Hybrid catalysts containing continuous additives for improving polymer properties in gas-phase polymerization.

Abstract

The present disclosure relates generally to methods of producing polyolefins in gas phase polymerization. In one embodiment, a method of producing polyethylene includes introducing ethylene and C3-C 40 An alpha-olefin is introduced into the reactor with a catalyst system and a continuity aid. The catalyst system includes an activator, an iron catalyst compound, and an unbridged Group 4 metallocene catalyst compound having one or more alkylsilyl substitutions. The method includes forming a polyethylene composition.

Description

Technical Field

[0001] This disclosure generally relates to a method for producing polyolefins in gas-phase polymerization. Background Technology

[0002] Olefin polymerization catalysts are widely used industrially to produce polyolefin compositions suitable for applications such as membranes. Despite significant efforts in developing olefin polymerization catalysts for the production of polyethylene compositions (e.g., linear low-density polyethylene (LLDPE)), producing polyethylene compositions and membranes with improved properties (e.g., processability, rigidity, and toughness) remains challenging. Achieving these performance properties is challenging because there are trade-offs among them. For example, increasing the rigidity and processability of an LLDPE composition often reduces its toughness.

[0003] Furthermore, a high bulk density is an ideal property because a large amount of polymer may remain in the reactor while the polymerization catalyst (one or more) continues to produce more polymer with sufficient catalytic activity to achieve high-yield polymer production. Additionally, a high bulk density (e.g., 0.45 g / cm³) is desirable. 3 (or higher) enables the efficient transport of large amounts of polymer product per unit volume. However, providing high packing density polymers also reduces catalyst productivity and catalyst activity while the polymer is still in the polymerization reactor.

[0004] Therefore, new and improved methods are still needed to produce LLDPE compositions with high activity and excellent bulk density while maintaining useful LLDPE properties such as processability, rigidity and toughness, each of which is important for membranes and other applications.

[0005] Documents that may be of potential reference value in this regard include WO2021 / 222016; WO2021 / 222280; and EP2183286. Summary of the Invention Invention Overview

[0007] This disclosure generally relates to a method for producing polyolefins in gas-phase polymerization.

[0008] In one embodiment, a method for producing polyethylene includes reacting ethylene and C3-C under polymerization conditions. 40 An α-olefin, a catalyst system, and a continuous additive are introduced into a reactor. The catalyst system comprises an activator, an iron catalyst compound, and an unbridged Group 4 metallocene catalyst compound having one or more alkylsilyl substituted compounds. The method includes forming a polyethylene composition. Invention Details

[0010] This disclosure generally relates to methods for producing polyolefins in gas-phase polymerization. For example, the methods of this disclosure may include producing linear low-density polyethylene (LLDPE) compositions at high catalyst activity and excellent bulk density while maintaining useful LLDPE properties such as processability, rigidity, and toughness, each of which may be important for membranes and other applications. It has been found that in polymerization reactions having the mixed catalyst system of this disclosure, the controlled addition of continuous additives (e.g., aluminum distearate) provides benefits such as excellent bulk density even at high catalyst activity. The LLDPEs of this disclosure may also have a broad orthogonal composition distribution ("BOCD"), which provides improved processability as well as rigidity and toughness sufficient to meet end-use applications. The catalyst systems of the methods of this disclosure include mixed catalyst systems of metallocene catalysts, such as group 4 cyclopentadienyl metallocene catalysts and 2,6-bis(imino)pyridyl iron complexes. For example, Group 4 cyclopentadienyl metallocenes can be non-bridged hafnium cyclopentadienyl catalysts having one or more alkyl-silyl-substituted cyclopentadienyl rings. As used herein, "non-bridged" refers to a catalyst that does not bridge structural portions (e.g., silyl bridges) other than the catalytic metal atoms.

[0011] The definitions of the terms used herein can be found in paragraphs

[0018] -

[0042] of WO2021 / 222016, which are incorporated herein by reference.

[0012] Unless otherwise stated, "catalyst activity" is a measure of how active a catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat) or the mass of product polymer (P) produced per mole of catalyst (cat) used (gP / gcat). Catalyst activity can also be expressed over a time period T of hours and reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used, in gP / mmolcat. -1 hr -1 Expressed in units.

[0013] Catalyst precursors and activators

[0014] In at least one embodiment of this disclosure, the catalyst system may comprise a metallocene catalyst (first catalyst compound), an iron catalyst (second catalyst compound), and an activator.

[0015] Metallocene catalysts

[0016] In this disclosure, the metallocene catalyst can be represented by the following formula (I):

[0017] (I).

[0018] In at least one embodiment, M in formula (I) is a Group 4 metal, such as titanium (Ti), hafnium (Hf), or zirconium (Zr), for example, hafnium.

[0019] In at least one embodiment, X of formula (I) 1 and X 2 Each of these is independently a monovalent anionic ligand, diene ligand, alkylidene ligand, or X 1 and X 2 They are joined to form a metallocyclic ring. X 1 and X 2 Each of these can independently be a halide, a hydride, an alkyl, an alkenyl, or an aralkyl group. In at least one embodiment, X 1 and X 2 Each of these groups is independently selected from halogenated, aryl, and C1 to C5 alkyl groups, such as phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloride. In at least one embodiment, X 1 and X 2 Each of them is a chlorine group.

[0020] In at least one embodiment, R of formula (I) 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each of these elements is independently selected from hydrogen, halogens, C1-C. 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, functional groups containing elements from groups 13 to 17 of the periodic table (e.g., –NR'2, –SR', –OR', –OSiR'3 or –PR'2, where each R' is independently hydrogen, halogen, C1-C). 10 Alkyl or C6-C 10 (aryl) or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 5 and R 6 R 6 and R 7 R 7 and R 8One or more pairs of elements join to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring, such as substituted or unsubstituted C4 to C5 rings. 62 A ring that is circular or multi-ringed.

[0021] In at least one embodiment, R of formula (I) 9 R 10 R 10 R 11 R 12 and R 13 Each of them is independently selected from hydrogen, C1-C 40 Hydrocarbon groups (e.g., C) 1-20 Hydrocarbon groups, such as C1-C 12 (Hydrocarbon group) or substituted C1-C 40 Hydrocarbon groups (e.g., substituted C) 1-20 Hydrocarbon groups, such as substituted C1-C 12 Hydrocarbon group), alkoxy group (alkoxide), or amide group (amide).

[0022] In at least one embodiment, R of formula (I) 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each of these groups is independently hydrogen, a halogen group, an alkoxy group, or a C1 to C1 group. 40 Substituted or unsubstituted hydrocarbon groups (e.g., C1-C) 12 (substituted or unsubstituted hydrocarbon group) or –R"–SiR'3 or –R"–CR'3, where R" is a C1 to C4 hydrocarbon group (e.g., –CH2–; –CH2CH2–; –(Me)CHCH2–; or –(Me)CH–, and each R' is independently C1-C 20 Substituted or unsubstituted hydrocarbon group and at least one R' is C1 to C2. 20 Substituted or unsubstituted hydrocarbon group. In at least one embodiment, each R' is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or isomers thereof, and R' is C1 to C2. 20 Alkyl or aryl, such as methyl, methylphenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl or di-tert-butylphenyl, provided that at least one R' is not H, or two R's are not H, or three R's are not H.

[0023] In at least one embodiment, C1-C 40 hydrocarbon group, C 1-20 Hydrocarbon group or C1-C 12The hydrocarbon group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isonyl, sec-nonyl, n-decyl, isodel, or sec-decyl.

[0024] In at least one embodiment, R of formula (I) 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each of these is independently hydrogen, –CH2–SiMe3, –CH2–SiEt3, –CH2–SiPr3, –CH2–SiBu3, –CH2–SiCy3, –CH2–C(CH3)3, –CH2–CH(CH3)2, –CH2CPh3, –CH2(C6Me5), –CH2–C(CH3)2Ph, –CH2–C(Cy)Ph2, –CH2–SiPh3, –CH2–Si(CH3)2Ph, –CH2–Si(CH3)2Ph, –CH2–Si(CH3)Ph2, –CH2–Si(Et)2Ph, –CH2–Si(Et)Ph2, –CH2–Si(Cy)Ph2, or –CH2–Si(Cy)2Ph.

[0025] The catalyst represented by formula (I) can be an asymmetric catalyst. Useful asymmetric catalysts are those that make it impossible to draw a mirror plane through the metal center, and whose cyclopentadienyl structural portions bridging to the metal center are structurally different.

[0026] In at least one embodiment, the metallocene catalyst represented by the following formula (I) is:

[0027] .

[0028] Other embodiments of the metallocene catalyst represented by formula (I) can be found in paragraphs

[0045] -

[0055] of WO2021 / 222016, which are incorporated herein by reference.

[0029] In at least one embodiment of this disclosure, the catalyst system may comprise a Group 4 metallocene catalyst represented by the following formula (III):

[0030] (III).

[0031] In at least one embodiment, M in formula (III) is a Group 4 metal such as hafnium (Hf) or zirconium (Zr), and in at least one embodiment, M is hafnium.

[0032] In at least one embodiment, X of formula (III) 1 and X 2 Each of these is independently a monovalent anionic ligand, diene ligand, alkylidene ligand, or X 1 and X 2 Joined to form a metal ring compound. X 1 and X 2 Each of these can be independently a halogenated, hydrogenated, alkyl, alkenyl, or aralkyl group. In at least one embodiment, X 1 and X 2 Each of these is selected from halogenated, aryl, and C1 to C5 alkyl groups, such as phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloro. In at least one embodiment, X 1 and X 2 Each of them is a chlorine group.

[0033] In at least one embodiment, R of formula (III) 1 R 2 R 3 R 4 R 5 R 6 R 14 R 15 and R 16 Each of these elements is independently selected from hydrogen, halogens, C1-C. 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, functional groups containing elements from groups 13 to 17 of the periodic table (e.g., -NR'2, -SR', -OR', -OSiR'3, or -PR'2, where each R' is independently hydrogen, halogen, C1-C...). 10 Alkyl or C6-C 10 (aryl) or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 4 and R 5 R 1 and R 5 R 14 and R 15 and R 15 and R 16 One or more pairs of elements join to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring, such as substituted or unsubstituted C4 to C5 rings. 62A ring, either cyclic or multi-ringed. In at least one embodiment, R 6 and R 13 Each of them is hydrogen. In at least one embodiment, R 1 R 2 R 3 R 4 and R 5 One or more of them are –CH2-Si-(CH3)3. In at least one embodiment, R 1 R 2 R 3 and R 4 Each is hydrogen and R 5 It is –CH2-Si-(CH3)3. In at least one embodiment, R 14 R 15 and R 16 Each of them is hydrogen.

