WO2025174367A1 - Mixed catalysts with continuity aid for improved polymer properties in gas phase polymerizations - Google Patents

Abstract

The present disclosure generally relates to methods of producing polyolefins in gas phase polymerizations. In an embodiment, a process for producing a polyethylene includes introducing, under polymerization conditions, ethylene and a C3-C40 alpha-olefin with a catalyst system and a continuity' aid in a reactor. The catalyst system includes an activator, an iron catalyst compound, and an unbridged Group 4 metallocene catalyst compound having one or more alkyl silyl substitutions. The process includes forming a polyethylene composition.

Description

MIXED CATALYSTS WITH CONTINUITY AID FOR IMPROVED POLYMER PROPERTIES IN GAS PHASE POLYMERIZATIONS FIELD _{[0001] The present disclosure generally relates to methods of producing polyolefins in} gas phase polymerizations. BACKGROUND _{[0002] Olefin polymerization catalysts are of great use in industry to produce polyolefin} compositions suitable for, e.g., film applications. Despite efforts in developing olefin polymerization catalysts for the production of polethylene compositions, such as linear low density polyethylene (LLDPE), the production of polethylene compositions and films having improved performance properties such as processability, stiffness, and toughness remains elusive. Achieving such performance properties is challenging because a trade-off exists among such properties. For example, improving a LLDPE composition’s stiffness and processability often reduces its toughness. _{[0003] In addition, bulk density of a polymer is a desirable property because a large} amount of polymer can be present in a reactor while the polymerization catalyst(s) continues to produce more polymer with sufficient catalyst activity for high throughput polymer production. In addition, a high bulk density (e.g., 0.45 g/cm³ or greater) provides opportunity for efficient transportation of large amounts of polymer product per volume. However, a polymer providing high bulk density also reduces catalyst productivity and catalyst activity while the polymer is still in the polymerization reactor. _{[0004] Therefore, there remains a need for new and improved methods of producing} LLDPE compositions at high activity and good bulk density, while maintaining useful LLDPE properties such as processability, stiffness, and toughness, each of which can be important for film and other applications. _{[0005] References of potential interest in this regard include WO2021/222016;} WO2021/222280; and EP 2183286. SUMMARY _{[0006] The present disclosure generally relates to methods of producing polyolefins in} gas phase polymerizations. _{[0007] In an embodiment, a process for producing a polyethylene includes introducing,} under polymerization conditions, ethylene and a C3-C40 alpha-olefin with a catalyst system and a continuity aid in a reactor. The catalyst system includes an activator, an iron catalyst compound, and an unbridged Group 4 metallocene catalyst compound having one or more alkyl silyl substitutions. The process includes forming a polyethylene composition. DETAILED DESCRIPTION _{[0008] The present disclosure generally relates to methods of producing polyolefins in} gas phase polymerizations. For example, methods of the present disclosure can include producing LLDPE compositions at high catalyst activity and good bulk density, while maintaining useful LLDPE properties such as processability, stiffness, and toughness, each of which can be important for film and other applications. It has been discovered that controlled addition of a continuity aid (such as aluminum distearate) to polymerizations having mixed catalyst systems of the present disclosure provides benefits such as good bulk density even at high catalyst activity. LLDPEs of the present disclosure can also have broad orthogonal composition distribution (“BOCD”), which provides for improved processability and sufficient stiffness and toughness for end use applications. Catalyst systems for processes of the present disclosure include a mixed catalyst system of a metallocene catalyst, such as a Group 4 cyclopentadienyl metallocene catalyst, and a 2,6-bis(imino)pyridyl iron complex. For example, a Group 4 cyclopentadienyl metallocene can be an unbridged hafnocene catalyst having one or more cyclopentadienyl ring having one or more alkylsilyl substitution. As used herein, “unbridged” refers to catalysts that do not bridging moieties (e.g., silyl bridge) in addition to the catalytic metal atom. _{[0009] Definitions of terms used herein may be found in paragraphs [0018]-[0042] of} WO2021/222016, incorporated herein by reference. _{[0010] Unless otherwise indicated, “catalyst activity” is a measure of how active the} catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP/molcat) or as the mass of product polymer (P) produced per mass of catalyst (cat) used (gP/gcat). Catalyst activity may also be expressed over a period of time T of hours and reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used and expressed in units of gPmmolcat^-1hr^-1. Catalyst Precursors and Activators _{[0011] In at least one embodiment of the present disclosure, the catalyst system can} include a metallocene catalyst (a first catalyst compound), an iron catalyst (a second catalyst compound), and an activator. Metallocene Catalyst _{[0012] In aspects of the present disclosure the metallocene catalyst can be represented by} Formula (I):

I). _{[0013] In at least one embodi ) is a Group 4 metal such as titanium} (Ti), hafnium (Hf) or zirconium (Zr), such as hafnium. _{[0014] In at least one embodiment, each of X1 and X2 of Formula (I) is independently a} univalent anionic ligand, a diene ligand, an alkylidene ligand, or X¹ and X² are joined to form a metallocyclic ring. Each of X¹ and X² can be independently a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group. In at least one embodiment, each of X¹ and X² is independently selected from halides, aryls, and C₁ to C₅ alkyl groups, such as phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloride group. In at least one embodiment, each of X¹ and X² are chloride. _{[0015] In at least one embodiment, each of R1, R2, R3, R4, R5, R6, R7, and R8 of Formula} (I) is independently selected from hydrogen, halogen, C₁-C₄₀ hydrocarbyl, substituted C₁-C₄₀ hydrocarbyl, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements (such as –NR'₂, –SR', –OR’, –OSiR'₃, or –PR'₂, wherein each R' is independently hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl) or one or more of R¹ and R², R² and R³, R³ and R⁴, R⁵ and R⁶, R⁶ and R⁷, R⁷ and R⁸ are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring, such as a substituted or unsubstituted C4 to C62 cyclic or polycyclic ring. _{[0016] In at least one embodiment, each of R9, R10, R10, R11, R12, and R13 of Formula (I)} is independently selected from hydrogen, C1-C40 hydrocarbyl (such as C1-20 hydrocarbyl, such as C1-C12 hydrocarbyl), or substituted C1-C40 hydrocarbyl (such as substituted C1-20 hydrocarbyl, such as substituted C1-C12 hydrocarbyl), alkoxide, or amide. _{[0017] In at least one embodiment, each of R1, R2, R3, R4, R5, R6, R7, and R8 of Formula} (I) is independently is independently hydrogen, halide, alkoxide or C1 to C40 substituted or unsubstituted hydrocarbyl (such as C₁ to C₁₂ substituted or unsubstituted hydrocarbyl), or – R''–SiR'3 or –R''–CR'3 where R'' is C1 to C4 hydrocarbyl (such as –CH2–; –CH2CH2–; _{–(Me)CHCH2–; or –(Me)CH–, and each R' is independently C1 to C20 substituted or} unsubstituted hydrocarbyl and at least one R' is C1 to C20 substituted or unsubstituted hydrocarbyl. In at least one embodiment, each