 1 It is zirconium.

[0197] Q 1 Q 2 Q 3 and Q 4 Each of these is independently oxygen or sulfur. In at least one embodiment, Q 1 Q 2 Q 3 and Q 4 At least one of them is oxygen, or alternatively Q 1 Q 2 Q 3 and Q 4 It's all oxygen.

[0198] R 1 and R 2 It is independently hydrogen, halogen, hydroxyl, hydrocarbon group, or substituted hydrocarbon group (such as C1-C). 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy group, C2-C 10 alkenyl, C2-C 40 alkenyl, C7-C 40 arylalkyl, C7-C 40 Alkyl aryl, C8-C 40 Arylalkenyl, or a conjugated diene optionally substituted with one or more hydrocarbon groups, tri(alkyl)silyl, or tri(alkyl)silylalkylalkyl groups, the diene having up to 30 atoms other than hydrogen. R 1 and R 2 It can be a halogen selected from fluorine, chlorine, bromine, or iodine. Preferably, R 1 and R 2 It is chlorine.

[0199] Alternatively, R 1 and R 2 They can also be linked together to form an alkyl group or with M. 1 Coordination of conjugated C4-C 40 Diene ligand. R 1 and R 2 It can also be the same or different conjugated dienes, which are optionally substituted with one or more hydrocarbon groups, tri(hydrosilyl)methylalkyl or tri(hydrosilyl)alkyl groups, and the dienes have hydrogens (not counting) and / or M 1The number of atoms forming π-complexes can reach up to 30.

[0200] Applicable to R 1 and or R 2 Exemplary groups may include 1,4-diphenyl, 1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl, 1,3-pentadiene, 1,4-dibenzyl, 1,3-butadiene, 1,4-xylyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene, and 1,4-dinathyl-1,3-butadiene. 1 and R 2 They can be the same and be C1-C3 alkyl or alkoxy, C6-C 10 aryl or aryloxy, C2-C4 alkenyl, C7-C 10 arylalkyl, C7-C 12 Alkyl aryl or halogen.

[0201] R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 and R 19 Each of these elements is independently hydrogen, halogen, C1-C. 40 Hydrocarbon group or C1-C 40 Substituted hydrocarbon groups (such as C1-C) 10 Alkyl, C1-C 10 Alkoxy group, C6-C 20 Aryl, C6-C 10 Aryloxy group, C2-C 10 Alkenyl, C2-C 40 Alkenyl, C7-C 40 Arylalkyl, C7-C 40 Alkyl aryl, C8-C 40 Arylalkenyl, or a conjugated diene optionally substituted with one or more hydrocarbon groups, tri(alkyl)silyl, or tri(alkyl)silylalkylalkyl groups, the diene having up to 30 atoms other than hydrogen), -NR'2, -SR', -OR, -OSiR'3, -PR'2, wherein each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 aryl, or R4 and R 5 R 5 and R 6 R 6 and R 7 R 8 and R 9 R 9 and R 10 R 10 and R 11 R 12 and R 13 R 13 and R 14 R 14 and R 15 R 16 and R 17 R 17 and R 18 and R 18 and R 19 One or more pairs are connected to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring. In at least one embodiment, C1-C 40 The hydrocarbon group is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isonyl, sec-nonyl, n-decyl, isodel, and sec-decyl. Preferably, R 11 and R 12 It is C6-C 10 Aryl groups, such as those optionally bound by C1-C 40 Hydrocarbon groups such as C1-C 10 Hydrocarbon-substituted phenyl or naphthyl groups. Preferably, R 6 and R 17 It is C 1-40 Alkyl groups, such as C1-C 10 alkyl.

[0202] In at least one embodiment, R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 13 R 14 R 15 R 16 R 17 R 18 and R 19 Each of them is independently hydrogen or C1-C 40 Hydrocarbon group. In at least one embodiment, C1-C40 The hydrocarbon group is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isonyl, sec-nonyl, n-decyl, isodel, and sec-decyl. Preferably, R 6 and R 17 Each of them is C1-C 40 hydrocarbon group, and R 4 R 5 R 7 R 8 R 9 R 10 R 13 R 14 R 15 R 16 R 18 and R 19 It is hydrogen. In at least one embodiment, C1-C 40 The hydrocarbon group is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isonyl, sec-nonyl, n-decyl, isodel, and sec-decyl.

[0203] R 3 It is C1-C 40 Unsaturated hydrocarbon groups or substituted C1-C 40 Unsaturated hydrocarbon groups (such as C1-C) 10 Hydrocarbon group, C1-C 10 Hydroxyl group, C6-C 20 Aryl, C6-C 10 Aryloxy group, C2-C 10 Alkenyl, C2-C 40 Alkenyl, C7-C 40 Arylalkyl, C7-C 40 Alkyl aryl, C8-C 40 Arylalkenyl, or a conjugated diene optionally substituted with one or more hydrocarbon groups, tri(alkyl)silyl, or tri(alkyl)silylalkyl hydrocarbon groups, the diene having up to 30 atoms other than hydrogen.

[0204] Preferably, R 3 It is a hydrocarbon group containing a vinyl moiety. As used herein, "vinyl" and "vinyl moiety" are used interchangeably and include terminal olefins, such as those composed of a structure Indicates. R 3 The hydrocarbon group can be further substituted (such as C1-C). 10 Alkyl, C1-C10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy group, C2-C 10 alkenyl, C2-C 40 alkenyl, C7-C 40 arylalkyl, C7-C 40 Alkyl aryl, C8-C 40 Arylalkenyl, or a conjugated diene optionally substituted with one or more hydrocarbon groups, tri(alkyl)silyl, or tri(alkyl)silylalkylalkyl groups, the diene having up to 30 atoms other than hydrogen. Preferably, R 3 It is the C1-C of vinyl. 40 C1-C unsaturated hydrocarbon group or substituted with vinyl group 40 Unsaturated hydrocarbon group. R 3 It can be represented by the following structure: -R'CH=CH2, where R' is Cl-C 40 Hydrocarbon group or C1-C 40 Substituted hydrocarbon groups (such as C1-C) 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy group, C2-C 10 alkenyl, C2-C 40 alkenyl, C7-C 40 arylalkyl, C7-C 40 Alkyl aryl, C8-C 40 Arylalkenyl, or a conjugated diene optionally substituted with one or more hydrocarbon groups, tri(alkyl)silyl, or tri(alkyl)silylalkyl hydrocarbon groups, the diene having up to 30 atoms other than hydrogen. In at least one embodiment, C1-C 40 The hydrocarbon group is selected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isonyl, sec-nonyl, n-decyl, isodel, and sec-decyl.