[0034] In at least one embodiment, R of formula (III) 7 R 8 R 9 R 10 R 11 R 12 and R 13 Each of these elements is independently selected from hydrogen, halogens, C1-C. 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, functional groups containing elements from groups 13 to 17 of the periodic table (e.g., -NR'2, -SR', -OR', -OSiR'3, or -PR'2, where each R' is independently hydrogen, halogen, C1-C...). 10 Alkyl or C6-C 10 (aryl) or R 7 R 8 R 9 R 10 R 11 R 12 and R 13 The two elements combine to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring, such as substituted or unsubstituted C4 to C5 rings. 62 A ring, either cyclic or multi-ringed. In at least one embodiment, R 7 R 8 R 9 R 10 R 11 R 12 and R 13 Each of them is hydrogen.

[0035] In at least one embodiment, R of formula (III) 1 R2 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 and R 16 Each of these groups is independently hydrogen, a halogen group, an alkoxy group, or a C1 to C1 group. 40 Substituted or unsubstituted hydrocarbon groups (e.g., C1-C) 12 (substituted or unsubstituted hydrocarbon group) or -R"-SiR'3 or -R"-CR'3, wherein R" is a C1 to C4 hydrocarbon group (e.g., -CH2-; -CH2CH2-; -(Me)CHCH2-; or -(Me)CH-, and each R' is independently C1-C 20 Substituted or unsubstituted hydrocarbon group and at least one R' is C1 to C2. 20 Substituted or unsubstituted hydrocarbon group. In at least one embodiment, each R' is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or isomers thereof, and R' is C1 to C2. 20 Alkyl or aryl, such as methyl, methylphenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl or di-tert-butylphenyl, provided that at least one R' is not H, or two R's are not H, or three R's are not H.

[0036] In at least one embodiment, C1-C 40 hydrocarbon group, C 1-20 Hydrocarbon group or C1-C 12 The hydrocarbon group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isonyl, sec-nonyl, n-decyl, isodel, or sec-decyl.

[0037] In at least one embodiment, R of formula (III) 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12R 13 R 14 R 15 and R 16 Each of these is independently hydrogen, –CH2–SiMe3, –CH2–SiEt3, –CH2–SiPr3, –CH2–SiBu3, –CH2–SiCy3, –CH2–C(CH3)3, –CH2–CH(CH3)2, –CH2CPh3, –CH2(C6Me5), –CH2–C(CH3)2Ph, –CH2–C(Cy)Ph2, –CH2–SiPh3, –CH2–Si(CH3)2Ph, –CH2–Si(CH3)2Ph, –CH2–Si(CH3)Ph2, –CH2–Si(Et)2Ph, –CH2–Si(Et)Ph2, –CH2–Si(Cy)Ph2, or –CH2–Si(Cy)2Ph.

[0038] In at least one embodiment, R of formula (III) 6 R 7 R 8 R 9 R 10 R 11 R 12 and R 13 Each of them is hydrogen and R 1 R 2 R 3 R 4 R 5 R 14 R 15 and R 16 Each of these is independently hydrogen, -CH2-SiMe3, -CH2-SiEt3, -CH2-SiPr3, -CH2-SiBu3, -CH2-SiCy3, -CH2-C(CH3)3, -CH2-CH(CH3)2, -CH2CPh3, -CH2(C6Me5), -CH2-C(CH3)2Ph, -CH2-C(Cy)Ph2, -CH2SiPh3, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)Ph2, -CH2-Si(Et)2Ph, -CH2-Si(Et)Ph2, -CH2-Si(Cy)Ph2, or -CH2-Si(Cy)2Ph.

[0039] In at least one embodiment, R of formula (III) 6 R 7 R 8 R 9 R 10 R11 R 12 R 13 R 14 R 15 and R 16 Each of them is hydrogen and R 1 R 2 R 3 R 4 and R 5 Each of these is independently hydrogen, -CH2-SiMe3, -CH2-SiEt3, -CH2-SiPr3, -CH2-SiBu3, -CH2-SiCy3, -CH2-C(CH3)3, -CH2-CH(CH3)2, -CH2CPh3, -CH2(C6Me5), -CH2-C(CH3)2Ph, -CH2-C(Cy)Ph2, -CH2SiPh3, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)Ph2, -CH2-Si(Et)2Ph, -CH2-Si(Et)Ph2, -CH2-Si(Cy)Ph2, or -CH2-Si(Cy)2Ph.

[0040] The catalyst represented by formula (III) can be an asymmetric catalyst. Useful asymmetric catalysts are those that make it impossible to draw a mirror plane through the metal center, and whose cyclopentadienyl structural portions bridging to the metal center are structurally different.

[0041] In at least one embodiment, the Group 4 metallocene catalyst represented by formula (III) is

[0042] .

[0043] Other embodiments of the metallocene catalyst represented by formula (III) can be found in paragraphs

[0052] -

[0065] of WO2021 / 222280, which are incorporated herein by reference.

[0044] Iron catalyst

[0045] In at least one embodiment, the iron catalyst can be represented by formula (IIa) and / or formula (IIb):

[0046] (IIa) or (IIb).

[0047] In at least one embodiment, R of formulas (IIa) and (IIb) 6a R 10a R 11a and R 15aEach of them is independently a halogen, -CF3, or C1-C. 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, aralkyl (wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms), NR'2, -OR', -SiR"3, or a penta-, hexa-, or heptaneous heterocyclic group containing at least one atom selected from N, P, O, and S. In at least one embodiment, R 6a R 10a R 11a and R 15a Each of these is independently fluorine, chlorine, bromine, or iodine. In at least one embodiment, R 6a R 10a R 11a and R 15a Each of them can be independently and optionally replaced by a halogen, -NR'2, -OR', or –SiR"3.

[0048] In at least one embodiment, R of formulas (IIa) and (IIb) 1a and R 2a Each of them is independently 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 a penta-, hexa-, or hepta-heterocyclic group comprising at least one atom selected from N, P, O, and S, wherein R 1a and R 2a Each of these can be optionally replaced by a halogen, -NR'2, -OR', or -SiR"3, where R 1a Optional with R 3a Bonding, and R 2a Optional with R 5a Bonding, in each case, independently forms five-, six-, or seven-membered rings. In at least one embodiment, R 1a and R 2a Independently, it is C1-C 22 -alkyl, substituted C1-C 22 -alkyl, unsubstituted phenyl, or substituted phenyl. In at least one embodiment, R 1a and R 2aEach of the following is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isonyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, and tert-decyl.

[0049] In at least one embodiment, R of formulas (IIa) and (IIb) 3a R 4a R 5a R 7a R 8a R 9a R 12a R 13a and R 14a Each of them is independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, aralkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 20 carbon atoms, halogens, -NR'2, -OR', -SiR"3, or penta-, hexa-, or hepta-heterocyclic groups containing at least one atom selected from N, P, O, and S. 3a R 4a R 5a R 7a R 8a R 9a R 12a R 13a and R 14a Each of them can be independently and optionally replaced by a halogen, -NR'2, -OR', or –SiR"3.

[0050] In at least one embodiment, R of formulas (IIa) and (IIb) 8a and R 13a Each of them is independently selected from C1-C 22 -alkyl, wherein R 8a and R 13a Each of these can be independently and optionally replaced by a halogen, -NR'2, -OR', or –SiR"3. In at least one embodiment, R 7a R 9a R 12a and R 14a It is hydrogen. In at least one embodiment, R 3a R 4a and R 5a Each of them is hydrogen.

[0051] In at least one embodiment, X of formula (IIa) and / or formula (IIb) 1a X 2a and X 3a Each of these elements is independently a halogen, hydrogen, or C1-C. 20 -alkyl, C2-C 10 -Alkenyl, C6-C 20 -aryl, aralkyl groups in which the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, -NR'2, -OR', -SR', -SO3R', -OC(O)R', -CN, -SCN, β-diketonate, -CO, -BF4 - -PF6 - Or bulky uncoordinated anions, or X 1a and X 2a Optionally bonded to form a five- or six-membered ring. Each R' is independently 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 –SiR''3, wherein R' is optionally substituted with a halogen or a nitrogen- or oxygen-containing group, or two R' groups are optionally bonded to form a five- or six-membered ring. Each R'' is independently 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, wherein each R'' is optionally substituted with a halogen or nitrogen- or oxygen-containing group, or two R'' groups are optionally bonded to form a five- or six-membered ring. In at least one embodiment, X 1a and X 2a It is a chlorine group.

[0052] In at least one embodiment, R of formulas (IIa) and (IIb) 6a R 10a R 11a and R 15a Each of them is chlorine; R 1a and R 2a Each of them is C1-C 20 hydrocarbon group; R 3a R 4a and R 5a Each of them is hydrogen; R 8a and R 13a Each of them is C1-C 20 hydrocarbon group; R 7a R9a R 12a and R 14a Each of them is independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, aralkyl groups having 1 to 10 carbon atoms and the aryl group having 6 to 20 carbon atoms, halogens, -NR'2, -OR', -SiR''3, or penta-, hexa-, or hepta-heterocyclic groups containing at least one atom selected from N, P, O, and S; R 1a R 2a R 3a R 4a R 5a R 7a R 8a R 9a R 12a and R 13a Optionally substituted with halogen, -NR'2, -OR', or –SiR"3; each R' is independently 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 –SiR"3, wherein R' is optionally substituted with a halogen, or the two R' groups are optionally bonded to form a five- or six-membered ring; each R'' is independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 - aryl or an aralkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 20 carbon atoms, or two R'' groups optionally bonded to form a five- or six-membered ring.

[0053] In at least one embodiment, the iron catalyst represented by formula (IIa) or formula (IIb) is one or more of the following substances:

[0054] or .

[0055] Other embodiments of the metallocene catalyst represented by formula (I) can be found in paragraphs

[0056] -

[0066] of WO2021 / 222016, which are incorporated herein by reference.

[0056] carrier material

[0057] In at least one embodiment of this disclosure, the catalyst system comprises a combination of one or more support materials. In some embodiments, the support material is a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support materials, or mixtures thereof. The terms "support" and "support material" are used interchangeably herein.

[0058] In at least one embodiment, the support material is a finely dispersed inorganic oxide. Inorganic oxide materials suitable for the supported catalyst systems described 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 oxide, zirconium oxide, etc. However, other suitable support materials can be used, such as finely dispersed functionalized polyolefins, such as finely dispersed polyethylene. Particularly useful supports include magnesium oxide, titanium oxide, zirconium oxide, montmorillonite, layered silicates, zeolites, talc, clay, etc. Furthermore, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium oxide, etc. Exemplary support materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof, such as SiO₂, Al₂O₃, or SiO₂ / Al₂O₃.

[0059] Other implementation schemes for the carrier material can be found in paragraphs

[0067] -

[0071] of WO2021 / 222016, which are incorporated herein by reference.

[0060] In several implementation schemes, the catalysts described herein (represented by two or more of formulas (I), (IIa) / (IIb), or (III)) are typically deposited on a support material at a loading level of approximately 10-100 micromoles of metal per gram of solid support; or approximately 20-80 micromoles of metal per gram of solid support; or approximately 40-60 micromoles of metal per gram of support. However, larger or smaller values ​​may be used as long as the total amount of solid complex does not exceed the pore volume of the support.