R' is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or an isomer thereof, R' is a C1 to C20 alkyl or aryl, such as methyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl, or di-t-butylphenyl, provided that at least one R' is not H, alternatively 2 R' are not H, alternatively 3 R' are not H. _{[0018] In at least one embodiment, C1-C40 hydrocarbyl, C1-20 hydrocarbyl, or C1-C12} hydrocarbyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, or sec-decyl. _{[0019] In at least one embodiment, each of R1, R2, R3, R4, R5, R6, R7, and R8 of Formula} (I) 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. [0020] A catalyst represented by Formula (I) can be an asymmetric catalyst. Useful} asymmetric catalysts can be such that a mirror plane cannot be drawn through the metal center and the cyclopentadienyl moieties bridged to the metal center are structurally different. _{[0021] In at least one embodiment, the metallocene catalyst represented by Formula (I)} is: _{[0022] Additional embodiments catalyst represented by Formula (I)} can be found in paragraphs [0045]-[0055] of WO2021/222016, incorporated by reference herein. _{[0023] In at least one embodiment of the present disclosure, the catalyst systems can} include a Group 4 metallocene catalyst represented by Formula (III):

I). _{[0024] In at least one ) is a group 4 metal such as} hafnium (Hf) or zirconium (Zr) in at least one embodiment, M is hafnium. _{[0025] In at least one embodiment, each of X1 and X2 of Formula (III) is independently a} univalent anionic ligand, a diene ligand, an alkylidene ligand, or X¹ and X² are joined to form a metallocyclic ring. Each of X¹ and X² can be independently a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group. In at least one embodiment, each of X¹ and X² is selected from halides, aryls, and C1 to C5 alkyl groups, such as phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloride group. In at least one embodiment, each of X¹ and X² are chloride. _{[0026] In at least one embodiment, each of R1, R2, R3, R4, R5, R6, R14, R15, and R16 of} Formula (III) is independently selected from hydrogen, halogen, C1-C40 hydrocarbyl, substituted C₁-C₄₀ hydrocarbyl, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements (such as –NR'2, –SR', –OR’, –OSiR'3, or –PR'2, wherein each R' is independently hydrogen, halogen, C₁-C₁₀ alkyl, or C₆-C₁₀ aryl), or one or more of R¹ and R², R² and R³, R³ and R⁴, R⁴ and R⁵, R¹ and R⁵, R¹⁴ and R¹⁵, and R¹⁵ and R¹⁶ are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring, such as a substituted or unsubstituted C4 to C62 cyclic or polycyclic ring. In at least one embodiment, each of R⁶ and R¹³ is hydrogen. In at least one embodiment, one or more of R¹, R², R³, R⁴, and R⁵ is –CH2-Si-(CH3)3. In at least one embodiment, R¹, R², R³, and R⁴ are each hydrogen and R⁵ is –CH2-Si-(CH3)3. In at least one embodiment, each of R¹⁴, R¹⁵, and R¹⁶ is hydrogen. _{[0027] In at least one embodiment, each of R7, R8, R9, R10, R11, R12, and R13 of Formula} (III) is independently selected from hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1- C40 hydrocarbyl, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements (such as –NR'₂, –SR', –OR’, –OSiR'₃, or –PR'₂, wherein each R' is independently hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl), or two of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring, such as a substituted or unsubstituted C4 to C62 cyclic or polycyclic ring. In at least one embodiment, each of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ is hydrogen. _{[0028] In at least one embodiment, each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11,} R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ of Formula (III) is independently hydrogen, halide, alkoxide or C1 to C₄₀ substituted or unsubstituted hydrocarbyl (such as C₁ to C₁₂ substituted or unsubstituted hydrocarbyl), or – R''–SiR'3 or –R''–CR'3 where R'' is C1 to C4 hydrocarbyl (such as –CH2–; _{–CH2CH2–; – (Me)CHCH2–; or –(Me)CH–, and each R' is independently C1 to C20} substituted or unsubstituted hydrocarbyl and at least one R' is C1 to C20 substituted or unsubstituted hydrocarbyl. In at least one embodiment, each R' is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or an isomer thereof, R' is a C₁ to C₂₀ alkyl or aryl, such as methyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl, or di-t-butylphenyl, provided that at least one R' is not H, alternatively 2 R' are not H, alternatively 3 R' are not H. _{[0029] In at least one embodiment, C1-C40 hydrocarbyl, C1-20 hydrocarbyl, or C1-C12} hydrocarbyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, or sec-decyl. _{[0030] In at least one embodiment, each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11,} R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ of Formula (III) 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. _{[0031] In at least one embodiment, each of R6, R7, R8, R9, R10, R11, R12, and R13 of} Formula (III) is hydrogen and each of R¹, R², R³, R⁴, R⁵, R¹⁴, R¹⁵, and R¹⁶ 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. [0032] In at least one embodiment, each of R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and} 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. [0033] A catalyst represented by Formula (III) can be an asymmetric catalyst. Useful} asymmetric catalysts can be such that a mirror plane cannot be drawn through the metal center and the cyclopentadienyl moieties bridged to the metal center are structurally different. _{[0034] In at least one embodiment, the Group 4 metallocene catalyst represented by} Formula (III) is . _{[0035] Additional catalyst represented by Formula (III)} can be found in paragraphs [0052]-[0065] of WO2021/222280, incorporated by reference herein. Iron Catalyst _{[0036] In at least one embodiment, the iron catalyst may be represented by Formula (IIa)} and/or Formula (IIb): . _and Formula (IIb) are independently halogen, -CF3, or C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl (wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms), NR'2, -OR', -SiR''3 or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S. In at least one embodiment, each of R^6a, R^10a, R^11a, and R^15a are independently fluorine, chlorine, bromine, or iodine. In at least one embodiment, each of R^6a, R^10a, R^11a, and R^15a is independently optionally substituted by halogen, -NR'2, -OR', or –SiR''3. _{[0038] In at least one embodiment, each of R1a and R2a of Formula (IIa) and Formula} (IIb) is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S, wherein each of R^1a and R^2a is optionally substituted by halogen, -NR'₂, -OR' or –SiR''₃, wherein R^1a optionally bonds with R^3a, and R^2a optionally bonds with R^5a, in each case to independently form a five-, six- or seven-membered ring. In at least one embodiment, R^1a and R^2a are independently C1-C22-alkyl, substituted C1-C22-alkyl, unsubstituted phenyl, or substituted phenyl. In at least one embodiment, each of R^1a and R^2a 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, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, and tert-decyl. _{[0039] In at least one embodiment, each of R3a, R4a, R5a, R7a, R8a, R9a, R12a, R13a, and R14a} of Formula (IIa) and Formula (IIb) is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, halogen, -NR'₂, -OR', -SiR''₃ or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S. Each of R^3a, R^4a, R^5a, R^7a, R^8a, R^9a, R^12a, R^13a, and R^14a is independently optionally substituted by halogen, -NR'₂, -OR', or – SiR''3. _{[0040] In at least one embodiment, each of R8a and R13a of Formula (IIa) and Formula} (IIb) is independently selected from C1-C22-alkyl, wherein each of R^8a and R^13a is independently optionally substituted by halogen, -NR'2, -OR', or –SiR''3. In at least one embodiment, R^7a, R^9a, R^12a, and R^14a is hydrogen. In at least one embodiment, each of R^3a, R^4a, and R^5a is hydrogen. _{[0041] In at least one embodiment, each of X1a, X2a, and X3a of Formula (IIa) and/or} Formula (IIb) is independently halogen, hydrogen, C1-C20-alkyl, C2-C10-alkenyl, C6-C20-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR'2, -OR', -SR', -SO3R', -OC(O)R', -CN, -SCN, ^-diketonate, -CO, -BF4⁻, -PF6⁻ or bulky non-coordinating anion, or X^1a and X^2a optionally bond to form a five- or six- membered ring. Each R' is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22- aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or –SiR''3, wherein R' is optionally substituted by halogen or nitrogen- or oxygen- containing groups, or two R' radicals optionally bond to form a five- or six-membered ring. Each R'' is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, wherein each R'' is optionally substituted by halogen or nitrogen- or oxygen-containing groups, or two R'' radicals optionally bond to form a five- or six-membered ring. In at least one embodiment, X^1a and X^2a are chlorine. _{[0042] In at least one embodiment, each of R6a, R10a, R11a, and R15a of Formula (IIa) and} Formula (IIb) is chlorine; each of R^1a and R^2a is C₁-C₂₀ hydrocarbyl; each of R^3a, R^4a, and R^5a is hydrogen; each of R^8a and R^13a is C1-C20 hydrocarbyl; each of R^7a, R^9a, R^12a and R^14a is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, halogen, -NR'2, -OR', - SiR''₃ or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from the group consisting of 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 are optionally substituted by halogen, -NR'₂, -OR' or –SiR''₃; each R' is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or –SiR''₃, wherein R' is optionally substituted by halogen, or two R' radicals optionally bond to form a five- or six-membered ring; each R'' is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or two R'' radicals optionally bond to form a five- or six-membered ring. _{[0043] In at least one embodiment, an iron catalyst represented by Formula (IIa) or} Formula (IIb) is one or more of: . _{[0044] Formula (I)} can be found in paragraphs [0056]-[0066] of WO2021/222016, incorporated by reference herein. Support Material _{[0045] In at least one embodiment of the present disclosure, the catalyst systems include} the product of the combination of one or more support materials. In some embodiments, a support material is a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, or mixtures thereof. As used herein, “support” and “support material” are used interchangeably. _{[0046] In at least one embodiment, a support material is an inorganic oxide in a finely} divided form. Suitable inorganic oxide materials for use in the supported catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed, either alone or in combination, with the silica or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins such as finely divided polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica- alumina, silica-titania, and the like. Exemplary support materials include Al2O3, ZrO2, SiO2, and combinations thereof, such as, SiO₂, Al₂O₃, or SiO₂/Al₂O₃. _{[0047] Additional embodiments of support material can be found at paragraphs [0067]-} [0071] of WO2021/222016, incorporated by reference herein. _{[0048] In several classes of embodiments, the above catalysts (represented by two or} more of Formula (I), Formula (IIa)/(IIb), or Formula (III)) described herein are generally deposited on a support material at a loading level of about 10-100 micromoles of metal per gram of solid support; alternatively about 20-80 micromoles of metal per gram of solid support; or about 40-60 micromoles of metal per gram of support. But greater or lesser values may be used provided that the total amount of solid complex does not exceed the support’s pore volume. Activator _{[0049] The terms “cocatalyst” and “activator” are used herein interchangeably. The} catalyst systems described herein can typically include a catalyst complex as described above and an activator such as alumoxane or a non-coordinating anion and may be formed by combining the catalyst components described herein with activators in any manner known from the literature including combining them with supports, such as silica. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). Catalyst systems of the present disclosure may have one or more activators and one, two or more catalyst components. Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation. Non-limiting activators, for example, include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Suitable activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, σ-bound, metal ligand making the metal compound cationic and providing a charge-balancing noncoordinating or weakly coordinating anion, e.g. a non-coordinating anion. Ionizing/Non Coordinating Anion Activators _{[0050] The term "non-coordinating anion" (NCA) means an anion which either does not} coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a Lewis base. For descriptions of some suitable activators and activator combinations for use in methods of the present disclosure, please see US 8,658,556 and US 6,211,105, incorporated by reference herein; as well as U.S. Patent Publication 2021/0179650, and in particular Paragraphs [0084] – [0135] of WIPO Patent Publication No. WO2021/257264, which description is incorporated by reference herein (including the various descriptions that are incorporated by reference therein, such as WO2004/026921 page 72, paragraph [00119] to page 81, paragraph [00151] and WO2004/046214 page 72, paragraph [00177] to page 74, paragraph [00178]). Alumoxane Activators _{[0051] Alumoxane activators are utilized as activators in the catalyst systems described} herein. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, such as when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be suitable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, as described in U.S. Pat. No. 5,041,584, which is incorporated by reference herein). Another useful alumoxane is solid polymethylaluminoxane as described in U.S. Pat. Nos. 9,340,630, US 8,404,880, and US 8,975,209, which are incorporated by reference herein. _{[0052] When the activator is an alumoxane (modified or unmodified), and in at least one} embodiment, an amount of activator at up to a 5,000-fold molar excess Al/M over the catalyst compound (per metal catalytic site) may be used. The minimum activator-to-catalyst-compound may be a 1:1 molar ratio. Alternate ranges may include about 1:1 to about 500:1, alternately about 1:1 to about 200:1, alternately about 1:1 to about 100:1, or alternately about 1:1 to about 50:1. _{[0053] In an alternate embodiment, little or no alumoxane is used in the polymerization} processes described herein. For example, alumoxane can be present at zero mol%, alternately the alumoxane can be present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1. Optional Scavengers, Co-Activators, Chain Transfer Agents _{[0054] In addition to the activators, scavengers, chain transfer agents or co-activators} may be used. Aluminum alkyl or organoaluminum compounds which may be utilized as co- activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethyl zinc, tri-n-butylaluminum, diisobutylaluminum hydride, or combinations thereof. _{[0055] In at least one embodiment, the catalyst systems can additionally comprise one or} more scavenging compounds. Here, the term “scavenger” means a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability. For example, the scavenging compound will be an organometallic compound such as the Group–13 organometallic compounds of