[0205] In at least one embodiment, R 3 It is 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, or 1-decenyl.

[0206] In at least one embodiment, the catalyst is a metal compound containing a group 15 metal, represented by formula (XVI) or (XVII):

[0207]

[0208] Wherein M is a transition metal of Groups 3 to 12, or a main metal of Group 13 or 14, or a metal of Groups 4, 5, or 6. In many embodiments, M is a Group 4 metal, such as zirconium, titanium, or hafnium. Each X is independently a leaving group, such as an anionic leaving group. Leaving groups may include hydrogen, hydrocarbon, heteroatom, halogen, or alkyl; y is 0 or 1 (when y is 0, group L' is absent). The term 'n' is the oxidation state of M. In various embodiments, n is +3, +4, or +5. In many embodiments, n is +4. The term 'm' represents the formal charge of the YZL or YZL' ligand and is 0, -1, -2, or -3 in various embodiments. In many embodiments, m is -2. L is a Group 15 or 16 element, such as nitrogen or oxygen; L' is a Group 15 or 16 element or a group containing a Group 14 element, such as carbon, silicon, or germanium. Y is a Group 15 element, such as nitrogen or phosphorus. In many embodiments, Y is nitrogen. Z is a Group 15 element, such as nitrogen or phosphorus. In many embodiments, Z is nitrogen. R 1 and R 2 Independently, they are C1 to C 20 A hydrocarbon group, or a heteroatom-containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus. In many embodiments, R 1 and R 2 It is C2 to C 20 Alkyl, aryl, or aralkyl, such as C2 to C4 20 Straight-chain, branched or cyclic alkyl, or C2 to C3 20 Hydrocarbon group. R 1 and R 2 They can also be connected to each other. R 3 It may be absent or may be a hydrocarbon group, hydrogen, halogen, or a heteroatom-containing group. In many embodiments, R 3 It does not exist (e.g., if L is oxygen), or it is hydrogen, or a straight-chain, cyclic, or branched alkyl group having 1 to 20 carbon atoms. R 4 and R 5 Independently, it is an alkyl, aryl, substituted aryl, cyclic alkyl, substituted cyclic alkyl, cyclic aralkyl, substituted cyclic aralkyl, or polycyclic system, typically having up to 20 carbon atoms. In many embodiments, R 4 and R 5 It has between 3 and 10 carbon atoms, or C1 to C2. 20 Hydrocarbon groups, C1 to C 20 Aryl or C1 to C 20 Aryl groups, or groups containing heteroatoms. R 4 and R 5 They can be connected to each other. R 6 and R 7Independently, it is absent, hydrogen, alkyl, halogen, heteroatom, or hydrocarbon group, such as a straight-chain, cyclic, or branched alkyl group having 1 to 20 carbon atoms. In many embodiments, R 6 and R 7 It does not exist. R* may not exist, or it may be hydrogen, a group containing a group 14 atom, a halogen, or a group containing a heteroatom.

[0209] "Form charge of YZL or YZL' ligands" refers to the charge of the entire ligand in the absence of the metal and leaving group X. "R" 1 and R 2 "Can also be interconnected" means R 1 and R 2 They can combine directly with each other or through other groups. "R" 4 and R 5 "Can also be interconnected" means R 4 and R 5 They can combine directly with each other or through other groups. The hydrocarbon group can be straight-chain, branched alkyl, alkenyl, alkynyl, cycloalkyl, aryl, acyl, aromatic acyl, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- or dialkyl-carbamoyl, acyloxy, acylamino, aromatic acylamino, straight-chain, branched, or cyclic alkylene, or combinations thereof. Araneyl is defined as a substituted aryl group.

[0210] In one or more embodiments, R 4 and R 5 Independently represented by the group indicated by the structure (XVIII):

[0211]

[0212] Where R 8 To R 12 Each is independently hydrogen, C1 to C 40 Alkyl groups, halogen groups, heteroatoms, and heteroatom-containing groups containing up to 40 carbon atoms. In many embodiments, R 8 To R 12 It is C1 to C 20 Straight-chain or branched alkyl groups, such as methyl, ethyl, propyl, or butyl. Any two of these R groups can form cyclic and / or heterocyclic groups. These cyclic groups can be aromatic. In one embodiment, R... 9 R 10 and R 12 Independently, it is methyl, ethyl, propyl, or butyl (including all isomers). In another embodiment, R 9 R 10 and R 12 It is methyl, and R8 and R 11 It is hydrogen.

[0213] In one or more embodiments, R 4 and R 5 Both are groups represented by the structure (XIX):

[0214]

[0215] Where M is a Group 4 metal, such as zirconium, titanium, or hafnium. In at least one embodiment, M is zirconium. Each of L, Y, and Z can be nitrogen. R 1 and R 2 Each of these can be -CH2-CH2-. R 3 It can be hydrogen, and R 6 and R 7 It can be non-existent.

[0216] In some embodiments, the catalyst may be represented by one of the following formulas:

[0217]

[0218]

[0219]

[0220] Wherein R is independently H, a hydrocarbon group, a substituted hydrocarbon group, a halogen group, a substituted heteroatom group, or SiR3; R can be combined to form a ring; when an aromatic ring is present, any one or more of the ring CR can be substituted to form a heterocycle; G is a neutral Lewis base derived from a substituted OR, SR, NR2, or PR2 group; E is O, S, NR, or PR; Y is G or E; J is independently a formal dibase O, S, NR, PR, CR2, or SiR2; L is a formally neutral ligand or Lewis acid; X is a halide, hydride, hydrocarbon group, or an unstable anionic group capable of being converted into a metal hydrocarbon group; M is a metal of Groups 3-12; n is the formal oxidation state of the metal, between 0 and 6; m is the sum of the formal anionic charges on non-X ligands, between -1 and -6; p = 0 to 4; r = 1 to 20; k = 1 to 4.

[0221] In some respects, the catalyst compound comprises one or more of the following metallocenes or their isomers:

[0222]

[0223] Where X is a halogen group, hydrogen group, hydrocarbon group, or an unstable anionic group that can be converted into a metal hydrocarbon group.