[0061] Activator

[0062] The terms “co-catalyst” and “activator” are used interchangeably herein. Catalyst systems described herein may generally comprise catalyst complexes as described above and activators such as aluminoxanes or noncoordinate anions, and can be formed by combining the catalyst components described herein with activators in any manner known in the literature, including combining them with a support such as silica. Catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in monomers). Catalyst systems disclosed herein may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the above-described catalyst compounds by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators include, for example, aluminoxanes, alkylaluminum, ionized activators (which may be neutral or ionic), and conventional types of co-catalysts. Suitable activators generally include aluminoxane compounds, modified aluminoxane compounds, and ionized anionic precursor compounds that abstract reactive, σ-bonded metal ligands, thereby cationizing the metal compound and providing a noncoordinated or weakly coordinated anion, such as a noncoordinated anion, to balance the charge.

[0063] Ionized / noncoordinated anion activators

[0064] The term "noncoordinate anion" (NCA) refers to an anion that is not coordinated to the cation or is only weakly coordinated to the cation, thereby remaining sufficiently unstable to be replaced by a Lewis base. For a description of certain suitable activators and combinations of activators used in the methods of this disclosure, see US 8,658,556 and US 6,211,105, which are incorporated herein by reference; and US Patent Publication No. 2021 / 0179650, and in particular WIPO Patent Publication No. WO2021 / 257264, paragraphs

[0084] -

[0135] , which are incorporated herein by reference (including various descriptions incorporated by reference, such as paragraphs

[00119] on page 72 to paragraph

[00151] on page 81 of WO2004 / 026921, and paragraphs

[00177] on page 72 to paragraph

[00178] on page 74 of WO2004 / 046214).

[0065] Aluminoxane activator

[0066] Aluminoxane activators are used as activators in the catalyst systems described herein. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, for example, when the abstractable ligand is alkyl, halogen, alkoxy, or amide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Visually transparent methylaluminoxanes can be suitable for use. Turbid or gelled aluminoxanes can be filtered to prepare a clear solution or clear aluminoxane can be decanted from the turbid solution. A useful aluminoxane is modified methylaluminoxane (MMAO) co-catalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane Type 3A, as described in U.S. Patent No. 5,041,584, which is incorporated herein by reference). Another useful aluminoxane is solid polymethylaluminoxane, as described in U.S. Patent Nos. 9,340,630, 8,404,880, and 8,975,209, which are incorporated herein by reference.

[0067] When the activator is an aluminoxane (modified or unmodified), and in at least one embodiment, an activating dose of up to 5,000 molar excess Al / M relative to the catalyst compound (per metal catalytic site) can be used. The minimum activator-to-catalyst compound ratio can be 1:1 molar ratio. Optional ranges may include about 1:1 to about 500:1, or about 1:1 to about 200:1, or about 1:1 to about 100:1, or about 1:1 to about 50:1.

[0068] In an alternative embodiment, the polymerization method described herein uses little or no aluminum oxane. For example, the aluminum oxane may be present at zero molar percentage, or alternatively, the aluminum oxane may be present at a molar ratio of aluminum to the catalyst compound transition metal of less than 500:1, for example less than 300:1, for example less than 100:1, for example less than 1:1.

[0069] Optional scavengers, co-activators, chain transfer agents

[0070] In addition to the activators mentioned above, scavengers, chain transfer agents, or co-activators may also be used. Aluminum alkyl or organoaluminum compounds that can be used as co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylzinc, tri-n-butylaluminum, diisobutylaluminum hydride, or combinations thereof.

[0071] In at least one embodiment, the catalyst system may additionally comprise one or more scavenging compounds. Here, the term "scavenger" refers to a compound that removes polar impurities from the reaction environment. These impurities adversely affect the catalyst activity and stability. For example, the scavenging compound would be an organometallic compound, such as the Group 13 organometallic compounds described in U.S. Patents 5,153,157, 5,241,025, and WO 1991 / 009882, WO 1994 / 003506, WO 1993 / 014132, and WO 1995 / 007941. Exemplary compounds include triethylaluminum, triethylborane, tri-isobutylaluminum, methylaluminoxane, isobutylaluminoxane, and tri-n-octylaluminum.

[0072] Alkyl aluminum or organoaluminum compounds that can be used as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylzinc.

[0073] Chain transfer agents can be used in the compositions and / or methods described herein. Useful chain transfer agents may be diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0074] In some implementations, the cleaning agent may be of formula AlR (3-a) Xa is an aluminum hydrocarbon compound, wherein R is an alkyl, cycloalkyl, aryl, or hydride group. Each alkyl group may be a straight or branched chain containing 1 to 20 carbon atoms, or 1 to 10 carbon atoms. X is a halogen or hydride group, such as chlorine, bromine, or iodine, preferably chlorine; a is 0, 1, or 2.

[0075] Illustrative but non-limiting examples of such compounds may include: when M is aluminum (Al) or boron (B), trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tricyclopentylaluminum, tri-n-hexylaluminum, tri(4-methylpentyl)aluminum, tri(3-methylpentyl)aluminum, tricyclohexylaluminum; alkylaluminum such as dimethylethylaluminum, methyldiethylaluminum, ethyldimethylaluminum, dimethyl-n-propylaluminum, methyldi-n-propylaluminum, dimethylisopropylaluminum, dimethylcyclohexylaluminum, methylethylpropylaluminum, etc.; aryl and alkyl-substituted aluminum, such as triphenylaluminum, tri-p-tolylaluminum, tri-m-tolylaluminum, tri-p-ethylaluminum. Other non-limiting examples of typical scavengers include dialkylaluminum halides, such as diethylaluminum chloride, ethylaluminum dichloride, bromide, and iodide, as well as dialkylaluminum sesquichloride, bromide, and iodide; aluminum alkoxides and aromatic oxides, such as dimethylmethoxyaluminum, dimethylethoxyaluminum, diethylethoxyaluminum, diethylisopropoxyaluminum, methylethylmethoxyaluminum, dimethyl(4-methylphenoxy)aluminum, dimethyl(3-methylphenoxy)aluminum, dimethyl(2,6-diisopropylphenoxy)aluminum, and dimethyl(2,6-di-tert-butyl-4-methylphenoxy)aluminum.

[0076] Generally, preferred cleaning agents are those compounds in the above formula where M is aluminum or boron. Among aluminum compounds of Group 13 elements, alkyl aluminum compounds, such as trialkyl aluminum compounds, are most commonly used as cleaning agents, with triethylaluminum, triisobutylaluminum, and trimethylaluminum being the most preferred.

[0077] The aluminum alkyl compound can be, for example, triethylaluminum (TEAL), trimethylaluminum (TMAL), triisobutylaluminum (TIBAL), and tri-n-hexylaluminum (TNHAL), as well as diethylaluminum chloride (DEAC).

[0078] Preparation of mixed catalyst systems

[0079] Two or more catalyst types described above can be combined to form a mixed catalyst system. When combined, in contact with an activator, or in contact with a support material or a supported activator, two or more catalysts can be added in the desired proportions. Catalyst compounds can be added sequentially or simultaneously to the mixture. The molar ratio of the catalyst represented by formula (I) or formula (III) to the catalyst represented by formula (IIa) / (IIb) can vary depending on the desired balance between the processability and physical properties of the polymer. For example, the molar ratio of (I):(IIa) / (IIb) or (III):(IIa) / (IIb) can range from about 20:1 to about 1:1, or from about 1:1 to about 20:1, for example from about 1:1 to about 5:1, for example from about 1:1 to about 3:1, or from about 0.6:0.4 to about 0.8:0.2, or from about 0.6:0.4 to about 0.9:0.2 or from about 0.7:0.2 to about 0.8:0.2.

[0080] Other procedures for combining catalysts are also possible, such as those described in paragraphs

[0091] -

[0099] of WO2021 / 2222016 and paragraphs

[0114] -

[0122] of WO2021 / 222280, each of which is incorporated herein by reference.

[0081] In at least one embodiment, according to the present disclosure, the catalyst system has a catalyst activity greater than about 5,000 gP / gcat, for example greater than about 10,000 gP / gcat, for example greater than about 15,000 gP / gcat, for example about 5,000 gP / gcat to about 25,000 gP / gcat, for example about 10,000 gP / gcat to about 20,000 gP / gcat, for example about 12,000 gP / gcat to about 18,000 gP / gcat, or about 10,000 gP / gcat to about 15,000 gP / gcat, or about 15,000 gP / gcat to about 20,000 gP / gcat.

[0082] polymerization

[0083] Polymerization methods can include gas-phase polymerization, particularly fluidized bed gas-phase polymerization. Generally, in gas fluidized bed methods for preparing polymers, a gaseous 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 includes a condenser, typically a noncoordinate inert liquid that is converted to gas during polymerization, such as isopentane, isohexane, or isobutane. The gaseous stream is discharged from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product is discharged from the reactor and fresh monomers are added to replace the polymerized monomers. (See, for example, U.S. Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661 and 5,668,228; all of which are incorporated herein by reference in their entirety.) Gas-phase polymerization can be carried out in any suitable reactor system, such as stirred or paddle reactor systems. See U.S. Patent Nos. 7,915,357; 8,129,484; 7,202,313; 6,833,417; 6,841,630; 6,989,344; 7,504,463; 7,563,851; and 8,101,691 for their discussions of suitable gas-phase fluidized bed polymerization systems, which are incorporated herein by reference.

[0084] In such polymerization methods, the gas-phase fluidized bed process involves continuously passing a stream containing ethylene and olefin comonomers through a fluidized bed reactor at a velocity sufficient to keep the solid particle bed suspended under reaction conditions and in the presence of a catalyst composition. The stream containing unreacted ethylene and olefin comonomers (which may be referred to as the "recycled gas" stream) is continuously removed from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled back to the reactor. The resulting polyethylene copolymer is removed from the reactor, and replacement ethylene and olefin comonomers are added to the recycled stream. In some embodiments, a gas inert to the catalyst composition and reactants is present in the gas stream.

[0085] The reactor pressure during polymerization can be from about 100 psig (680 kPag) to about 500 psig (3448 kPag), for example from about 200 psig (1379 kPag) to about 400 psig (2759 kPag), for example from about 250 psig (1724 kPag) to about 350 psig (2414 kPag). In some embodiments, the reactor is operated at temperatures from about 60°C to about 120°C, such as from about 60°C to about 115°C, such as from about 70°C to about 110°C, such as from about 70°C to about 95°C, such as from about 80°C to about 90°C. The ratio of hydrogen to ethylene can be from about 10 to about 30 ppm / mol%, such as from about 15 to about 25 ppm / mol%, such as from about 16 to about 20 ppm / mol.