U.S. Pat. Nos. 5,153,157; 5,241,025; and WO 1991/009882; WO 1994/003506; WO 1993/014132; and that of WO 1995/007941. Exemplary compounds include triethyl aluminum, triethyl borane, tri-iso-butyl aluminum, methyl alumoxane, iso-butyl alumoxane, and tri-n-octyl aluminum. _{[0056] Aluminum alkyl or organoaluminum compounds which may be utilized as} scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc. _{[0057] Chain transfer agents may be used in the compositions and/or processes described} herein. Useful chain transfer agents can be diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof. _{[0058] In some embodiments, a scavenger may be a hydrocarbon aluminum compound of} the formula AlR_(3-a)Xa where R is alkyl, cycloalkyl, aryl or a hydride radical. Each alkyl radical may be straight or branched chain having from 1 to 20 carbon atoms, alternatively, 1 to 10 carbon atoms. X is a halogen or hydride for example chlorine, bromine or iodine, chlorine is preferred; a is 0, 1 or 2. _{[0059] Illustrative, but non-limiting examples of such compounds of the above formula} can include when M is aluminum (Al) or boron (B), the trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-isopropyl aluminum, tri-n-butyl aluminum, tri-sec-butyl aluminum, tri-t-butyl aluminum, triisobutyl aluminum, tri-n-pentyl aluminum, tricyclopentyl aluminum, tri-n-hexyl aluminum, tri-(4-methylpentyl) aluminum, tri-(3-methylpentyl) aluminum, tricyclohexyl aluminum; alkyl aluminums such as dimethylethyl aluminum, methyldiethyl aluminum, ethyldimethyl aluminum, dimethyl-n- propyl aluminum, methyl di-n-propyl aluminum, dimethylisopropyl aluminum, dimethylcyclohexyl aluminum, methylethylpropyl aluminum, and the like, aryl and alkyl- substituted aluminums, such as triphenyl aluminum, tri-p-tolyl aluminum, tri-m-tolyl aluminum, tri-p-ethyl aluminum. Other non-limiting examples of typical scavengers include dialkyl aluminum halides, for instance diethylaluminum chlorides, ethyl aluminum dichlorides, bromides and iodides and dialkyl aluminum sesquichlorides, bromides and iodides; aluminum alkoxides and aryloxides such as dimethyl aluminum methoxide, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diethyl aluminum isopropoxide, methyl ethyl aluminum methoxide, dimethyl aluminum 4-methylphenoxide, demethyl aluminum 3- methylphenoxide, dimethyl aluminum 2,6-diisopropylphenoxide, dimethyl aluminum 2,6-di- t-butyl4-methylphenoxide. _{[0060] Scavengers typically preferred are those in the above formula wherein M is} aluminum or boron. Of the aluminum species of Group 13 element compounds, the most often used as scavengers are alkylaluminum compounds, such as trialkylaluminum compounds, the most preferred being triethylaluminum, triisobutyl aluminum, and trimethylaluminum. _{[0061] Aluminum alkyl compounds may be, for example, triethylaluminum (TEAL),} trimethylaluminum (TMAL), tri-isobutylaluminum (TIBAL) and tri-n-hexylaluminum (TNHAL), and diethyl aluminum chloride (DEAC). Preparation of Mixed Catalyst Systems _{[0062] The above two or more catalyst types can be combined to form a mixed catalyst} system. The two or more catalysts can be added together in a desired ratio when combined, contacted with an activator, or contacted with a support material or a supported activator. The catalyst compounds may be added to the mixture sequentially or simultaneously. The molar ratio of a catalyst represented by Formula (I) or Formula (III) to a catalyst represented by Formula (IIa)/(IIb), can vary depending on the balance of processability versus physical characteristics of the desired 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, such as from about 1:1 to about 5:1, such as 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. _{[0063] Other procedures for combining the catalysts are possible, such as those described} in WO2021/222016, paragraphs [0091]-[0099] and WO2021/222280, paragraphs [0114]- [0122] each of which is incorporated herein by reference. _{[0064] In at least one embodiment, according to the present disclosure, a catalyst system} has a catalyst activity of greater than about 5,000 gP/gcat, such as greater than about 10,000 _{gP/gcat, such as greater than about 15,000 gP/gcat, such as about 5,000 gP/gcat to about} 25,000 gP/gcat, such as about 10,000 gP/gcat to about 20,000 gP/gcat, such as about 12,000 gP/gcat to about 18,000 gP/gcat, alternatively about 10,000 gP/gcat to about 15,000 gP/gcat, alternatively about 15,000 gP/gcat to about 20,000 gP/gcat. Polymerizations _{[0065] A polymerization process can include a gas phase polymerization reaction, and in} particular a fluidized bed gas phase polymerization reaction. Generally, in a fluidized gas bed process used for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. In some embodiments, the reaction medium includes condensing agents, which are typically non-coordinating inert liquids that are converted to gas in the polymerization processes, such as isopentane, isohexane, or isobutane. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See, for example, US 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.) The gas-phase polymerization may be carried out in any suitable reactor system, e.g., a stirred- or paddle-type reactor system. See U.S. Pat. Nos. 7,915,357; 8,129,484; 7,202,313; 6,833,417; 6,841,630; 6,989,344; 7,504,463; 7,563,851; and 8,101,691 for discussion of suitable gas phase fluidized bed polymerization systems, which are incorporated herein by reference. _{[0066] In such polymerization processes, a gas-phase, fluidized-bed process is conducted} by passing a stream containing ethylene and an olefin comonomer continuously through a fluidized-bed reactor under reaction conditions and in the presence of a catalyst composition at a velocity sufficient to maintain a bed of solid particles in a suspended state. A stream (which may be called a “cycle gas” stream) containing unreacted ethylene and olefin comonomer is continuously withdrawn from the reactor, compressed, cooled, optionally partially or fully condensed, and recycled back to the reactor. Prepared polyethylene copolymer is withdrawn from the reactor and replacement ethylene and olefin comonomer are added to the recycle stream. In some embodiments, gas inert to the catalyst composition and reactants is present in the gas stream. _{[0067] The reactor pressure during polymerization may be about 100 psig (680 kPag)-} about 500 psig (3448 kPag), such as about 200 psig (1379 kPag)- about 400 psig (2759 kPag), such as about 250 psig (1724 kPag)- about 350 psig (2414 kPag). In some embodiments, the reactor is operated at a temperature of about 60°C to about 120°C, such as about 60°C to about 115°C, such as about 70°C to about 110°C, such as about 70°C to about 95°C, such as about 80°C to about 90°C. A ratio of hydrogen gas to ethylene can be about 10 to about 30 ppm/mol%, such as about 15 to about 25 ppm/mol%, such as about 16 to about 20 ppm/mol%. _{[0068] The mole percent of ethylene (based on total monomers) may be about 25- about} 90 mole percent, such as about 50- about 90 mole percent, or about 70- about 85 mole percent, and the ethylene partial pressure (in the reactor) can be about 75 psia (517 kPa)- about 300 psia (2069 kPa), or about 100 psia - about 275 psia (689-1894 kPa), or about 150 psia - about 265 psia (1034-1826 kPa), or about 180 psia - about 200 psia. Ethylene concentration in the reactor can also range from about 35 mol% - about 95 mol%, such as within the range from a low of 35, 40, 45, 50, or 55 mol% to a high of 70, 75, 80, 85, 90, or 95 mol% and further where ethylene mol% is measured on the basis of total moles of gas in the reactor (including, if present, ethylene and/or comonomer gases as well as inert gases such as one or more