[0224] In at least one embodiment, the maximum amount of aluminum oxane is up to 5000 times molar excess Al / M relative to the catalyst compound (per metal catalytic site). The minimum aluminum oxane to catalyst compound molar ratio is 1:1. Preferred alternative ranges include 1:1 to 500:1, alternatively 1:1 to 200:1, alternatively 1:1 to 100:1, or alternatively 1:1 to 50:1.

[0225] catalyst system

[0226] The embodiments disclosed herein include a method for preparing a catalyst system, the method comprising contacting a supported aluminoxane with at least one catalyst compound having Group 3 to Group 12 metal atoms or lanthanide metal atoms in an aliphatic solvent. The catalyst compound having Group 3 to Group 12 metal atoms or lanthanide metal atoms may be a metallocene catalyst compound containing a Group 4 metal.

[0227] In at least one embodiment, the supported aluminoxane is heated before contact with the catalyst compound.

[0228] The supported aluminoxane can be slurried in an aliphatic solvent, and the resulting slurry is contacted with a solution of at least one catalyst compound. Alternatively, the catalyst compound can be added as a solid to the slurry of the aliphatic solvent and SMAO. In at least one embodiment, the contact between the slurry of the supported aluminoxane and the catalyst compound is maintained for a period ranging from about 0.02 hours to about 24 hours, such as from about 0.1 hours to about 1 hour, 0.2 hours to 0.6 hours, 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

[0229] In at least one embodiment of this disclosure, one or more catalyst compounds have a pre-catalyst loading of between 1 and 1,000 micromoles per gram of supported catalyst. In a preferred embodiment, one or more catalyst compounds have a pre-catalyst loading of between 1 and 100 micromoles per gram of supported aluminoxane. In even more preferred embodiments, one or more catalyst compounds have a pre-catalyst loading of between 1 and 50 micromoles per gram of supported aluminoxane.

[0230] In at least one embodiment of this disclosure, the catalyst system used in the polymerization comprises an aluminoxane, wherein the molar ratio of aluminum to the transition metal of the catalyst compound is less than 2000:1, preferably 50:1 to 1000:1, preferably 75:1 to 500:1, preferably 85:1 to 250:1; preferably 95:1 to 175:1, such as 85:1 to 125:1.

[0231] The mixture of catalyst compound and supported aluminoxane can be heated to a temperature ranging from about 0 degrees Celsius to about 70 degrees Celsius, such as from about 23 degrees Celsius to about 60 degrees Celsius, for example, room temperature. The contact time can range 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.

[0232] As described above, a suitable aliphatic solvent is a material in which all reactants used herein (e.g., supported aluminoxanes and catalyst compounds) are at least partially soluble and are liquid at the reaction temperature. Non-limiting examples of solvents include those having the formula C1. n H (n+2) Noncyclic alkanes, wherein n = 4-30, such as isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and those having the formula C n H n Cycloalkanes, where n = 5-30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc. Suitable aliphatic solvents also include any mixtures of the above.

[0233] The solvent can be loaded into the reactor, followed by the loading of a supported aluminoxane. A catalyst, such as a solution of the catalyst in an aliphatic solvent or as a solid, can then be loaded into the reactor. The mixture can be stirred at a temperature such as room temperature. Additional solvents can be added to the mixture to form a slurry with a desired consistency, such as from about 2 cc / g silica to about 20 cc / g silica, or, for example, about 4 cc / g. The solvent is then removed. Solvent removal dries the mixture and can be carried out under a vacuum atmosphere, by purging with an inert atmosphere, by heating the mixture, or a combination thereof. To heat the mixture, any suitable temperature that evaporates the aliphatic solvent can be used. It should be understood that, depending on the reactor pressure, depressurization under vacuum will lower the boiling point of the aliphatic solvent. Solvent removal temperatures can range from about 10 degrees Celsius to about 200 degrees Celsius, such as from about 60 degrees Celsius to about 140 degrees Celsius, such as from about 60 degrees Celsius to about 120 degrees Celsius, for example, about 80 degrees Celsius or lower, such as about 70 degrees Celsius or lower. In at least one embodiment, solvent removal includes applying heat, applying a vacuum, and applying nitrogen gas (by purging the mixture from the bottom of the container by bubbling nitrogen gas through the mixture). The mixture is then dried.

[0234] Aggregation methods

[0235] The embodiments disclosed herein include polymerization methods in which monomers (such as ethylene or propylene) and optionally comonomers (such as ethylene, propylene, 1-butene, 1-hexene, 1-octene) are contacted with a catalyst system comprising at least one catalyst compound and a supported aluminoxane. The at least one catalyst compound and the supported aluminoxane can be combined in any order, and typically before contact with the monomers. In at least one embodiment of this disclosure, the contact between the at least one catalyst compound and the supported aluminoxane can occur almost immediately before the catalyst is injected into the reactor.

[0236] In at least one embodiment of this disclosure, the method includes polymerizing an olefin to produce a polyolefin composition by contacting at least one olefin with a catalyst system of this disclosure and obtaining a polyolefin composition. The polymerization method of this disclosure can be carried out in any suitable manner. Any suitable solution, slurry, or gas-phase polymerization method can be used. Such methods can be operated in batch, semi-batch, or continuous modes. Polymerization can be carried out at temperatures ranging from about 0°C to about 300°C and at pressures ranging from about 0.35 MPa to about 10 MPa.

[0237] Monomers that can be used in this paper include substituted or unsubstituted C2 to C3 monomers. 40 α-olefins, preferably C2 to C3 20 α-olefins, preferably C2 to C3 12 α-olefins, preferably ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, and their isomers. In preferred embodiments, the olefin comprises a monomer of propylene and one or more optional comonomers, the comonomers comprising one or more ethylene or C4 to C4 olefins. 40 Olefins, preferably C4 to C5 20 Olefins, or preferably C6 to C4 olefins. 12 Alkenes. C4 to C 40 Olefin monomers can be straight-chain, branched, or cyclic. (C4 to C5) 40 Cyclic olefins can be strained or unstrained, monocyclic or polycyclic, and may include one or more heteroatoms and / or one or more functional groups. In another preferred embodiment, the olefin comprises a monomer for ethylene and optionally a comonomer containing one or more C3 to C4 atoms. 40 Olefins, preferably C4 to C5 20 Olefins, or preferably C6 to C6 olefins. 12 Olefins. C3 to C 40 Olefin monomers can be straight-chain, branched, or cyclic. (C3 to C4) 40 Cycloolefins can be strained or unstrained, monocyclic or polycyclic, and can include heteroatoms and / or one or more functional groups.