[0086] The mol% of ethylene (based on total monomers) can be about 25 to about 90 mol%, for example, about 50 to about 90 mol%, or about 70 to about 85 mol%, and the partial pressure of ethylene (in the reactor) can be about 75 psia (517 kPa) to about 300 psia (2069 kPa), or about 100 psia to about 275 psia (689-1894 kPa), or about 150 psia to about 265 psia (1034-1826 kPa), or about 180 psia to about 200 psia. The ethylene concentration in the reactor can also be in the range of about 35 mol% to about 95 mol%, for example, from the lower limit of 35, 40, 45, 50 or 55 mol% to the upper limit of 70, 75, 80, 85, 90 or 95 mol%, and further wherein the ethylene mol% is measured based on the total number of moles of gases in the reactor (including, if present, ethylene and / or comonomer gases and one or more inert gases, such as nitrogen, isopentane, etc.); as with vol-ppm hydrogen, for convenience, this measurement can be performed at the recirculated gas outlet rather than in the reactor itself. The comonomer concentration can be about 0.2 to about 1 mol%, for example, from the lower limit of 0.2, 0.3, 0.4 or 0.5 mol% to the upper limit of 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95 or 1.0 mol%.

[0087] In at least one embodiment, the α-olefin suitable as a starting material for the preparation of LLDPE can be one or more substituted or unsubstituted C2 to C3 olefins. 40 α-olefins, such as C2-C 32 α-olefins, such as C4-C 32 α-olefins, such as C6-C 30 α-olefins, such as C6-C 24 α-olefins, such as C6-C 18 α-olefins, C6-C16 α-olefins, C6-C 12 α-olefins or combinations thereof. In at least one embodiment, C2 to C3 40 α-olefins can be linear, branched, or cyclic. The C2 to C3... 40 Cyclic olefins can be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups. Non-limiting examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecanene, 1-hexadecene, branched isomers such as 4-methyl-1-pentene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, 5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene, their substituted derivatives and isomers, and combinations thereof.

[0088] In at least one embodiment, the method provides polymerization of ethylene with at least one comonomer containing 3 to 8 carbon atoms (e.g., 4 to 8 carbon atoms). Specifically, the comonomer may be propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, and 1-octene, such as 1-hexene, 1-butene, 1-octene, or combinations thereof. In at least one embodiment, the method provides polymerization of one or more monomers selected from propylene, 1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and combinations thereof.

[0089] Suitable polymerization can be operated at any temperature and / or pressure suitable for obtaining the desired ethylene polymer. Suitable temperatures and / or pressures can include temperatures from about 0°C to about 300°C, for example from about 20°C to about 200°C, for example from about 35°C to about 150°C, for example from about 40°C to about 120°C, for example from about 45°C to about 80°C; and / or pressures from about 0.35 MPa to about 10 MPa, for example from about 0.45 MPa to about 6 MPa, for example from about 0.5 MPa to about 4 MPa. In at least one embodiment, the reactor temperature is greater than about 100°C, or about 105°C, or about 110°C, or in the range of about 100°C, or about 105°C, or about 110°C to about 130°C, or about 140°C, or about 150°C, or about 160°C. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 to about 50 psig (about 0.007 to about 345 kPa), for example about 0.01 to about 25 psig (about 0.07 to about 172 kPa), for example about 0.1 to about 10 psig (about 0.7 to about 70 kPa).

[0090] In at least one embodiment, aluminum oxanes are used almost entirely or not at all in the method for preparing the polymer. The aluminum oxane may be present at about zero mol%, or at a molar ratio of aluminum to transition metal of less than about 500:1, for example less than about 300:1, for example less than about 100:1, for example less than about 1:1. In at least one embodiment, scavengers are used almost entirely or not at all in the method for preparing the ethylene polymer. For example, scavengers (e.g., trialkylaluminum) may be present at zero mol%, or at a molar ratio of scavenger metal to transition metal of less than about 100:1, for example less than about 50:1, for example less than about 15:1, for example less than about 10:1.

[0091] In at least one embodiment, the polymerization is carried out at a temperature of about 0 to about 300°C (e.g., about 25 to about 150°C, about 40 to about 120°C, about 100°C or greater); and at a pressure of about atmospheric pressure to about 10 MPa (e.g., about 0.35 to about 10 MPa, about 0.45 to about 6 MPa, about 0.5 to about 4 MPa). The polymerization is carried out under a pressure of MPa); 3) in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; e.g., wherein an aromatic compound (e.g., toluene) may be present in the solvent at less than 1% by weight, e.g., less than 0.5% by weight, e.g., 0% by weight, based on the weight of the solvent); 4) wherein the catalyst system includes an aluminoxane activator; 5) the polymerization occurs in a reaction zone; and / or 6) optionally a scavenger (e.g., a trialkylaluminum compound) (e.g., present at zero molar %, or the scavenger is present at a molar ratio of scavenger metal to transition metal of less than about 100:1, e.g., less than about 50:1, e.g., less than about 15:1, e.g., less than about 10:1); 7) a continuous additive is present at about 1 ppm to about 60 ppm. The amount is present in ppm; and / or 8) optionally, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 to about 50 psig (about 0.007 to about 345 kPa) (e.g., about 0.01 to about 25 psig (about 0.07 to about 172 kPa), e.g., about 0.1 to about 10 psig (about 0.7 to about 70 kPa)).

[0092] Addition of continuous additives

[0093] The continuous additives disclosed herein can be any suitable continuous additives, such as those described below. In some embodiments, the total amount of continuous additives (one or more) present in the reactor is about 60, 50, 40, 30, 20, or 10 ppm (based on the weight of the polymer produced), or greater than about 1, 3, 5, 7, 10, 12, 14, 15, 17, or 20 ppm (based on the weight of the polymer produced, typically expressed in pounds or kilograms per unit time). Any of these lower limits can be combined with any upper limit. The amount of these continuous additives covers one, two, three, four, or more continuous additives, and the total amount of one, two, or more continuous additives in the reactor should be understood to be consistent with the total amount just disclosed above. Continuous additives can be added directly to the reactor via a dedicated feed line and / or to any convenient feed stream, including monomer (e.g., ethylene feed stream), comonomer feed stream, catalyst feed line (e.g., in a trimming process), or recirculation line. If more than one continuous additive is used, each additive can be added to the reactor as a separate feed stream, or as a separate feed stream or any combination of the additives.

[0094] The method disclosed herein includes introducing at least one continuous additive into a catalyst mixture, injecting the catalyst mixture (containing at least one continuous additive) into a reactor, and additionally or alternatively introducing at least one continuous additive into the reactor via a dedicated continuous additive feed line separate from the catalyst mixture, thereby introducing said at least one continuous additive in a sufficient concentration directly or indirectly into the reactor. Any one or a combination of these feeding methods may be employed. The continuous additive in the catalyst / continuous additive mixture may be the same as or different from the continuous additive added via a separate continuous additive feed line.

[0095] If a combination of continuous additives is used, the total amount present in the reactor can be as described above.

[0096] Continuous additives

[0097] Continuous additives may exist in the form of slurry or suspension, and may optionally contain, in addition to conventional active substances, a class of pre-added scavengers, such as those used to neutralize moisture. As used herein, "neutralization" refers to the ability of the scavenger to react with catalyst poisons (such as water) in a way that does not adversely affect catalyst activity. "Adverse effect" as used herein refers to a loss of catalyst activity measured relative to a predetermined level of 1% or more, or 5% or more, or 10% or more, or 15% or more, or 20% or more, or 25% or more, or 30% or more.

[0098] The continuous additives disclosed herein can be prepared using any suitable method, such as those described in paragraphs

[0058] -

[0067] of EP2183286, which are incorporated herein by reference.

[0099] The adjuvant is often referred to as a continuous adjuvant because it promotes a continuous reaction process by preventing interruptions such as flakes or lumps.

[0100] According to a preferred embodiment, the continuous additive comprises a substance characterized in that, when introduced into a polymerization reactor system in an effective amount, it is capable of reducing, preventing, or mitigating at least one of scaling, flocculing, and static charge levels of the material present in the polymerization reactor system.

[0101] According to another embodiment, the continuous additive comprises a substance characterized by its ability, when introduced into the polymerization reactor system in an effective amount, to reduce, prevent, or mitigate the effects of at least one of scaling, flocculing, and electrostatic charge levels present in the polymerization reactor system. A cleaning agent may contact the continuous additive, thereby removing water from the cleaning agent and the water in contact with it. As measured before adding the cleaning agent, the cleaning agent may be present at a concentration of 0.25 to 5.0 mol cleaning agent per mol of water in the continuous additive. It should be noted that higher or lower amounts of cleaning agent may also be added. In another type of embodiment, the amount of cleaning agent contacting the continuous additive is 0.8 to 1.50 mol cleaning agent per mol of the measured amount of water.

[0102] In some embodiments, the amount of scavenger present does not exceed the approximate amount required to neutralize the moisture in the continuous additive, in order to minimize any potential interference of the scavenger on the active substances in the continuous additive and / or the reaction in the reactor system.

[0103] In some embodiments, the continuous additive is aluminum distearate. In some embodiments, the continuous additive may include one or more compounds selected from alkoxylated amines and carboxylates.

[0104] Ethoxylated stearamine is commercially available from Cargill and supplied under the trade name ATMER163.

[0105] Continuous additives may include aluminum stearate, aluminum distearate, aluminum oleate, and oxolaluminum stearate. Other additives are commercially available under the trade names OCTASTAT and STADIS and are described in U.S. Patent No. 5,026,795.

[0106] In another type of embodiment, the continuous additive may comprise a mixture of two or more of the above-mentioned materials. Such mixtures may include: alkoxylated amines and carboxylates; or alkoxylated amines and polysulfones; or alkoxylated amines and polyamines; or alkoxylated amines and sulfonic acids; or carboxylates and polysulfones; or carboxylates and polyamines; or carboxylates and sulfonic acids; or polysulfones and polyamines; or polysulfones and sulfonic acids; or polyamines and sulfonic acids. Also considered are alkoxylated amines, carboxylates and polysulfones; or alkoxylated amines, polyamines and sulfonic acids; or carboxylates, polysulfones and polyamines; or carboxylates, sulfonic acids and polysulfones; alkoxylated amines, carboxylates and polyamines; alkoxylated amines, carboxylates and sulfonic acids; alkoxylated amines, polysulfones and sulfonic acids; alkoxylated amines, polyamines and polysulfones; polysulfones, polyamines and sulfonic acids; carboxylates, polyamines and sulfonic acids. Combinations of three, four or more of these continuous additives are also considered. These combinations can be made in weight ratios of about 10:90 to 90:10, or 25:75 to 75:25, or 40:60 to 60:40, or 50:50, or in the case of three continuous adjuvants, in weight ratios of 10:10:80 to 80:10:10 or 10:80:10.

[0107] Another continuous additive used in this disclosed embodiment includes a mixture of 1-decene-polysulfone, the reaction product of N-tallow-1,3-diaminopropane and epichlorohydrin, dodecylbenzenesulfonic acid, and a hydrocarbon solvent. Such mixtures are available from Octel Starreon and its affiliates under the trade names OCTASTAT3000 (also available as STADIS 450) or OCTASTAT 2000 (also available as STADIS 425).