of nitrogen, isopentane, etc.); as with vol-ppm hydrogen, this measurement may for convenience be taken in the cycle gas outlet rather than in the reactor itself. Comonomer concentration can be about 0.2 - about 1 mol%, such as from a low of 0.2, 0.3, 0.4 or 0.5 mol% to a high of 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 1.0 mol%. _{[0069] In at least one embodiment, alpha-olefins suitable for use as starting material in} the preparation of the LLDPE can be one or more substituted or unsubstituted C2 to C40 alpha-olefins, such as C₂-C₃₂ alpha-olefins, such as C₄-C₃₂ alpha-olefins, such as C₆-C₃₀ alpha-olefins, such as C6-C24 alpha-olefins, such as C6-C18 alpha-olefins, C6 to C16 alpha- olefins, C₆-C₁₂ alpha-olefins, or a combination thereof. In at least one embodiment, the C₂ to C40 alpha-olefins may be linear, branched, or cyclic. The C2 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may, optionally, include heteroatoms and/or one or more functional groups. Non-limiting examples of alpha-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, branched chain 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, substituted derivatives thereof, and isomers thereof, and a combination thereof. _{[0070] In at least one embodiment, a process provides polymerization of ethylene and at} least one comonomer having from 3 to 8 carbon atoms, such as 4 to 8 carbon atoms. Particularly, the comonomers can be propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1- pentene, 1-hexene and 1-octene, for example 1-hexene, 1-butene, 1-octene., or a combination thereof. In at least one embodiment, a process provides polymerization of one or more monomers selected from the group consisting of propylene, 1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and a combination thereof. _{[0071] Suitable polymerizations can be run at any temperature and/or pressure suitable to} obtain the desired ethylene polymers. Suitable temperatures and/or pressures may include a temperature in the range of from about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about 150°C, such as from about 40°C to about 120°C, such as from about 45°C to about 80°C; and/or a pressure in the range of from about 0.35 MPa to about 10 MPa, such as from about 0.45 MPa to about 6 MPa, such as 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 within a range from 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), such as from about 0.01 to about 25 psig (about 0.07 to about 172 kPa), such as about 0.1 to about 10 psig (about 0.7 to about 70 kPa). _{[0072] In at least one embodiment, little or no alumoxane is used in the process to} produce the polymers. Alumoxane can be present at about zero mol%, alternatively the alumoxane can be present at a molar ratio of aluminum to transition metal less than about 500:1, such as less than about 300:1, such as less than about 100:1, such as less than about 1:1. In at least one embodiment, little or no scavenger is used in the process to produce the ethylene polymer. For example, scavenger (such as trialkyl aluminum) can be present at zero mol%, alternatively the scavenger can be present at a molar ratio of scavenger metal to transition metal of less than about 100:1, such as less than about 50:1, such as less than about 15:1, such as less than about 10:1. _{[0073] In at least one embodiment, the polymerization: 1) is conducted at temperatures of} about 0 to about 300°C (such as about 25 to about 150°C, such as about 40 to about 120°C, such as about 100°C or greater); 2) is conducted at a pressure of about atmospheric pressure to about 10 MPa (such as about 0.35 to about 10 MPa, such as from about 0.45 to about 6 MPa, such as from about 0.5 to about 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; such as where aromatics (such as toluene) can be present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as at 0 wt% based upon the weight of the solvents); 4) wherein the catalyst system includes a alumoxane activator; 5) the polymerization occurs in one reaction zone; and/or 6) optionally scavengers (such as trialkyl aluminum compounds) are absent (e.g., present at zero mol%, alternatively the scavenger is present at a molar ratio of scavenger metal to transition metal of less than about 100:1, such as less than about 50:1, such as less than about 15:1, such as less than about 10:1); 7) continuity aid is present in an amount of about 1 ppm to about 60 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) (such as from about 0.01 to about 25 psig (about 0.07 to about 172 kPa), such as about 0.1 to about 10 psig (about 0.7 to about 70 kPa)). Addition of Continuity Aid _{[0074] Continuity aids of the present disclosure can be any suitable continuity aid, such} as those described below. In some embodiments, the total amount of continuity aid or aids to be present in the reactor is about 60, or 50, or 40, or 30, or 20 or 10 ppm (parts per million by weight of polymer being produced) or greater than about 1, or 3, or 5, or 7, or 10, or 12, or 14, or 15, or 17, or 20 ppm based on the weight of polymer being produced (usually expressed as pounds or kilograms per unit of time). Any of these lower limits are combinable with any upper limit. These amounts of continuity aid contemplate one, two, three, four or more continuity aids, the total amount of one or two or more continuity aids in the reactor will be understood to be aid with the total disclosed immediately above. The continuity aid can be added directly to the reactor through a dedicated feed line and/or added to any convenient feed stream, including the monomer, e.g., ethylene feed stream, a comonomer feed stream, a catalyst feed line (e.g., in a trim process), or the recycle line. If more than one continuity aid is used, each one may be added to the reactor as separate feed streams, or as any combination of separate feed streams or mixtures. _{[0075] Methods of the present disclosure include introducing at least one continuity aid in} the catalyst mixture, inject the catalyst mixture (containing at least one continuity aid) into the reactor, and additionally or alternatively introduce at least one continuity aid into the reactor via a dedicated continuity aid feed line independent of the catalyst mixture, so that a sufficient concentration of the at least one continuity aid is introduced directly or indirectly into the reactor. Either of these feed schemes or both together may be employed. The continuity aid in the catalyst/continuity aid mixture and the continuity aid added via the separate continuity aid feed line, may be the same or different. _{[0076] If a combination of continuity aids is used, the total present in the reactor may be} as noted above. Continuity Aids _{[0077] The continuity aid may be in the form of a slurry or suspension that, in addition to} a traditional active substance, also optionally, includes some type of scavenger that has been added, for example, to neutralize the water therein. As use herein, "neutralize" refers to ability of the scavenger to react with catalyst poisons, such as water, so that the catalyst activity is not adversely effected. "Adversely effected" as used here refers to a loss of 1% or more, alternatively, 5% or more, alternatively, 10% or more, alternatively, 15% or more, alternatively, 20% or more, alternatively, 25% or more, and, alternatively, 30% or more of catalyst activity as measured from a predetermined level. _{[0078] Continuity aids of the present disclosure may be prepared using any suitable} method, such as those described in EP2183286 at paragraphs [0058]-[0067], incorporated herein by reference. _{[0079] The aid is typically called a continuity aid because it promotes a continuous} reaction process by preventing