[0238] Examples C2 to C40 The olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives and isomers, 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 their substituted derivatives, preferably norbornene, norbornadiene and dicyclopentadiene.

[0239] In at least one embodiment, based on the total weight of the composition, one or more dienes are present in the polymer produced herein at up to about 10% by weight, such as from about 0.00001 to about 1.0% by weight, such as from about 0.002 to about 0.5% by weight, such as from about 0.003 to about 0.2% by weight. In at least one embodiment, about 500 ppm or less of dienes are added to the polymer, 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 dienes are added to the polymer, or about 100 ppm or more, or 150 ppm or more.

[0240] Diene monomers include any hydrocarbon structure having at least two unsaturated bonds, preferably C4 to C5. 30At least two of these unsaturated bonds are readily incorporated into the polymer by one or more stereooriented or non-stereooriented catalysts. More preferably, the diene monomer is selected from α,ω-diene monomers (i.e., divinyl monomers). In at least one embodiment, the diene monomer is a linear divinyl monomer, such as those containing from 4 to 30 carbon atoms. Non-limiting examples of dienes include butadiene, pentadiene, hexadiene, heptadecadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, heptadecanadiene, octadecadiene, nonadecadiene, eicosadiene, icosadiene, icosadiene, icosadiene, tridecadiene, icosadiene, icosadiene, icosadiene, icosadiene, icosadiene, triadecadiene, and triadecadiene. Particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tetadecanadiene, 1,13-tetradecadiene, and low molecular weight polybutadiene (Mw less than 1000 g / mol). Non-limiting examples of cyclic dienes include cyclopentadiene, vinyl norbornene, norbornene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, or dienes containing higher rings, which may or may not have substituents at various ring positions.

[0241] In at least one embodiment, when butene is a comonomer, the butene source can be a mixed butene stream containing various isomers of butene. It is anticipated that 1-butene monomer will be preferentially consumed by the polymerization process compared to other butene monomers. Using such mixed butene streams will provide economic benefits because these mixed streams are typically from waste streams of refining processes, such as C4 raffinate streams, and are therefore significantly cheaper than pure 1-butene.

[0242] Hydrogen can be added to the reactor for molecular weight control of polyolefins. In at least one embodiment, hydrogen is present in the polymerization reactor at a concentration between 0 and 30 mol%. In a preferred embodiment, hydrogen is present in the polymerization reactor at a concentration between 0 and 10 mol%. In a more preferred embodiment, hydrogen is present in the polymerization reactor at a concentration between 0 and 1 mol%. In even more preferred embodiments, hydrogen is present in the polymerization reactor at a concentration between 0 and 0.2 mol%.

[0243] In preferred embodiments, little or no scavenging agents are used in the method for producing the polyolefin composition. Preferably, the scavenging agent (such as trialkylaluminum or dialkylzinc) is present at zero mol%. Alternatively, the scavenging agent is present at a molar ratio of scavenging agent metal to transition metal of the catalyst 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. Such scavenging agents can also be used as chain transfer agents at an amount of scavenging agent metal:transition metal of >10:1.

[0244] In at least one embodiment of this disclosure, the method includes polymerizing an olefin in the presence of a hydrocarbon. Available hydrocarbons include C2-C64 hydrocarbons. 20 Hydrocarbons. Preferred hydrocarbons contain between three and twelve carbon atoms. Even more preferred hydrocarbons contain between three and six carbon atoms. Examples of preferred hydrocarbons include, but are not limited to, propane, butane, isobutane, isopentane, pentane, cyclopentane, isohexane, and hexane.

[0245] Preferred polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polyolefin. Typical temperatures and / or pressures include temperatures 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 pressures from about 0.35 MPa to about 10 MPa, such as from about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa.

[0246] In at least one embodiment of this disclosure, polymerization occurs in one or more “reaction zones.” A “reaction zone,” also known as a “polymerization zone,” is a container in which polymerization takes place, such as a batch or continuous reactor. When multiple reactors are used in series or parallel configurations, each reactor is considered a separate polymerization zone. For multi-stage polymerization in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In another embodiment, a series of polymerization zones includes gradients of temperature, solvent, or monomer concentration within a reactor body.

[0247] Gas phase polymerizationTypically, in fluidized bed processes for producing polymers, a gas stream containing one or more monomers is continuously circulated through a fluidized bed under reactive conditions in the presence of a catalyst. In some embodiments, the reaction medium comprises a condenser, typically a noncoordinate inert liquid converted to gas during the polymerization process, such as isopentane, isohexane, or isobutane. The gas stream is removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product is removed from the reactor and fresh monomers are added to replace the monomers used in polymerization. (See, for example, U.S. Patents 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are incorporated herein by reference in their entirety.)

[0248] Slurry phase aggregation Slurry polymerization is typically operated at pressures ranging from 1 to 50 atmospheres (15 psi to 735 psi, 103 kPa to 5068 kPa) or even higher, and at temperatures ranging from 0°C to 120°C. In slurry polymerization, a suspension of solid particulate polymer is formed in a liquid polymerization diluent medium, to which monomers and comonomers, as well as a catalyst, are added. The suspension, including the diluent, is removed from the reactor intermittently or continuously, whereby volatile components are separated from the polymer and optionally recycled back to the reactor after distillation. The liquid diluent used in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under polymerization conditions. When propane is used as the medium, the method should be operated at temperatures and pressures above the critical temperature and pressure of the reaction diluent. Preferably, hexane or isobutane is used as the medium.

[0249] polymer products

[0250] This disclosure also relates to polymer products produced via the catalyst systems disclosed herein, such as polyolefin compositions, like resins. The polymer products disclosed herein may be free of detectable aromatic solvents. Alternatively, the polymer products disclosed herein may be substantially free of aromatic solvents, for example, less than about 0.1 wt% of solvent, such as less than about 1 ppm, based on the weight of the polymer product.

[0251] In at least one embodiment, the method includes using the catalyst system disclosed herein to produce propylene homopolymers or propylene copolymers, such as propylene-ethylene and / or propylene-α-olefins (preferably C3 to C5) having a Mw / Mn ratio greater than about 2, such as greater than about 3, such as greater than about 4, such as greater than about 5. 20Copolymers (such as propylene-hexene copolymers or propylene-octene copolymers).