[0108] Aggregates using trim

[0109] The polymerization method of this disclosure can be performed using a "trimming" method. Trimming processes are described, for example, in U.S. Patent Publication No. 2021 / 0395404, particularly in conjunction with Figure 1 therein and paragraphs

[0113] -

[0124] , which are incorporated herein by reference. An overview of such processes, which are particularly useful to this disclosure, is also provided below.

[0110] A second catalyst solution (e.g., a catalyst slurry having at least one catalyst of formula (I), formula (IIa) / (IIb) or formula (III)) may be added (i.e., "trimmed") to the slurry of the first catalyst (one or more) (at least one of formula (I), formula (IIa) / (IIb) or formula (III)) to "in situ" adjust one or more properties of the polymer being formed in the reactor. The catalyst (one or more) of the slurry of the first catalyst (one or more) may be the same as or different from the second catalyst (one or more).

[0111] Therefore, methods for polymerizing olefins (one or more) may include the use of a multi-catalyst system (e.g., by in-situ loading of a second or third catalyst).

[0112] In some embodiments, the method includes contacting a first composition with a second composition in a pipeline leading to a reactor to form a third composition. The first composition includes a first catalyst (or catalyst compound), a support, and a diluent. The first catalyst or catalyst compound may be referred to herein as a "primary catalyst" or "base catalyst." The second composition includes a second catalyst (or catalyst compound) and a second diluent. The second catalyst or catalyst compound may be referred to as a "trimming catalyst," and particularly in the method described herein, the trimming process is preferably used to adjust the ratio of the first catalyst to the second catalyst by increasing or decreasing the relative amount of the trimming catalyst relative to the primary catalyst. The method includes introducing the third composition in the pipeline into a gas-phase fluidized bed reactor and subjecting the third composition to polymerization conditions. The method includes obtaining a polyolefin.

[0113] The process may include adjusting reactor conditions, such as adjusting the amount of a second catalyst supplied to the reactor (via a pipeline leading to the reactor), to control the properties of one or more polymers of polyolefin obtained from the reactor.

[0114] Further details regarding the finishing process can be found in paragraphs

[0123] -

[0127] of WO2021 / 222280, which may be incorporated herein by reference.

[0115] Polymer products

[0116] This disclosure further provides compositions that can be produced by the methods of this disclosure. In at least one embodiment, the methods described herein produce ethylene homopolymers or ethylene copolymers, such as ethylene-α-olefins (e.g., C3 to C4). 40 For example, C3-C 20 α-olefins, such as C3 to C4 12 α-olefins, such as propylene, butene, hexene, octene, decene, and dodecene, and copolymers of propylene, butene, hexene, and octene (e.g., ethylene-butene copolymers, ethylene-hexene copolymers, and / or ethylene-octene copolymers). In some embodiments, the α-olefin is a C4 to C8 α-olefin.

[0117] In at least one embodiment, when measured according to GPC-IR5-LS-VIS, the LLDPE may have an ethylene content of about 65 wt% or higher, for example, about 80 wt% to about 99.9 wt%, for example, about 85 wt% to about 99.5 wt%, for example, about 90 wt% to about 99 wt%, for example, about 91 wt% to about 98 wt%, for example, about 92 wt% to about 97 wt%, for example, about 93 wt% to about 96 wt%, for example, about 94 wt% to about 95 wt%, for example, about 92 wt% to about 98 wt%. In some embodiments, the ethylene content may be about 65 wt% or higher, for example, about 90 wt% to about 96 wt%.

[0118] In at least one embodiment, when measured according to GPC-IR5-LS-VIS, the LLDPE may have a comonomer content of about 35 wt% or less, for example, about 0.1 wt% to about 20 wt%, for example, about 0.5 wt% to about 15 wt%, for example, about 1 wt% to about 10 wt%, for example, about 2 wt% to about 9 wt%, for example, about 3 wt% to about 8 wt%, for example, about 4 wt% to about 7 wt%, for example, about 5 wt% to about 6 wt%. In some embodiments, the comonomer content may be about 35 wt% or less, for example, about 4 wt% to about 10 wt%.

[0119] In some implementations, LLDPE can have a number-average molecular weight (Mn) of about 5,000 g / mol to about 30,000 g / mol when measured according to GPC-IR5-LS-VIS.

[0120] In at least one embodiment, LLDPE can have a weight-average molecular weight (Mw) of about 75,000 g / mol to about 200,000 g / mol when measured according to GPC-IR5-LS-VIS.

[0121] In at least one embodiment, LLDPE can have a Z-average molecular weight (Mz) of about 500,000 g / mol to about 1,800,000 g / mol when measured according to GPC-IR5-LS-VIS.

[0122] In some embodiments, LLDPE may have a molecular weight distribution (MWD) of about 2 to about 10, such as about 2.5 to about 9, such as about 3 to about 8, as measured by GPC-IR5-LS-VIS, defined as Mw / Mn. In at least one embodiment, Mw / Mn may be about 2 to about 8, such as about 3 to about 7, such as about 4 to about 6, such as about 5 or 5.5.

[0123] In some implementations, when measured according to GPC-IR5-LS-VIS, LLDPE may have a g'vis of about 0.9 or more and 0.97 or less.

[0124] In at least one embodiment, the LLDPE may have a melt index (MI, I2) of about 0.3 g / 10min to about 20 g / 10min, such as about 0.5 g / 10min to about 3 g / 10min, such as about 6 g / 10min to about 1.5 g / 10min, as measured according to ASTM D1238 (190°C, 2.16 kg load).

[0125] In at least one embodiment, the LLDPE may have a high load melt index (HLMI) of about 10 g / 10min to about 60 g / 10min, such as about 15 g / 10min to about 40 g / 10min, such as about 15 g / 10min to about 25 g / 10min, or about 25 g / 10min to about 35 g / 10min as determined by ASTM D1238 (190°C, 2.16 kg load).

[0126] In at least one embodiment, the LLDPE may have an HLMI / MI ratio of about 15 to about 50, such as about 20 to about 30, such as about 20 to about 25, or about 25 to about 30, as determined by ASTM D1238 (190°C, 2.16 kg load).

[0127] In at least one embodiment, LLDPE may have a density gradient column method of approximately 0.91 g / cm³ as determined by ASTM D1505. 3 To approximately 0.94 g / cm 3 For example, approximately 0.915 g / cm³ 3 Approximately 0.935 g / cm³ 3 For example, approximately 0.92 g / cm³ 3 Approximately 0.93 g / cm³ 3 The gradient density. In some implementations, the gradient density can be approximately 0.917 g / cm³. 3 To approximately 0.94 g / cm 3 For example, approximately 0.918 g / cm³ 3 Approximately 0.935 g / cm³ 3 .

[0128] In at least one embodiment, LLDPE may have a content of approximately 0.45 g / cm³ as determined by ASTM D-1895. 3 To approximately 0.52 g / cm3 For example, approximately 0.455 g / cm³ 3 To approximately 0.5 g / cm 3 For example, approximately 0.45 g / cm³ 3 Approximately 0.46 g / cm³ 3 Or approximately 0.46 g / cm³ 3 Approximately 0.49 g / cm³ 3 For example, approximately 0.47 g / cm³ 3 Approximately 0.49 g / cm³ 3 For example, approximately 0.48 g / cm³ 3 Approximately 0.49 g / cm³ 3 The packing density.

[0129] Wide orthogonal composition distribution

[0130] "BOCD" refers to a broadly orthogonal compositional distribution, in which the comonomers of the copolymer are primarily bound to the high molecular weight chains or substances of the polyolefin polymer or composition. The distribution of short chain branches can be measured using, for example, the TREF-IR5 procedure described in the "Test Methods" section below. BOCD has been described, for example, in U.S. Patent No. 8,378,043, column 3, lines 34 through 4, lines 19; and in U.S. Patent No. 8,476,392, lines 43 through 16, lines 54.

[0131] The BOCD properties of the polyethylene copolymers of the present invention can be quantified by the composition distribution width index (CDBI). For example, the ethylene copolymers described herein may have a composition distribution width index (CDBI) value, wherein the CDBI% of the ethylene copolymer may be within the range of any lower limit of about 40, 45, 50, 55, 60, 65, 70, 75 or 80% to any upper limit of about 99, 95, 90, 85, 80, 75, 70, 65 or 60%; the range from any of the aforementioned lower limits to any of the aforementioned upper limits is considered herein (e.g., about 50% to about 85%, for example about 55% to about 75%, or about 70% to about 85%, or about 75% to about 85%). In some embodiments, the ethylene copolymer described herein may have a compositional distribution width index (CDBI) value, wherein the CDBI% of the ethylene copolymer may be in the range of any lower limit of about 30, 35, 40, 45, 50 or 55% to any upper limit of about 70, 65, 60, 55, 50 or 45%; the range from any of the aforementioned lower limits to any of the aforementioned upper limits is considered herein (e.g., about 35% to about 65%, such as about 40% to about 50%, or about 50% to about 65%, such as about 50% to about 60%).

[0132] CDBI is defined as the weight percentage of copolymer molecules with a comonomer content within + / - 50% of the median comonomer mol% value, as described on pages 18-19 of WO 1993 / 003093 in conjunction with Figure 17 therein. This means that for a copolymer with a median comonomer mol% value (Cmed) of 8 mol% comonomer on the polymer chain, CDBI is the weight percentage of the copolymer chain with a comonomer mol% between (0.5 × Cmed) and (1.5 × Cmed). In this example, CDBI is the weight percentage of the copolymer chain with a comonomer mol% between (0.5 × 8) and (1.5 × 8) or a comonomer content between 4 mol% and 12 mol%. WO 1993 / 003093 also describes the use of chromatography and C... 13 A method for determining the weight fraction vs. composition curve (i.e., composition distribution curve) of a polymer by NMR and determining the median comonomer composition Cmed from it, refer to Figures 16 and 17 of that disclosure. See also Wild et al., J. Poly. Sci., Poly. Phys. Ed., vol. 20, p. 441 (1982) and U.S. Patent No. 5,008,204, which are also incorporated herein by reference.

[0133] Test methods

[0134] A. Resin Analysis

[0135] Melt index (MI, also known as I2) is determined according to ASTM D1238 at 190°C under a load of 2.16 kg, unless otherwise specified. The unit of MI is g / 10 min or dg / min. High load melt index (HLMI, also known as I2) 21 HLMI is the melt flow rate measured according to ASTM D-1238 at 190°C and a load of 21.6 kg. The unit of HLMI is g / 10 min or dg / min. The melt index ratio (MIR) is the ratio of the high-load melt index to the total melt index, or I... 21 / I2. Density was measured on a compression-molded specimen using a density gradient column as described in ASTM D1505; the specimen had been cooled to room temperature according to ASTM D4703-10a procedure C and then subjected to ASTM D618-08 (23) prior to testing. o Condition for 40 hours at ±2℃ and 50±10% relative humidity.