discontinuity events such as sheeting, chunking, etc. _{[0080] A continuity aid according to one preferred embodiment includes a substance} characterized by an ability to reduce, prevent, or mitigate at least one of fouling, sheeting, and static level of a material present in a polymerization reactor system when introduced to the reactor system in an effective amount. _{[0081] A continuity aid according to another embodiment includes a substance} characterized by an ability to reduce, prevent, or mitigate the effects of at least one of fouling, sheeting, and static level of a material present in a polymerization reactor system when introduced to the reactor system in an effective amount. A scavenger may be contacted with the continuity aid, the scavenger neutralizing water coming in contact therewith. The scavenger may be present in an amount of between 0.25 and 5.0 mole of scavenger per mole of water in the continuity aid, as measured prior to addition of the scavenger thereto. Note that higher and lower amounts of scavenger may be added. In another class of embodiments, the amount of scavenger contacted with the continuity aid is in an amount of from 0.8 to 1.50 mole of scavenger per mole of water measured. _{[0082] In some embodiments, the amount of scavenger present is not more than about} that needed to neutralize the water in the continuity aid so as to minimize any potential interference of the scavenger with the active substance in the continuity aid and/or with the reaction in the reactor system. _{[0083] In some embodiments, a continuity aid is aluminum distearate. In some} embodiments, a continuity aid may include one or more compounds selected from alkoxylated amines and carboxylic acid salts. _{[0084] Ethoxylated stearyl amines are commercially available from Cargill and supplied} under the trade name ATMER 163. _{[0085] Continuity aids can include aluminum stearate, aluminum distearate, aluminum} oleate, and oxol aluminum stearate. Still others can be supplied commercially under the trade names OCTASTAT and STADIS and may be described in U.S. Pat. No.5,026,795. _{[0086] In another class of embodiments, the continuity aid may include a mixture of two} or more of the above-discussed materials. Such mixtures may include: alkoxylated amines and carboxylic acid salts; or alkoxylated amines and polysulfones; or alkoxylated amines and polymeric polyamines; or alkoxylated amines and sulfonic acids; or carboxylic acid salts and polysulfones; or carboxylic acid salts and polymeric polyamines; or carboxylic acid salts and sulfonic acids; or polysulfones and polymeric polyamines; or polysulfones and sulfonic acids; or polymeric polyamines and sulfonic acids. Additionally contemplated are alkoxylated amines, carboxylic acid salts and polysulfones; or alkoxylated amines, polymeric polyamines and sulfonic acids; or carboxylic acid salts, polysulfones and polymeric polyamines; or carboxylic acid salts, sulfonic acids and polysulfones; alkoxylated amines, carboxylic acid salts and polymeric polyamines; alkoxylated amines, carboxylic acid salts and sulfonic acids; alkoxylated amines, polysulfones and sulfonic acids; alkoxylated amines, polymeric polyamines and polysulfones; polysulfones, polymeric polyamines and sulfonic acids; carboxylic acid salts, polymeric polyamines and sulfonic acids. Combinations of three or four or more of these continuity aids are also contemplated. These combinations may be combined at 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 continuity aids, 10:10:80 to 80:10:10 or 10:80:10. _{[0087] Another continuity aid for use in embodiments of the present disclosure includes a} mixture of 1-decene-polysulfone, a reaction product of N-tallow-1,3-diaminopropane and epichlorohydrin, dodecylbenzenesulfonic acid, and a hydrocarbon solvent. Such mixture can be commercially available from Octel Starreon and its affiliates under the tradename OCTASTAT 3000 (which may also be available as STADIS 450) or OCTASTAT 2000 (which may also be available as STADIS 425). Polymerizations Using Trim _{[0088] Polymerization processes of the present disclosure can be performed using a} “trim” process. Trim processes are described, e.g., in U.S. Patent Publication No. 2021/0395404, especially in connection with FIG. 1 therein, and at Paragraphs [0113] – [0124] therein, which description is incorporated herein by reference. An overview of such processes of particular use for the present disclosure is also provided below. _{[0089] A solution of second catalyst (such as a catalyst slurry having a catalyst of at least} one of Formula (I), Formula (IIa)/(IIb), or Formula (III)) can be added (i.e. “trimmed”) to the slurry of the first catalyst(s) (of at least one of Formula (I), Formula (IIa)/(IIb), or Formula (III)) to adjust one or more properties “in-situ” of polymer being formed in a reactor. The catalyst(s) of the slurry of first catalyst(s) can be the same as or different than the second catalyst(s). _{[0090] Accordingly, processes for polymerizing olefin(s) can include using multicatalyst} systems (e.g., by supporting a second or third catalyst in situ). _{[0091] In some embodiments, a method includes: contacting a first composition with a} second composition in a line leading to the 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 can be referred to as a “trim catalyst”, particularly insofar as in methods described herein, the trim process is preferably used to adjust ratio of first to second catalyst by increasing or decreasing relative amount of trim catalyst to primary catalyst. The method includes introducing the third composition from the line into a gas-phase fluidized bed reactor and exposing the third composition to polymerization conditions. The method includes obtaining a polyolefin. _{[0092] Processes can include adjusting reactor conditions, such as an amount of second} catalyst fed to the reactor (via the line to the reactor), to control one or more polymer properties of the polyolefin obtained from the reactor. _{[0093] Additional details regarding trim processes can be found in paragraphs [0123] –} [0127] of WO2021/222280, which can be incorporated herein by reference. Polymerization Products _{[0094] The present disclosure further provides for compositions that can be produced by} the methods of the present disclosure. In at least one embodiment, a process described herein produces ethylene homopolymers or ethylene copolymers, such as ethylene-alpha-olefin (such as C3 to C40, such as a C3-C20 alpha-olefin, such as C3 to C12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene) copolymers (such as ethylene-butene copolymers, ethylene-hexene and/or ethylene- octene copolymers). In some embodiments, the alpha-olefin is a C₄ to C₈ alpha-olefin. _{[0095] In at least one embodiment, the LLDPE can have an ethylene content of about} 65 wt% or greater, such as from about 80 wt% to about 99.9 wt%, such as from about 85 wt% to about 99.5 wt%, such as from about 90 wt% to about 99 wt%, such as from about 91 wt% to about 98 wt%, such as from about 92 wt% to about 97 wt%, such as from about 93 wt% to about 96 wt%, such as from about 94 wt% to about 95 wt%, such as from about 92 wt% to about 98 wt%, when measured according to GPC-IR5-LS-VIS. In some embodiments, the ethylene content can be from about 65 wt% or more, such as from about 90 wt% to about 96 wt%. _{[0096] In at least one embodiment, the LLDPE can have a comonomer content of about} 35 wt% or less, such as from about 0.1 wt% to about 20 wt%, such as from about 0.5 wt% to about 15 wt%, such as from about 1 wt% to about 10 wt%, such as from about 2 wt% to about 9 such as from about 3 wt% to about 8 wt%, such as from about 4 wt% to about 7 wt%, such as from about 5 wt% to about 6 