[0252] In at least one embodiment, the method includes producing olefin polymers, preferably polyethylene and polypropylene homopolymers and copolymers, using the catalyst system disclosed herein. In at least one embodiment, the polymer produced herein is a homopolymer or copolymer of ethylene, preferably having one or more C3 to C4 groups from about 0 to 25 mol%. 20 Olefin comonomers (e.g., from about 0.5 to 20 mol%, from about 1 to about 15 mol%, from about 3 to about 10 mol%). The olefin comonomers can be C3 to C4. 12 α-olefins, such as one or more of propylene, butene, hexene, octene, decene, or dodecene, preferably propylene, butene, hexene, or octene. The olefin monomer may be ethylene or C4 to C6. 12 One or more of α-olefins, preferably ethylene, butene, hexene, octene, decene, or dodecene, and more preferably ethylene, butene, hexene, or octene.

[0253] The polymers produced herein may have a Mw of about 5,000 to about 10,000,000 g / mol (such as from about 25,000 to about 750,000 g / mol, such as from about 50,000 to about 500,000 g / mol), and / or a Mw / Mn of about 2 to about 50 (such as from about 2.5 to about 20, such as from about 3 to about 10, such as from about 4 to about 5).

[0254] The polymers produced herein may have a melt index (MI) of less than about 400 g / 10 min, such as less than about 100 (I2). Alternatively or alternatively, the polymers produced herein may have a high load melt index to melt index (HLMI / MI) ratio of from about 12 to about 100, such as from about 15 to about 50.

[0255] The polymers produced in this paper can have a g' value greater than about 0.900, such as greater than 0.955, such as greater than 0.995 (g'). vis ).

[0256] The polymer produced in this paper can have a content of approximately 0.920 g / cm³. 3 Approximately 0.918 g / cm³ 3 Approximately 0.880 g / cm³ 3 or ≥ 0.910 g / cm³ 3 For example, ≥ 0.919 g / cm³ 3 ≥0.92g / cm 3 ≥ 0.930 g / cm³ 3≥ 0.932 g / cm³ 3 The density. Additionally, the polyethylene composition can have a density of ≤ about 0.965 g / cm³. 3 For example, ≤ 0.945 g / cm³ 3 ≤0.940g / cm 3 ≤0.937g / cm 3 ≤0.935g / cm 3 ≤0.933g / cm 3 or ≤ 0.930 g / cm³ 3 The density. The explicitly disclosed range includes, but is not limited to, the range formed by any combination of the foregoing values, for example, from about 0.880 to about 0.965 g / cm³. 3 0.920 to 0.930 g / cm³ 3 0.925 to 0.935 g / cm³ 3 0.920 to 0.940 g / cm³ 3 wait.

[0257] blends

[0258] In at least one embodiment, a polymer (such as polyethylene or polypropylene) produced herein and not containing detectable aromatic solvents is combined with one or more other polymers before being formed into a film, molded part or other article. Other available polymers, which may or may not contain detectable amounts of aromatic solvents, include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene and ethylene, and / or butene, and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate, or any other polymer that can be polymerized by a high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrene block copolymers, polyamide, polycarbonate, PET resin, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), and polymers of aromatic monomers such as polystyrene, poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0259] In at least one embodiment, based on the weight of the total polymer in the blend, the polymer (such as polyethylene or polypropylene) is present in the above blend in amounts ranging from about 10 wt% to about 99 wt%, such as from about 20 wt% to about 95 wt%, such as from about 30 wt% to about 90 wt%, such as from about 40 wt% to about 90 wt%, such as from about 50 wt% to about 90 wt%, such as from about 60 wt% to about 90 wt%, such as from about 70 wt% to about 90 wt%.

[0260] The blends disclosed herein can be produced by mixing the polymers disclosed herein with one or more polymers (as described above), by connecting reactors in series to prepare reactor blends, or by using more than one catalyst in the same reactor to produce multiple polymers. These polymers can be mixed together before being fed into an extruder, or they can be mixed in the extruder.

[0261] The blends disclosed herein can be formed using conventional equipment and methods, such as by dry blending individual components (such as polymers) and subsequently melt-blending them in a mixer, or by directly blending these components together in a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single-screw or twin-screw extruder, which may include compounding extruders and side-arm extruders used directly downstream of the polymerization process (which may include blending resin powder or granules at the hopper of a film extruder). Additionally, additives are desired to be included in the blend, in one or more components of the blend, and / or in the product formed from the blend, such as a film. Such additives may include, for example: fillers; antioxidants (e.g., hindered phenols, such as IRGANOX, available from Ciba-Geigy). TM 1010 or IRGANOX TM 1076); phosphites (e.g., IRGAFOS available from Ciba-Geigy). TM 168); anti-cling additives; tackifiers, such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metals and glyceryl stearate and hydrogenated rosin; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc; mixtures thereof, etc.

[0262] In at least one embodiment, the polyolefin composition, such as a resin, which is a multimodal polyolefin composition, comprises low molecular weight fractions and / or high molecular weight fractions. In at least one embodiment, the polyolefin composition produced by the catalyst system disclosed herein has a comonomer content of from about 3 wt% to about 15 wt%, such as from about 4 wt% to about 10 wt%, such as from about 5 wt% to about 8 wt%. In at least one embodiment, the polyolefin composition produced by the catalyst system disclosed herein has a polydispersity index of from about 2 to about 6, such as from about 2 to about 5.

[0263] membrane

[0264] Any of the aforementioned polymers, such as the aforementioned polyethylene or blends thereof, can be used in a variety of end-use applications. Such applications include, for example, single-layer or multi-layer blow molding, extrusion, and / or shrink films. These films can be formed using any suitable extrusion or co-extrusion technology, such as blown film processing technology, in which the composition can be extruded in a molten state through an annular die and then expanded to form a uniaxially or biaxially oriented melt, then cooled to form a tubular blown film, which can then be axially cut and unfolded to form a flat film. The film can then be unoriented, uniaxially oriented, or biaxially oriented to the same or different degrees. One or more of the film layers can be oriented to the same or different degrees in the transverse and / or longitudinal directions. Uniaxial orientation can be achieved using typical cold-drawing or hot-drawing methods. Biaxial orientation can be achieved using tenter frame equipment or a bi-bubble method and can be performed before or after the individual layers are placed together. For example, a polyethylene layer can be extruded, coated, or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene can be co-extruded together into a film and then oriented. Similarly, oriented polypropylene can be laminated onto oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and then optionally, or even further, the combination can be oriented. Typically, these films are oriented in the machine direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the transverse direction (TD) at a ratio of up to 15, preferably between 7 and 9. However, in another embodiment, the film is oriented to the same degree in both the MD and TD directions.