[0136] Gel permeation chromatography (GPC)

[0137] Although GPC in CFC analysis also generates molecular weight distribution and moments, for the purposes of the claims, the molecular weight distribution and moments (Mw, Mn, Mw / Mn, etc.), comonomer content (C2, C3, C6, etc.), and branching index (g'vis) from GPC-IR5-LS-VIS are used.

[0138] The GPC-IR5-LS-VIS is a high-temperature gel permeation chromatography (Polymer Char GPC-IR) system equipped with a multi-channel bandpass filter-based infrared detector IR5, an 18-angle Wyatt Dawn Heleos light scattering detector, and a 4-capillary viscometer with a Wheatstone bridge configuration. Three Agilent PLGEL 10... The m-mix-B LS column was used to provide polymer separation. Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB) containing 300 ppm of the antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. This TCB mixture was filtered through 0.1... The solution is filtered through a Teflon filter and degassed using an in-line degasser before entering the GPC instrument. The nominal flow rate is 1.0 ml / min, and the nominal injection volume is 200 ml / min. L. The entire system, including the delivery lines, column, and viscometer detector, is loaded into an oven maintained at 145°C. The polymer sample is weighed and sealed in a standard finger tube, and 80 g of [unspecified substance] is added to it. L-flow marker (heptane). After the finger tube is inserted into the autosampler, the polymer is automatically dissolved in the instrument with 8 mL of added TCB solvent. The polymer is dissolved at 160 °C with continuous vibration for approximately 2 hours. The concentration (c) at each point in the chromatogram is calculated by subtracting the baseline IR5 broadband signal intensity (I) using the following equation: c = βI, where β is the mass constant. Mass recovery is calculated by the ratio of the integral area of ​​the concentration chromatography to the elution volume, and the injection mass is equal to the predicted concentration multiplied by the injection loop volume. Conventional molecular weight (IRMW) is determined by combining a universal calibration relationship with column calibration using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mol. MW is calculated for each elution volume using the following equation:

[0139]

[0140] Variables with the subscript "PS" represent polystyrene, while those without subscripts are the test samples. In this method, α... PS =0.67 and K PS=0.000175, while for other materials α and K are calculated and disclosed as described in the literature (e.g., Sun, T. et al. (2001) Macromolecules, Vol. 34, p. 6812), specifically, for linear ethylene polymers, α = 0.695 and K = 0.000579, and for linear propylene polymers, α = 0.705 and K = 0.0002288. Unless otherwise stated, concentration is expressed in g / cm3, molecular weight in g / mol, and intrinsic viscosity (therefore K in the Mark–Houwink equation) in dL / g. Here, unless otherwise stated, concentration is expressed in g / cm3. 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dl / g.

[0141] The comonomer composition was determined by the proportions corresponding to the IR5 detector intensities of the CH2 and CH3 channels, calibrated using a series of PE and PP homopolymer / copolymer standard samples, the nominal values ​​of which were determined beforehand by NMR or FTIR. Specifically, this provides the number of methyl groups / 1,000 total carbons as a function of molecular weight (CH3 / 1,000TC). The short-chain branching (SCB) content / 1000TC as a function of molecular weight (SCB / 1000TC) was then calculated as follows: a chain-end correction was applied to the CH3 / 1000TC functional groups, assuming each chain was linear and end-capped with a methyl group at each end.

[0142] The molecular weight (M) of LS at each point in the chromatogram was determined by analyzing the LS output using the Zimm model of static light scattering.

[0143] .

[0144] Here, ΔR(θ) is the scattering angle. The measured excess Rayleigh scattering intensity, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K... o These are the optical constants of the system:

[0145]

[0146] Where N A is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. The refractive index n of TCB at 145℃ and λ=665nm is 1.500. For the analysis of the PE polymer, dn / dc = 0.1048 ml / mg and A2 = 0.0015.

[0147] Specific viscosity is determined using a high-temperature polymer Char viscometer, which has four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector, and the other, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is... s Calculated from their outputs. The intrinsic viscosity [η] at each point in the chromatogram is given by the formula [η] = η s / c is calculated, where c is the concentration and is determined by the output of the IR5 broadband channel.

[0148] The branching index (g'vis) was calculated using the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity of the sample [η] avg The calculation is as follows:

[0149]

[0150] The sum is taken from all chromatogram slices i between the integration limits.

[0151] Branching index g' vis Defined as:

[0152] ,

[0153] Where Mv is the viscosity-average molecular weight based on the molecular weight determined by LS analysis, and K and α are for a reference linear polymer; for the purposes of this disclosure, α and K are the same as those described above for linear polyethylene polymers.

[0154] TREF-IR5

[0155] Temperature elution fractionation (TREF) analysis can be performed using a crystallization elution fractionation (CEF) instrument obtained from Polymer Char, SA, Valencia, Spain. An overview of the principles of CEF analysis and the specific equipment used is given in the paper Monrabal, B.; del Hierro, P. Anal. Bioanal. Chem. 2011, v. 399, pg. 1557. Figure 3 in that paper is a suitable schematic diagram of the specific equipment used; however, the connection of the 6-way valve shown in Figure 3 differs from the equipment to be used, in that the tubing connected to the 11 o'clock port is connected to the 9 o'clock port, and the tubing connected to the 9 o'clock port is connected to the 11 o'clock port. Details of the analytical method and characteristics of the equipment to be used are as follows.

[0156] The solvent used for sample solution preparation and elution was 1,2-dichlorobenzene (ODCB), which was stabilized by dissolving 1.6 g of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene) in a 4-L bottle of fresh solvent at ambient temperature. The stabilized solvent was then filtered through a 0.1 μm Teflon (Millipore) filter. The sample to be analyzed (6–10 mg) was dissolved in 8 mL of ODCB, measured at ambient temperature, by stirring (medium setting) at 150 °C for 90 min. Small volumes of the polymer solution were first filtered through an in-line filter (stainless steel, 10 μm), which was backwashed after each filtration. The filtrate was then used to completely fill the 200-μl injection valve circuit. The sample volume was then introduced into the loop near the center of a CEF column (15 cm long SS tubing, 3 / 8″ outer diameter, 7.8 mm inner diameter) filled with inert support (SS spheres) at 140 °C, and the column temperature was stabilized at 125 °C for 20 min. The sample volume was then allowed to crystallize in the column by cooling to 0 °C at a rate of 1 °C / min. The column was held at 0 °C for 10 min, and then ODCB fluid (1 ml / min) was injected into the column for 10 min to elute and measure the non-crystallizable polymer (soluble fraction). The broadband channel of the infrared detector (PolymerChar IR5) used generated an absorption signal that was proportional to the polymer concentration in the elution stream. A complete TREF profile was then generated as follows: the column temperature was increased from 0 °C to 140 °C at a rate of 2 °C / min while maintaining an ODCB flow rate of 1 ml / min to elute and measure the concentration of dissolved polymer.

[0157] Example

[0158] Catalyst Examples Synthesis

[0159] Unless otherwise specified, all reactions were carried out in a glove box purged with inert N2. All anhydrous solvents were purchased from Fisher Chemicals and degassed and dried on molecular sieves before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and dried on molecular sieves before use. Butyllithium (2.5 M hexane solution), dicyclopentadiene, and dimethyl sulfide (Me2S) were purchased from Sigma-Aldrich. Hafnium tetrachloride (HfCl4) 99+% and trimethylsilylmethyl trifluoromethanesulfonate were purchased from Strem Chemicals and TCI America, respectively, and used as received. MAO was methylaluminoxane (30 wt%, in toluene) obtained from Albemarle.

[0160] Example Synthesis of Metallocene Catalyst 1

[0161] Metallocene catalyst 1 is:

[0162] .

[0163] Synthesis of Trimethylsilylmethylcyclopentadiene, Me3SiCH2CpH. Pure trimethylsilylmethyltrifluoromethanesulfonate (25.0 g, 105.8 mmol) was dissolved in 300 mL of diethyl ether and cooled to -25 °C. Solid potassium cyclopentadienide (11.14 g, 106.9 mmol) was slowly added over a period of 10–15 minutes. The resulting mixture was stirred overnight at room temperature. Insoluble material was filtered off. Volatile substances in the reaction mixture were carefully removed under dynamic vacuum to avoid evaporation of volatile trimethylsilylmethylcyclopentadiene Me3SiCH2CpH. The reaction flask (250 mL round-bottom flask) and the flask with diatomaceous earth were weighed to calculate the product yield after extraction. The crude material was then extracted into pentane (3 × 50 mL) and used without further purification. The yield was calculated to be 15.47 g (95.2%) according to the above mathematical method. Record the 1H NMR spectrum of the crude material to ensure product formation. 1 H NMR (400 MHz, C6D6): δ-0.05(9H,s,Si-CH3),1.77(2H,d,J HH =1.2Hz,Me3Si-CH2),2.83(1H,sex,J HH =1.5Hz,Cp-CH),5.80-6.49(4H,m,Cp-CH)ppm.

[0164] Synthesis of trimethylsilylmethylcyclopentadienyl lithium Me3SiCH2CpLi. A hexane solution of n-butyllithium (41.5 mL, 103.8 mmol, 2.5 M solution) was added dropwise over a period of 40–50 minutes at -25 °C to a pre-cooled solution of Me3SiCH2CpLi (15.47 g, 101.7 mmol) (a 1:1 mixture of pentane and diethyl ether, 200 mL). The resulting mixture was gradually brought to room temperature and then stirred continuously overnight. Volatiles were removed under vacuum and the remaining crude material was vigorously washed with pentane. The final material was dried under vacuum to give 13.6 g (84.6%) of colorless crystalline solid of Me3SiCH2CpLi. 1 H NMR (400 MHz, THF-) d 8): δ-0.09(9H,s,Si-C H3), 1.84(2H,s,Me3Si-C H 2), 5.36(2H,t,J HH =2.6Hz,Cp-C H ),5.47(2H,t,J HH =2.6 Hz, Cp-C H )ppm.

[0165] Synthesis of dichlorobis-(trimethylsilylmethylcyclopentadiene)hafnium(Me3SiCH2Cp)2HfCl2. Solid HfCl4 (1.011 g, 3.16 mmol) was slurried in pre-cooled diethyl ether (30 mL) at -25 °C, and solid Me3SiCH2CpLi (1.0 g, 6.3 mmol) was added over a period of 3–5 minutes. The resulting mixture was stirred overnight at room temperature. All volatiles were removed under vacuum, and the crude material was then extracted into dichloromethane. The solvent was removed under reduced pressure to give spectroscopically pure (Me3SiCH2Cp)2HfCl2 as a colorless solid, in a yield of 1.13 g (70%). 1 H NMR(400 MHz C6D6): δ-0.11(18H,s,SiMe3-C H 3), 2.18(4H,s,Me3Si-C H 2), 5.68(8H,s,Cp-C H )ppm.