wt%, when measured according to GPC-IR5- LS-VIS. In some embodiments, the comonomer content can be about 35 wt% or less, such as from about 4 wt% to about 10 wt%. _{[0097] In some embodiments, the LLDPE can have a number average molecular weight} (Mn) of from about 5,000 g/mol to about 30,000 g/mol, when measured according to GPC- IR5-LS-VIS. _{[0098] In at least one embodiment, the LLDPE can have a weight average molecular} weight (Mw) of from about 75,000 g/mol to about 200,000 g/mol, when measured according to GPC-IR5-LS-VIS. _{[0099] In at least one embodiment, the LLDPE can have a z-average molecular weight} (Mz) of from about 500,000 g/mol to about 1,800,000 g/mol, when measured according to GPC-IR5-LS-VIS. _{[00100] In some embodiments, the LLDPE can have a molecular weight distribution} (MWD), defined as Mw/Mn, of from about 2 to about 10, such as from about 2.5 to about 9, such as from about 3 to about 8, when measured according to GPC-IR5-LS-VIS. In at least one embodiment, the Mw/Mn can be from about 2 to about 8, such as from about 3 to about 7, such as from about 4 to about 6, such as about 5 or 5.5. _{[00101] In some embodiments, the LLDPE can have a g’vis of about 0.9 or more and 0.97} or less when measured according to GPC-IR5-LS-VIS. _{[00102] In at least one embodiment, the LLDPE can have a melt index (MI, I2) of from} about 0.3 g/10 min to about 20 g/10 min, such as from about 0.5 g/10 min to about 3 g/10 min, such as from about 6 g/10 min to about 1.5 g/10 min, as measured according to ASTM D1238 (190°C, 2.16 kg load). _{[00103] In at least one embodiment, the LLDPE can have a high load melt index (HLMI)} of from about 10 g/10 min to about 60 g/10 min, such as from about 15 g/10 min to about | 40 g/10 min, such as from about 15 g/10 min to about 25 g/10 min or from about 25 g/10 min to about 35 g/10 min, as determined by ASTM D1238 (190°C, 2.16 kg load). _{[00104] In at least one embodiment, the LLDPE can have a HLMI/MI ratio of from about} 15 to about 50, such as from about 20 to about 30, such as from about 20 to about 25 or about 25 to about 30, as determined by ASTM D1238 (190°C, 2.16 kg load). _{[00105] In at least one embodiment, the LLDPE can have a gradient density from about of} from about 0.91 g/cm³ to about 0.94 g/cm³, such as from about 0.915 g/cm³ to about 0.935 g/cm³, such as from about 0.92 g/cm³ to about 0.93 g/cm³, as determined by density-gradient column method according to ASTM D1505. In some embodiments, the gradient density can be from about 0.917 g/cm³ to about 0.94 g/cm³, such as from about 0.918 g/cm³ to about 0.935 g/cm³. _{[00106] In at least one embodiment, the LLDPE can have a bulk density from about of} from about 0.45 g/cm³ to about 0.52 g/cm³, such as from about 0.455 g/cm³ to about 0.5 g/cm³, such as from about 0.45 g/cm³ to about 0.46 g/cm³, alternatively about 0.46 g/cm³ to about 0.49 g/cm³, such as about 0.47 g/cm³ to about 0.49 g/cm³, such as about 0.48 g/cm³ to about 0.49 g/cm³ as determined by ASTM D-1895. Broad Orthogonal Composition Distribution _{[00107] “BOCD” refers to a broad orthogonal composition distribution in which the} comonomer of a copolymer is incorporated predominantly in the high molecular weight chains or species of a polyolefin polymer or composition. The distribution of the short chain branches can be measured, for example, the TREF-IR5 procedure described in the Test Methods section below. BOCD has been described, for example, in U.S. Patent Nos. 8,378,043, Col. 3, line 34, bridging Col. 4, line 19, and 8,476,392, line 43, bridging Col. 16, line 54. _{[00108] The BOCD nature of the present polyethylene copolymers can be quantified in the} composition distribution breadth index (CDBI). For instance, polyethylene copolymers described herein can have a value of composition distribution breadth index (CBDI), in which the polyethylene copolymers may have a CBDI % within a range from a low of any one of about 40, 45, 50, 55, 60, 65, 70, 75, or 80 % to a high of any one of about 99, 95, 90, 85, 80, 75, 70, 65, or 60%; with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e.g., about 50% to about 85%, such as about 55% to about 75%, alternatively about 70% to about 85%, alternatively about 75% to about 85%). In some embodiments, polyethylene copolymers described herein can have a value of composition distribution breadth index (CBDI), in which the polyethylene copolymers may have a CBDI % within a range from a low of any one of about 30, 35, 40, 45, 50, or 55 % to a high of any one of about 70, 65, 60, 55, 50, or 45 %; with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e.g., about 35% to about 65%, such as about 40% to about 50%, alternatively about 50% to about 65%, such as about 50% to about 60%). _{[00109] CDBI is defined as the weight percent of the copolymer molecules having a} comonomer content within +/-50% of the median comonomer mol% value, as described at pp. 18-19 of WO 1993/003093 in conjunction with FIG. 17 therein. This means that for a copolymer having median comonomer mol% value (Cmed) of 8mol% comonomer on a polymer chain, CDBI is the wt% of copolymer chains having comonomer mol% that is between (0.5 x Cmed) and (1.5 x Cmed). In this example, CDBI is the wt% of copolymer chains having comonomer mol% between (0.5 x 8) and (1.5 x 8), or comonomer content between 4 mol% and 12 mol%. WO 1993/003093 also describes the process for determining the weight fraction of polymer vs. composition curve (i.e., the composition distribution curve) using chromatography and C¹³ NMR, and determining the median comonomer composition Cmed therefrom, with reference to Figures 16 and 17 of that publication. 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. TEST METHODS A. Resin Analysis _{[00110] Melt Index (MI, also referred to as I2) is measured according to ASTM D1238 at} 190°C, under a load of 2.16 kg unless otherwise noted. The units for MI are g/10 min or dg/min. High Load Melt Index (HLMI, also referred to as I21) is the melt flow rate measured according to ASTM D-1238 at 190°C, under a load of 21.6 kg. The units for HLMI are g/10 min or dg/min. Melt Index Ratio (MIR) is the ratio of the high load melt index to the melt index, or I₂₁/I₂. Density is measured by density-gradient column, as described in ASTM D1505, on a compression-molded specimen that has been cooled to room temperature following ASTM D4703-10a, Procedure C, then conditioned under ASTM D618-08 (23° ± 2°C and 50±10% Relative Humidity) for 40 hours before testing. Gel Permeation Chromatography (GPC) _{[00111] While the GPC in the CFC analysis also generated the distributions and the moments of molecular weight, for the purposes of the claims, the distributions and the} moments of molecular weight (Mw, Mn, Mw/Mn, etc.), the comonomer content (C2, C3, C6, etc.) and the branching index (g'vis) from GPC-IR5-LS-VIS was used. _{[00112] GPC-IR5-LS-VIS is a high temperature Gel Permeation Chromatography} (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle Wyatt Dwan Heleos light scattering detector and a 4-capillary viscometer with Wheatstone bridge configuration. Three Agilent PLgel 10-µm Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1-µm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate is 1.0 ml/min and the nominal injection volume is 200 µL. The whole system including transfer lines, columns, and viscometer detector are contained in ovens maintained at 145°C. The polymer sample is weighed and sealed in a standard vial with 80-µL flow marker (Heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 ml added TCB solvent. The polymer is dissolved at 160°C with continuous shaking for about 2 hour. The concentration (c), at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal intensity (I), using