[0265] The thickness of these films can vary depending on the intended application; however, films with thicknesses ranging from 1 μm to 50 μm may be suitable. Films intended for packaging are typically 10 μm to 50 μm thick. The thickness of the sealing layer is typically 0.2 μm to 50 μm. The sealing layer can be present on both the inner and outer surfaces of the film, or it can be present only on the inner or outer surface.

[0266] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave treatment. In a preferred embodiment, one or both of these surface layers are modified by corona treatment.

[0267] The polymers produced herein can be combined with one or more other polymers prior to being formed into films, molded parts, or other articles. Other available polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene and ethylene, and / or butene, and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate, or any other polymer that can be polymerized by a high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrene block copolymers, polyamide, polycarbonate, PET resin, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene. Additionally, additives may be included in the blend, in one or more components of the blend, and / or in products formed from the blend, such as films.

[0268] In summary, it has been found that easily stored and transportable aluminoxane precursors can be used to form supported aluminoxane precursors and supported aluminoxanes. The shelf life of both aluminoxane precursors and supported aluminoxane precursors is longer than that of MAO, an intermediate product in conventional methods for forming supported aluminoxanes.

[0269] Example

[0270] General comments. Effervescent methacrylic acid (MAA) with N2 just before use. Alkyl aluminum and solvent were obtained from Aldrich Chemical Company. Anhydrous heptane and toluene were effervescent with N2 and then stored in a dry place. Molecular sieves. ES70, 5% Al on ES70, ES70X, and PD14024 silica were obtained from PQ Corporation. Silica was dehydrated in a tube furnace under a flowing N2 stream; the dehydration temperature in degrees Celsius (°C) is indicated in parentheses in the text. (PrCp)2HfMe2(MCN 1) was obtained from Boulder Scientific. The semi-alkoxide Me2Al(μ-Me)(μ-OCMe2CMe=CH2)AlMe2 was prepared by treating trimethylaluminum (TMA) in pentane at low temperature with 1 / 2MeC(O)CMe=CH2. The chemisorption of TMA on the support was determined by tracking the loss of TMA in solutions containing C6D6 or other inert deuterated solvents relative to an internal standard after correcting for TMA loss in glassware, etc., once combined with the support.

[0271] Example 1 - Comparison. A 250 mL three-necked flask equipped with a mechanical stirrer was placed in a cold bath at 0°C. Pure TMA (7.5055 g, 104 mmol) and pentane (48 mL) were added to the flask to prepare a TMA solution. Pure MAA (2.9895 g, 34.6 mmol) was slowly added to the cold-stirred TMA solution at a rate of 0.3 mL / 12 s. After completion, the mixture was stirred at a cold temperature for 20 minutes, then heated to room temperature and stirred for another 20 minutes. Aliquots of the mixture were taken out, and the aliquots were... 1 The vinyl region of the HNMR (C6D6) spectrum is shown in Figure 1 16.0147 g of ES70 (875) was added to a flask, followed by 10 mL of pentane, and the slurry was stirred for 20 minutes. The pentane was removed under vacuum for 3 hours to obtain the SMAO precursor (yield 24.02 g). An aliquot of the precursor (3.5514 g) was placed in a stainless steel bomb and heated at 120 °C for 3 hours. After a 5-minute run, a solution of MCN 1 (43.7 mg, 0.1 mmol) and pentane (5 mL) was added dropwise to the top-stirred slurry of the obtained SMAO and pentane (20 mL), and the mixture was stirred for another hour. The mixture was then filtered and vacuum dried to obtain the supported catalyst.

[0272] Example 2a. Representative preparation of the precursor. TMA (116.3 g, 1.61 mol) and pentane (700 mL) were loaded into a 3 L three-necked flask equipped with a mechanical stirrer, a feeding funnel, and a highly efficient condenser with a removable connector (similar to a dry ice condenser – cooled to -55 °C with finger freezers and heptane), and stirred at 120 RPM. A solution of MAA (36.35 g, 0.42 mol) and pentane (300 mL) was then added at a rate maintaining controlled reflux. After the addition, reflux was maintained by gentle heating for 1 hour.

[0273] Example 2b. Preparation of a representative SMAO from a precursor. ES70 (200) silica (210.6 g) was added fractionally to the precursor solution. The slurry was stirred for 30 minutes. The pentane was then removed by simple distillation. A flask was then fitted with a vacuum-jacketed Vigereaux column and a distillation head with the outlet connected to a cold trap. The flask was heated to approximately 120°C and stirred for 5 hours, allowing the volatiles to distill into the cold trap. The solid was then dried under vacuum at the specified temperature for 3 hours. The yield was 293.2 g of SMAO.

[0274] Example 2c. Representative large-scale catalyst preparation. Pentane (900 mL) and SMAO (260.34 g) obtained from Example 2b were charged into a 3 L three-necked flask equipped with a mechanical stirrer and stirred at 120 RPM. Then, a solution of MCN 1 (4.4818 g, 10.6 mmol) and pentane (100 mL) was added via a feeding funnel over a 1-hour process. After stirring for another 2 hours, the slurry was filtered, returned to the stirrer-equipped flask, and the solid was dried at 40 °C for 2 hours with gentle stirring. The yield was 261.4 g of white catalyst.

[0275] Examples 3-5. For each of Examples 3 and 5, the precursor, SMAO, and catalyst were prepared according to the procedures of Examples 2a, 2b, and 2c. For Example 4, the precursor and SMAO were prepared according to the procedures of Examples 2a and 2b, and the catalyst was prepared from SMAO according to the procedure of Example 6c, except that the SMAO was Soxhlet extracted with hexane for 6 hours and then pre-dried. Further details of the catalysts prepared in Examples 3-5 are described in Table 3.