[0166] Synthesis of dimethylbis-(trimethylsilylmethylcyclopentadienyl)hafnium(Me3SiCH2Cp)2HfMe2 (metallocene catalyst 1). An ether solution of MeLi (2.56 mL, 4.1 mmol) was added dropwise to a pre-cooled ether solution of (Me3SiCH2Cp)2HfCl2 (1.12 g, 2.03 mmol) over a period of 3–5 minutes at -25 °C. The mixture was stirred overnight at room temperature to ensure complete reaction. The insoluble material was filtered through a diatomaceous earth (celite) mat. Volatiles were removed from the filtrate under vacuum. The crude product was ground with pentane, then extracted into pentane, followed by solvent removal to give a colorless crystalline material of (Me3SiCH2Cp)2HfMe2 in a yield of 875 mg (84.2%). 1 H NMR(400 MHz,C6D6): δ-0.23(6H,s,Hf-C H 3), 0.02(18H,s,SiMe3-C H 3), 1.89(4H,s,Me3Si-C) H 2), 5.54-5.48(8H,m,Cp-C H )ppm.

[0167] Examples of synthesis of metallocene catalyst 2

[0168] Metallocene catalyst 2 is dichloro-(tetrahydroindenyl)(trimethylsilyl-methylcyclopentadienyl)hafnium:

[0169] .

[0170] Preparation of dichloro·(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)hafnium(H4Ind)(Me3SiCH2Cp)HfCl2. Platinum oxide (0.04 g, 0.18 mmol, 2.7 wt%) was added to a pale yellow solution of dichloro·indyl(trimethylsilylmethylcyclopentadienyl)hafnium (1.50 g, 2.91 mmol) in dichloromethane (30 mL) to give a brown mixture. Hydrogen gas at 100 psi was added to the mixture and the reaction was stirred vigorously for 1 h. The reaction was vented and filtered to give a colorless solution and a black solid. The solution was evaporated under vacuum, leaving a white solid, the subject compound dichloro·(tetrahydroindyl)(trimethylsilylmethylcyclopentadienyl)hafnium(H4Ind)(Me3SiCH2Cp)HfCl2. Yield: 1.43 g (95%). 1 HNMR(CD2Cl2): δ6.23(t,1H), 6.15(t,2H), 5.88(t,2H), 5.67(d,2H), 2.85-2.92(m,2H),2.59-2.66(m,2H),2.09(s,2H),1.77-1.80(m,2H),1.60-1.63(m,2H),-0.02(s,9H).

[0171] Preparation of dichloro-indyl(trimethylsilylmethylcyclopentadienyl)hafnium Ind(Me3SiCH2Cp)HfCl2. Lithium indide (0.57 g, 4.75 mmol, 1.00 equivalent) was added to a white suspension of trichloro-(trimethylsilylmethylcyclopentadienyl)hafnium (1,2-dimethoxyethane) (2.50 g, 4.75 mmol, 1.00 equivalent) in ether (30 mL), yielding a light-colored mixture. The mixture was stirred for 21 hours and then evaporated under vacuum, leaving a solid. The solid was extracted with dichloromethane (25 mL, then 3 × 5 mL) and the extract was filtered to give a pale yellow solution and a white solid. The solution was evaporated under vacuum, leaving a pale yellow solid. The solid was washed with pentane (10 mL) and dried under vacuum to provide the subject compound (dichloro-indenyl(trimethylsilylmethylcyclopentadienyl)hafnium, Ind(Me3SiCH2Cp)HfCl2). Yield: 2.27 g (93%) pale yellow powder. 1H NMR(CD2Cl2): δ 7.65(m,2H),7.26(m,2H),6.87(t,1H),6.37(d,2H),5.77(t,2H),5.65(t,2H),1.99(s,2H),-0.06(s,9H).

[0172] Preparation of trichloro-(trimethylsilylmethylcyclopentadienyl)hafnium(1,2-dimethoxyethane) ((Me3SiCH2Cp)HfCl3(dme)). A turbid, pale yellow solution was obtained by adding dimethyl sulfide (6.80 g, 109 mmol, 3.01 equivalents) to a white suspension of hafnium tetrachloride (11.65 g, 36.4 mmol, 1.00 equivalents) in dichloromethane (120 mL) at -35 °C. A turbid, amber solution was obtained by adding tributyl(trimethylsilylmethylcyclopentadienyl)stanane (16.85 g, 38.2 mmol, 1.05 equivalents) dropwise to this solution. The mixture was allowed to warm to room temperature and stirred for 3 hours. 1,2-Dimethoxyethane (10.00 g, 109 mmol, 2.99 equivalents) was then added to the reaction mixture, and the mixture was filtered to obtain an amber solution and a small amount of white solid. The solution was evaporated under vacuum, leaving a moist white solid. The solid was washed with pentane (100 mL, followed by 3 × 40 mL) and dried under vacuum to give the subject compound (Me3SiCH2Cp)HfCl3(dme). 18.15 g (95%) of white powder was produced. 1 H NMR(CD2Cl2): δ 6.29(t,2H), 4.13(br s,4H), 3.91(3,6H), 2.33(s,2H), -0.01(s,9H).

[0173] Preparation of tributyl(trimethylsilylmethylcyclopentadienyl)stanane Bu3Sn(Me3SiCH2Cp). Lithium (trimethylsilylmethylcyclopentadienyl) (6.10 g, 38.5 mmol, 1.00 equivalent) was added to a colorless solution of tributylstanane (12.55 g, 38.6 mmol, 1.00 equivalent) in ether (60 mL) to give a turbid, light-colored mixture. The reaction was stirred for 4 h, then dried under vacuum, leaving the mixture. The mixture was extracted with pentane (50 mL, then 2 × 20 mL) and the extract was filtered to give a yellow solution and a solid. The solution was evaporated under vacuum, leaving a yellow liquid containing the main compound (Bu3Sn(Me3SiCH2Cp)). Yield: 16.88 g (99%). 1H NMR(C6D6): δ 6.08(m,2H),5.56(m,4H), 1.99(s,2H),1.51(m,6H), 1.33(m,6H),0.92(t,9H), 0.83(m,6H), 0.09(s,9H).

[0174] Example of synthesis of iron catalyst 1

[0175] Iron catalyst 1 is:

[0176]

[0177] 2-Chloro-4,6-dimethylaniline, 2,6-diacetylpyridine, ferric chloride, and formic acid (95-97%) were all purchased from Sigma-Aldrich and used as received. 1 H NMR measurements were recorded on a 400 MHz Bruker spectrometer.

[0178] Synthesis of 2,6-bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine. Solid 2,6-diacetylpyridine (5.0 g, 31 mmol) was dissolved in methanol (100 mL). Then, solid 2-chloro-4,6-dimethylaniline (9.537 g, 62 mmol) and formic acid (0.5 mL) were added. The resulting mixture was stirred at room temperature for 48 hours, during which a colorless solid precipitate formed. The colorless crystalline solid was filtered off and washed with cold methanol. The 1H NMR spectrum of the crude material showed that the ratio of the precursor compound to the starting material 2-chloro-4,6-dimethylaniline was 1:1. The desired compound was purified by column chromatography using a mixture of hexane and ethyl acetate (8:2 ratio) as the eluent, and the solvent was removed to give a colorless crystalline solid (2,6-bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine), with a yield of 2.5 g (18.6%). 1 H NMR (400 MHz, CD2Cl2): δ 2.06(6H,s,CH3 side arm), 2.29(6H,s,CH3), 2.31(6H,s,CH3),6.99(2H,s,Ar-CH),7.11(2H,s,Ar-CH),7.95(1H,t,Ar-CH), 8.47(2H,d,Ar-CH)ppm.

[0179] Synthesis of ferrous chloride in 2,6-bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine (iron catalyst 1). The solid ligand precursor 2,6-bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine was dissolved in THF (40 mL) and cooled to -25 °C. Pre-dried solid ferric chloride was added to the solution. The mixture was stirred overnight at room temperature. During the reaction, the mixture changed color from brown to blue, and the desired iron complex precipitated as a blue solid. The blue iron compound was filtered off and washed with hexane. The crude material was further redissolved in dichloromethane to remove any insoluble iron-containing impurities and ionic compounds formed during the reaction, which are impermeable due to their faster relaxation rate (paramagnetism) on the NMR timescale. 1 Identification was performed by ¹H NMR. The solvent was removed under reduced pressure to give a blue crystalline solid of ferrous 2,6-bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine, with a yield of 1.89 g (81.9%). 1 HNMR (400 MHz, CD2Cl2): δ-23.2,-21.0, 3.7,9.1, 12.2,15.3,18.4, 19.3,22.0,22.2,32.9,33.9,81.9,84.2(bs)ppm.

[0180] Preparation of supported mixed catalysts:

[0181] Metallocene catalyst 2: Iron catalyst 1 60:40 Prep 2,22 μmol

[0182] 1800 g of toluene (Sigma Aldrich) and 894 g of methylaluminoxane (30 wt% toluene solution, Albemarle) were added to a stirred vessel. 741 g of ES70 (Ineos) – calcined silica at 875 °C was added to this solution. The mixture was stirred at 80 °C for 3 hours, then the temperature was lowered and the reaction was allowed to cool to ambient temperature. Then, 6.86 g (13.2 mmol) of hafnium dichloro(tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl) was dissolved in toluene (250 g) and added to the vessel, followed by stirring for one hour. The mixing rate was then reduced and the mixture was stirred slowly while drying under vacuum for 65 hours, yielding 984 g of silica-supported catalyst.

[0183] Metallocene catalyst 2: Iron catalyst 1 80:20 Prep 2.22 umol

[0184] 1800 g of toluene (Sigma Aldrich) and 894 g of methylaluminoxane (30 wt% toluene solution, Albemarle) were added to a stirred vessel. 741 g of ES70 (Ineos) – calcined silica at 875 °C was added to this solution. The mixture was stirred at 80 °C for 3 hours, then the temperature was lowered and the reaction was allowed to cool to ambient temperature. Then, 9.15 g (17.6 mmol) of dichloro-(tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl)hafnium chloride and 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridineferrous chloride(II) (2.49 g, 4.40 mmol) were dissolved in toluene (250 g) and added to the vessel, and stirred for one hour. The mixing rate was then reduced and the mixture was stirred slowly while drying under vacuum for 65 hours, yielding 992 g of silica-supported catalyst.

[0185] Metallocene catalyst 1: Iron catalyst 1 80:20 Prep 2,30 umol

[0186] 1668 g of toluene (Sigma Aldrich) and 925 g of methylaluminoxane (30 wt% toluene solution, Albemarle) were added to a stirred vessel. 734 g of ES70 (Ineos) – calcined silica at 875 °C was added to this solution. The mixture was stirred at 80 °C for 3 hours, then the temperature was lowered and the reaction was allowed to cool to ambient temperature. Subsequently, dimethylbis(trimethylsilylmethylcyclopentadienyl)hafnium chloride (12.27 g, 24.00 mmol) and 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridineferrous chloride(II) (3.39 g, 6.00 mmol) dissolved in toluene (250 g) were added to the vessel and stirred for one hour. The mixing rate was then reduced and the mixture was stirred slowly while drying under vacuum for 65 hours, yielding 1036 g of silica-supported catalyst.