[0276] Example 6a. Representative preparation of a concentrated precursor. TMA (90.85 g, 1.26 mol) and pentane (700 mL) were charged into a 3 L three-necked flask equipped with a mechanical stirrer, a feeding funnel, and a highly efficient condenser with a disconnector (similar to a dry ice condenser – cooled to -55°C with a finger freezer and heptane), and stirred for 15 min. A solution of MAA (36.17 g, 0.42 mol) and pentane (300 mL) was then added over a controlled reflux rate over a 60-minute process. After the addition, the reflux was maintained by gentle heating for 1 h. The pentane was removed by simple distillation to obtain a colorless oil MAO precursor. The oil was stored at -45°C until use. The yield was 151 g. NMR analysis showed that the oil contained 17.6 wt% pentane and 2.88 equivalents of MAA / g oil. Concentrated Precursor 1 H NMR (C6D6) shows Figure 2 and 3 In the middle. The 1H NMR (C6D6) of the concentrated precursors of both before and after the addition of the semi-alkoxide Me2Al(μ-Me)(μ-OCMe2CMe=CH2)AlMe2 is shown in Figure 4 middle.

[0277] Example 6b. Preparation of a representative SMAO from a concentrated precursor. A 250 mL three-necked flask was equipped with a mechanical stirrer, a vacuum-jacketed Vigereaux column, and a distillation head connected to a high-efficiency cold trap. Pentane (100 mL), TMA (1.611 mL, 16.8 mmol), and concentrated precursor oil (6.9784 g, 20.1 mmol equivalent of MAA) were added to the flask, and the mixture was stirred for 5 minutes. ES70 (200) (10.03 g) was added to the stirred solution, and the slurry was stirred at room temperature for 30 minutes. The pentane was distilled off from the slurry. The temperature was then increased until the inner wall temperature of the flask was approximately 120 °C. Heating was continued for 3 hours while the volatiles were distilled off from the reaction, followed by 2 hours under vacuum. The yield was 13.9 g of SMAO as a white solid.

[0278] Example 6c. A solution of MCN 1 (36.1 mg, 0.085 mmol) in pentane (5 mL) was added to a top-stirred slurry of SMAO (2.0309 g) and pentane (25 mL). After 30 minutes, the slurry was filtered and the solid was dried under vacuum for 1 hour. The yield was 1.82 g of white solid.

[0279] Examples 7-13. For each of Examples 7-11, the precursor, SMAO, and catalyst were prepared according to the procedures of Examples 6a, 6b, and 6c. For Example 12, the precursor and SMAO were prepared according to the procedures of Examples 6a and 6b, and the catalyst was prepared from the SMAO according to the procedure of Example 6c, except that the SMAO was extracted with hexane using a Soxhlet extractor and then pre-dried. For Example 13, the precursor and SMAO were prepared according to the procedures of Examples 6a and 6b, and the catalyst was prepared from the SMAO according to the procedure of Example 6c, except that the SMAO was extracted with hexane using a Soxhlet extractor and then pre-dried, and the catalyst was prepared using approximately twice the amount of MCN 1 used in Example 6c.

[0280] Example 14. For Example 14, the precursor, SMAO, and catalyst were prepared according to the procedure of Example 6, except that the catalyst was separated from the slurry by removing the solvent through vacuum instead of by filtration.

[0281] Example 15a. A mixture of 6 wt% (NH4)2SiF6 and 94 wt% 5% Al on an ES70 was fluidized with a stream of dry air and heated to 650°C at 30°C-50°C / h, held for 3 hours, then cooled to ambient temperature, and then purged with N2 to remove air.

[0282] Example 15b. FAS-SMAO was prepared according to the procedure of Example 6b, except that the FAS prepared in Example 15a was used instead of ES70. Further details are shown in Table 3.

[0283] Example 15c. A catalyst was prepared from FAS-SMAO of Example 15b according to the procedure of Example 6c. Further details of the catalyst prepared in Example 15c are described in Table 3.

[0284] Example 16a. Preparation and characterization of [Me₂Al(μ-O₂CCMe=CH₂)]₂. TMA (10.8 g; 150 mmol) in isohexane (50 mL) was cooled to -47 °C with stirring. MAA (13.0 g; 150 mmol) was dissolved in isohexane (approximately 30 mL) and kept cooled just above the temperature at which MAA would begin to crystallize. After approximately 30 minutes, it was added dropwise in approximately 1 mL portions. A colorless precipitate formed. After the addition was complete, the reaction was stirred at -47 °C for 10 minutes, then heated. The precipitate redissolved, except for some solid adhering to the sides of the flask. Approximately 25 mL of solvent was evaporated, and the solution was decanted into a 100 mL flask and cooled to -47 °C for approximately half an hour. A colorless crystalline solid formed, which was separated by decantation and dried under vacuum, approximately half of the expected product. The supernatant was dried to a clear, colorless liquid; isohexane (approximately 25 mL) was added, and the mixture was cooled to -24 °C. A solid product (approximately 11 g) was obtained. A portion of the solid (0.662 g) was dissolved in isohexane (approximately 10 mL), and the mixture was cooled to -24 °C. The solution was concentrated to approximately 7 mL and cooled to -24 °C. Most of the isohexane was removed, and the sample was redissolved in approximately 2 mL of pentane, and the mixture was cooled to -24 °C. Some crystals grew. A crystal was mounted on a crystal holder in a drying oven by placing it in a small plastic pipette filled with silicone grease, with one end of the pipette attached to the crystal holder. This gave good diffraction. Crystallographic data for [Me2Al(μ-O2CCMe=CH2)]2 are shown in Table 1. The Oak Ridge thermal ellipsoid is illustrated in... Figure 5 In the middle. The precursor solution 1 H NMR (C6D6) shows Figure 6 middle.

[0285] Table 1. Crystallographic data of [Me2Al(μ-O2CCMe=CH2)]2

[0286]

[0287] Example 16b. Preparation of SMAO from [Me₂Al(μ-O₂CCMe=CH₂)]₂. A 250 mL three-necked flask was equipped with a mechanical stirrer and a vacuum-jacketed Vigereaux column. A solution of pentane (100 mL), [Me₂Al(μ-O₂CCMe=CH₂)]₂ (2.8497 g, 10.0 mmol), and pentane (5 mL) was added to the flask, followed by TMA (4.0955 g, 56.8 mmol). The mixture was heated to mild reflux for 2 hours (stopping the top of the column), and then stirred overnight without heating. The mixture was slightly turbid. ES70 (200) (10.04 g) was added, and the slurry was stirred at room temperature for 5 minutes. The pentane was distilled off from the slurry. The temperature was then increased so that the inner wall temperature of the flask was approximately 120 °C. Heating was continued for 3 hours while distilling off the volatiles from the reaction, and then a vacuum was applied for 2 hours. The yield is 14.0g SMAO, which is a white solid.