[0187] Process Overview

[0188] The polymerization reaction was carried out in an 18.5-foot-high gas-phase fluidized bed reactor with a 10-foot-high main body and an 8.5-foot-high expansion zone. Recirculated gas and feed gas entered the reactor main body through a porous distribution plate, and the reactor was controlled at a pressure of 290 psig and an ethylene concentration of 67 mol%. The reactor temperature was controlled by adjusting the temperature of the recirculated gas loop. A continuous additive (CA-300, from Univation) was co-fed into the reactor bed through a second carrier nozzle, and the feed rate of the continuous additive was adjusted to maintain a weight concentration of 20 ppm to 40 ppm in the bed.

[0189] Excellent reactor operability was observed under various conditions, including adjusting the catalyst ratio using trimming techniques. Typically, adding continuous additives improves reactor operability at the expense of catalyst activity. For these catalysts, high activity was observed at a CA-300 concentration of 30 ppm while maintaining a high deposition resin bulk density. In one instance, trimming was also used to adjust the catalyst ratio.

[0190] As the C6 / C2 ratio increased (batches 1 and 2), the activity appeared to improve, while the MIR decreased, suggesting a greater contribution from Met.Cat.2 at lower densities. Changing the catalyst ratio from 60:40 to 80:20 (see batches 2 and 5) also resulted in a decrease in MIR, although much less C6 was present in the reactor at higher densities.

[0191] At the same catalyst ratio (batches 5 and 6), the Met.Cat.1:IronCat.1 catalyst system generally appears to have a lower molecular weight capability (higher MI at a lower H2 / C2 ratio) and a slightly lower hexene introduction rate than the Met.Cat.2:IronCat.1 catalyst system. However, the Met.Cat.1:IronCat.1 catalyst system exhibits very high catalyst activity, excellent operability, and high packing density.

[0192]

[0193] In general, the methods of this disclosure can include the production of LLDPE compositions at high catalyst activity and excellent packing density while maintaining useful LLDPE properties, such as processability, rigidity, and toughness, each of which may be important for membranes and other applications. Adding a continuous accelerant (e.g., aluminum distearate) to the polymerization reaction having the mixed catalyst system of this disclosure provides several benefits, such as achieving excellent packing density even at high catalyst activity. The LLDPEs of this disclosure may also have a broad orthogonal compositional distribution ("BOCD"), which provides improved processability as well as rigidity and toughness sufficient for end-use applications. The catalyst system of the methods of this disclosure includes a metallocene catalyst, such as a group 4 cyclopentadienyl metallocene catalyst and a mixed catalyst system of 2,6-bis(imino)pyridyl iron complex. For example, the group 4 cyclopentadienyl metallocene can be a non-bridged hafnium cyclopentadienyl catalyst having one or more alkylsilyl-substituted cyclopentadienyl rings.

[0194] All documents described herein, including any priority documents and / or experimental procedures, are incorporated by reference to all rights, without prejudice to the present invention. It will be apparent from the foregoing overview and specific embodiments that, 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 that this disclosure be limited thereto. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements precedes the transitional term “comprising,” it should be understood that the same composition or group of elements preceding the enumerated composition, element, or element, and vice versa, is also considered to have the transitional terms “consistently composed of,” “composed of,” “selected from,” or “is” preceding the enumerated composition, element, or elements.

[0195] For simplicity, only certain numerical ranges are explicitly disclosed in this document. However, a lower limit can be combined with any other upper limit to define a range that is not explicitly stated, and similarly, a lower limit can be combined with any other lower limit to define a range that is not explicitly stated; likewise, an upper limit can be combined with any upper limit to define a range that is not explicitly stated. Furthermore, even if not explicitly stated, every point or individual value between the two endpoints is included within the range. Therefore, each point or individual value itself can serve as a lower or upper limit, combined with other points or individual values ​​or other lower or upper limits to define a range that is not explicitly stated.

Claims

1. A method for preparing a polyethylene composition, comprising: Under polymerization conditions, ethylene and C3-C 40 An α-olefin and a catalyst system and a continuous additive are introduced into a reactor. The catalyst system includes an activator, an iron catalyst compound, and an unbridged Group 4 metallocene catalyst compound having one or more alkylsilyl substituted compounds. and A polyethylene composition is formed.

2. The method of claim 1, wherein: The catalyst system has a catalytic activity of approximately 10,000 gP / gcat to approximately 20,000 gP / gcat, and The polyethylene composition has a content of about 0.45 g / cm³. 3 To approximately 0.52 g / cm 3 The packing density.

3. The method of claim 2, wherein the bulk density is about 0.46 g / cm³. 3 Approximately 0.49 g / cm³ 3 .

4. The method of claim 1 or any one of claims 2-3, wherein the continuous additive is present in the reactor at an amount of about 10 ppm to about 75 ppm, based on the weight of the polyethylene composition formed.

5. The method of claim 4, wherein the continuous additive is present in the reactor at an amount of about 20 ppm to about 40 ppm.

6. The method of claim 1 or any one of claims 2-5, wherein the continuous additive is aluminum stearate, aluminum distearate, aluminum oleate, aluminum oxostearate, or a combination thereof.

7. The method of claim 1 or any one of claims 2-5, wherein the continuous additive is an alkoxylated amine, a carboxylate, or a combination thereof.

8. The method of claim 1 or any one of claims 2-7, wherein C3-C 40 The α-olefin is 1-hexene.

9. The method of claim 1 or any one of claims 2-8, wherein the iron catalyst compound is represented by formula (IIa) or formula (IIb): (IIa) or (IIb) in: R 6a R 10a R 11a and R 15a Each of them is independently a halogen, -CF3, or C1-C. 22 -alkyl, or -OR'; R 1a and R 2a Each of them is independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, wherein the alkyl group has 1-10 carbon atoms and the aryl group has 6-20 carbon atoms, or a penta-, hexa-, or hepta-heterocyclic group containing at least one atom selected from N, P, O, and S, wherein R 1a and R 2a Each of these can be optionally replaced by a halogen, -NR'2, -OR', or –SiR''3, where R 1a Optional with R 3a Bonding, and R 2a Optional with R 5a Bonding, forming five-, six-, or seven-membered rings independently in each case; R 3a R 4a R 5a R 7a R 8a R 9a R 12a R 13a and R 14a Each of them is independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, aralkyl groups having 1-10 carbon atoms and the aryl group having 6-20 carbon atoms, halogens, -NR'2, -OR', -SiR''3, or penta-, hexa-, or hepta-heterocyclic groups containing at least one atom selected from N, P, O, and S; and X 1a X 2a and X 3a Each of these elements is independently hydrogen, halogen, C1-C. 20 -alkyl, C2-C 10 -Alkenyl, C6-C 20 -aryl, aralkyl groups in which the alkyl group has 1-10 carbon atoms and the aryl group has 6-20 carbon atoms, -NR'2, -OR', -SR', -SO3R', -OC(O)R', -CN, -SCN, β-diketone, -CO, -BF4 - -PF6 - Or large-volume uncoordinated anions, or X 1a and X 2a Optionally bonded to form five- or six-membered rings.

10. The method of claim 9, wherein the iron catalyst compound is: 。 11. The method of any one of claims 9 or 10, wherein the unbridged Group 4 metallocene catalyst compound is represented by the following formula (I): (I) in: In equation (I), M is Ti, Hf, or Zr; X of equation (I) 1 and X 2 Each of them is independently C1 to C 20 Hydrocarbon group, functional groups containing elements from groups 13 to 17 of the periodic table, or X 1 and X 2 Joined together to form C4 to C 62 Ring structures, either cyclic or multi-ringed; R in equation (I) 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each of these elements is independently selected from hydrogen, halogens, C1-C. 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, functional groups containing elements from groups 13 to 17 of the periodic table, or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 5 and R 6 R 6 and R 7 R 7 and R 8 One or more pairs of elements join to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring, such as substituted or unsubstituted C4 to C5 rings. 62 Rings, either circular or multi-ringed; and R in equation (I) 9 R 10 R 10 R 11 R 12 and R 13 Each of them is independently selected from hydrogen, C1-C 40 Hydrocarbon group or substituted C1-C 40 Hydrocarbon group.

12. The method of claim 11, wherein the unbridged Group 4 metallocene catalyst compound is: 。 13. The method of any one of claims 9 or 10, wherein the unbridged Group 4 metallocene catalyst compound is represented by formula (III): (III), in: In equation (III), M is Ti, Hf, or Zr; X of equation (III) 1 and X 2 Each of them is independently C1 to C 20 Hydrocarbon group, functional groups containing elements from groups 13 to 17 of the periodic table, or X 1 and X 2 Joined together to form C4 to C 62 Ring structures, either cyclic or multi-ringed; R in equation (III) 1 R 2 R 3 R 4 R 5 R 6 R 14 R 15 and R 16 Each of these elements is independently selected from hydrogen, halogens, C1-C. 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, -NR'2, -SR', -OR', -OSiR'3 or -PR'2, where each R' is independently hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 Aryl, or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 4 and R 5 R 1 and R 5 R 14 and R 15 and R 15 and R 16 One or more pairs of them join together to form C4 to C 62 Ring structures, either cyclic or multi-ringed; R in equation (III) 7 R 8 R 9 R 10 R 11 R 12 R 13 Each of these elements is independently selected from hydrogen, halogens, C1-C. 40 Hydrocarbon group, substituted C1-C 40 Hydroxyl, aryl, substituted aryl, -NR'2, -SR', -OR', -OSiR'3 or -PR'2, where each R' is independently hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 Aryl, or R 7 and R 8 R 8 and R 10 and R 10 and R 12 One or more pairs of rings are joined to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring.

14. The method of claim 13, wherein the unbridged Group 4 metallocene catalyst compound is 。 15. The method of claim 1 or any one of claims 2-14, wherein the reactor is a gas-phase fluidized bed reactor.

16. The method of claim 15, wherein the polymerization conditions include: 1) Reactor temperature from approximately 40°C to approximately 120°C; 2) Reactor pressure from approximately 0.45 MPa to approximately 6 MPa; 3) Aliphatic hydrocarbon solvents are present; 4) The activator mentioned above is an aluminum oxane activator; 5) The continuous additive is present in an amount of about 20 ppm to about 40 ppm, based on the weight of the formed polyethylene composition; and 6) The molar ratio of the group 4 metallocene catalyst compound to the iron catalyst compound is about 1:1 to about 9:

1.

17. The method of claim 1 or any one of claims 2-16, further comprising introducing about 0.25 moles to about 5 moles of scavenger / moles of water into the continuous additive, measured before adding the scavenger.

18. The method of claim 1 or any one of claims 2-17, wherein the continuous additive is aluminum distearate.

19. The method of claim 1, wherein the polyethylene composition has about 0.91 g / cm³ 3 Approximately 0.94 g / cm³ 3 The gradient density.

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