[0288] Example 16c. A catalyst was prepared from SMAO of Example 16b according to the procedure of Example 6c.

[0289] Example 17a. Concentrated precursor synthesis. After 1 hour, a solution of methacrylic acid (30.16 g, 0.35 mol) and pentane (300 mL) was added to a solution of TMA (75.7 g, 1.05 mol) and pentane (500 mL) prepared according to the procedure of Example 6a. The mixture was heated to reflux for another hour, and then converted to oil by distillation of the pentane. NMR analysis showed 19 wt% pentane and 2.8 mmol MAA equivalent / g oil.

[0290] Example 17b. Precursor stability study. A series of solutions (samples AI) were prepared from the concentrated precursor prepared according to Example 17a and heptane. These are shown in Table 2. Sample AC was stored at -10°C, sample DF at room temperature, and sample GI at 40°C for three weeks in each case. At -10°C, no significant changes were observed in NMR between the concentrate and the solution. At room temperature, the concentrate showed trace amounts of 2,3-dimethyl-pent-2-ene, but the solution remained largely unchanged. At 40°C, the concentrate decomposed into a glassy solid with a complex NMR spectrum, while the solution showed only minor changes. Apart from this exception, no other solids were observed, which, together with the NMR studies, indicates good storage stability of the precursor solution. The NMR spectra are shown in Table 2. Figure 7-9 middle.

[0291] Table 2. Precursor concentrations used for stability testing

[0292]

[0293] Catalytic polymerization test. NaCl (350 g) and TIBAL-SiO2 scavenger (4 to 6 g of 1.9 mmol TIBAL / g ES70(100)) were charged into a 2 L autoclave under N2 and heated at ≥85 °C for 30 min. The reactor was cooled to approximately 81 °C. 1-Hexene (2.5 mL) and 10 mol% H2 (120 SCCM) in N2 were added, and stirring was started (450 RPM). A solid catalyst (approximately 10 mg) was injected into the reactor along with ethylene (+220 psia). After injection, the reactor temperature was maintained at 85 °C, and ethylene was allowed to flow into the reactor to maintain pressure. H2 in N2 and hexene were fed at ratios of 0.5 mg / g and 0.1 g / g relative to the ethylene flow, respectively. Polymerization was stopped by venting the reactor after approximately 60 min. The polymer was washed with water to remove salts and then dried. Productivity is reported in Table 3 in units of (g Pol / g cat h).

[0294]

[0295] All references described herein are incorporated herein by reference, including any priority documents and / or test procedures, provided they do not contradict this document. As will be apparent from the foregoing general description and specific embodiments, while the form of this disclosure has been illustrated and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, it is not intended to limit this disclosure. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, the term “comprising” includes the terms “substantially constitutes,” “is,” and “consisting of,” and wherever “comprising” is used, “substantially constitutes,” “is,” or “consisting of” may be substituted for it.

Claims

1. A composition comprising: (i) a reaction product containing at least one non-hydrolyzable oxygen compound and at least one hydrocarbon-based aluminum; and (ii) an aliphatic hydrocarbon fluid, wherein the molar ratio of aluminum to non-hydrolyzable oxygen in the composition is greater than or equal to 1.5, wherein the reaction product has a... 1 The first group of signals in the H NMR spectrum in the region from 4.5 ppm to 5.1 ppm and in 1 A second group of signals in the H NMR spectrum in the region from 5.1 ppm to 6.5 ppm, wherein the ratio of the first group of signals to the second group of signals is greater than or equal to 2.8, wherein the composition comprises an aliphatic hydrocarbon fluid from 1 wt% to 50 wt% based on the total weight of the composition; and The at least one compound containing non-hydrolyzable oxygen comprises methacrylic acid, and the at least one hydrocarbon aluminum comprises trimethylaluminum.

2. The composition of claim 1, wherein, Based on the total weight of the composition, the composition contains from 1 wt% to 20 wt% of the aliphatic hydrocarbon fluid.

3. The composition according to any one of claims 1-2, wherein, The aliphatic hydrocarbon fluid is C3 to C4. 12 Alkanes.

4. A composition comprising: a carrier material comprising a plurality of particles coated with the composition according to any one of claims 1-2.

5. The composition of claim 4, further comprising a catalyst compound.

6. A method for preparing an aluminoxane precursor, comprising: A solution is formed by combining at least one hydrocarbon aluminum with at least one compound containing non-hydrolyzable oxygen in an aliphatic hydrocarbon fluid, wherein the at least one compound containing non-hydrolyzable oxygen comprises methacrylic acid and wherein the at least one hydrocarbon aluminum comprises trimethylaluminum; The molar ratio of aluminum to non-hydrolyzed oxygen in the solution is greater than or equal to 1.5; the aliphatic hydrocarbon fluid has a boiling point of less than 70 degrees Celsius; and the combination is carried out at the reflux temperature of the aliphatic hydrocarbon fluid. The solution is distilled at a pressure greater than 0.5 atm to form the aluminoxane precursor, wherein the precursor comprises an aliphatic hydrocarbon fluid ranging from 0 wt% to 50 wt% based on the total weight of the precursor.

7. The method of claim 6, wherein, Based on the total weight of the precursor, the precursor contains from 1 wt% to 20 wt% aliphatic hydrocarbon fluid.

8. The method of claim 6 or 7, wherein, The aliphatic hydrocarbon fluid is C3 to C4. 12 Alkanes.

9. The method of claim 6 or 7, wherein the at least one non-hydrolyzable oxygen-containing compound comprises methacrylic acid, the at least one hydrocarbon aluminum comprises trimethylaluminum, and the aliphatic hydrocarbon fluid is pentane, and the solution is prepared by adding a solution of methacrylic acid in pentane to a solution of trimethylaluminum in pentane at a rate sufficient to maintain controlled reflux, i.e., maintaining the reaction temperature at the boiling point of pentane.

10. A composition wherein, The composition comprises a compound represented by formula (III):

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