the following equation: c = ^I, _{where ^ is the mass constant. The mass recovery is calculated from the ratio of the integrated} area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm/mole. The MW at each elution volume is calculated with following equation: log(K^PS / K ) a ^P + 1 log _M = + ^S _log M a + 1 a + 1 PS where the variables with those without a subscript are for the test samples. In while ^ and K are for other materials as calculated and published in literature (Sun, T. et al. Macromolecules 2001, v.34, pg. 6812), specifically, α = 0.695 and K = 0.000579 for linear ethylene polymers, α = 0.705 and K = 0.0002288 for linear propylene polymers. Concentrations are expressed in g/cm3, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark–Houwink equation) is expressed in dL/g unless otherwise noted. Here the concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark–Houwink equation) is expressed in dL/g unless otherwise noted. _{[00113] The comonomer composition is determined by the ratio of the IR5 detector} intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyl number per 1,000 total carbons (CH3/1000TC) as a function of molecular weight. The short-chain branch (SCB) content per 1000TC (SCB/1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH₃/1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. _{[00114] The LS molecular weight (M) at each point in the chromatogram is determined by} analyzing the LS output using the Zimm model for static light scattering K ^o c 1 ∆ = +2A 2 c R _{( . [00115] Here, ^R(^) is the scattering intensity at scattering} angle θ, c is the polymer concentration determined from the IR5 analysis, A₂ is the second virial coefficient, P(^) is the form factor for a monodisperse random coil, and K_o is the optical constant for the system: 4 π2n2(dn/dc ) 2 = λ 4 N A where N_A is Avogadro’s number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145°C and ^=665 nm. For analyzing PE polymers, dn/dc=0.1048 ml/mg and A₂=0.0015. _{[00116] A high temperature Polymer Char viscometer, which has four capillaries arranged} in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ^_s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [^], at each point in the chromatogram is calculated from the equation [^]= ^_s/c, where c is concentration and is determined from the IR5 broadband channel output. _{[00117] The branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VIS} method as follows. The average intrinsic viscosity, [^]_avg, of the sample is calculated by: ] avg = _^ c _{[ η ]} [η i i ^ where the summations are over the i, between the integration limits. _{[00118] The branching index g'vis is defined as} [ η ] g _' avg vis ₌ α _, where M_v is the viscosity-average based on molecular weights determined by LS analysis and the K and α are for the reference linear polymer, which are, for purposes of the present disclosure, α and K are the same as described above for linear polyethylene polymers. TREF-IR5 _{[00119] Temperature Rising Elution Fractionation (TREF) analysis can be done using a} Crystallization Elution Fractionation (CEF) instrument from Polymer Char, S.A., Valencia, Spain. The principles of CEF analysis and a general description of the particular apparatus used are given in the article Monrabal, B.; del Hierro, P. Anal. Bioanal. Chem. 2011, v.399, pg.1557. Fig. 3 of the article is an appropriate schematic of the particular apparatus to be used; however, the connections to the 6-port valve shown in Fig. 3 differ from the apparatus 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. Pertinent details of the analysis method and features of the apparatus to be used are as follows. _{[00120] The solvent used for preparing the sample solution and for elution is} 1,2-Dichlorobenzene (ODCB) which is 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 is then filtered using a 0.1-^m Teflon filter (Millipore). The sample (6–10 mg) to be analyzed was dissolved in 8 ml of ODCB metered at ambient temperature by stirring (Medium setting) at 150°C for 90 min. A small volume of the polymer solution is first filtered by an inline filter (stainless steel, 10 ^m), which is back-flushed after every filtration. The filtrate is then used to completely fill a 200-^l injection-valve loop. The volume in the loop is then introduced near the center of the CEF column (15-cm long SS tubing, 3/8” o.d., 7.8 mm i.d.) packed with an inert support (SS balls) at 140°C, and the column temperature is stabilized at 125°C for 20 minutes. The sample volume is then allowed to crystallize in the column by reducing the temperature to 0°C at a cooling rate of 1°C/min. The column is kept at 0°C for 10 minutes before injecting the ODCB flow (1 ml/min) into the column for 10 minutes to elute and measure the polymer that did not crystallize (soluble fraction). The wide-band channel of the infrared detector used (Polymer Char IR5) generates an absorbance signal that is proportional to the concentration of polymer in the eluting flow. A complete TREF curve is then generated by increasing the temperature of the column from 0°C to 140°C at a rate of 2°C/min while maintaining the ODCB flow at 1 ml/min to elute and measure the concentration of the dissolving polymer. EXAMPLES Example Synthesis of Catalysts _{[00121] All reactions were performed in an inert N2 purged glove box unless otherwise} stated. All anhydrous solvents were purchased from Fisher Chemical and were degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and dried over molecular sieves prior to use. n-Butyl lithium (2.5 M solution in hexane), dicyclopentadiene, dimethyl sulfide (Me2S) and 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 is methyl alumoxane (30 wt% in toluene) obtained from Albemarle. Example Synthesis of Metallocene Catalyst 1 _{[00122] Metallocene Catalyst 1 is:} ^^_{^ ^^^ ^^} ^^ _^ . _{[00123] Synthesis of Me3SiCH2CpH. A neat} trimethylsilylmethyl trifluoromethanesulfonate (25.0 g, 105.8 dissolved in 300 mL of diethyl ether and cooled to -25°C; to this a solid (11.14g, 106.9 mmol) was slowly added over a period of 10-15 minutes. The resulting mixture was stirred overnight at room temperature. Insoluble materials were filtered out. Volatiles from the reaction mixture were carefully removed under dynamic vacuum to avoid evaporating the volatile trimethylsilylmethyl cyclopentadiene, Me₃SiCH₂CpH. The reaction flask (250 mL round bottom flask) and frit with celite were weighted to calculate yield of the product after extraction. The crude materials were then extracted into pentane (3 x 50 mL) and used without any further purification. Based on above mathematical method, the yield is calculated as 15.47 g (95.2%). The ¹H NMR spectrum was recorded for the crude material to ensure the product formation. ¹H NMR (400 MHz, C6D6): ^ -0.05 (9H, s, Si-CH3), 1.77 (2H, d, J_HH=1.2 Hz, Me₃Si-CH₂), 2.83 (1H, sex, J_HH=1.5 Hz, Cp-CH), 5.80-6.49 (4H, m, Cp-CH) ppm. _{[00124] Synthesis of lithium trimethylsilylmethyl cyclopentadienide, Me3SiCH2CpLi. A} hexane solution of n-butyl lithium (41.5 mL, 103.8 mmol, 2.5 M solution) was added drop wise to a precooled solution (1:1 mixture of pentane and diethyl ether, 200 mL) of Me3SiCH2CpH (15.47 g, 101.7 mmol) over a period of 40-50 minutes at -25°C. The resulting mixture was gradually brought to room temperature and then continuously stirred overnight. Volatiles were removed in vacuo and remaining crude materials were thoroughly washed with pentane. The final materials were dried under vacuum to obtain a colorless crystalline solid of Me₃SiCH₂CpLi in 13.6 g (84.6%) yield. ¹H NMR (400 MHz, THF-d₈): ^ -0.09 (9H, s, Si-CH₃), 1.84 (2H, s, Me₃Si-CH₂), 5.36 (2H, t, J_HH=2.6 Hz, Cp-CH), 5.47 (2H, t, J_HH=2.6 Hz, Cp-CH) ppm. _{[00125] Synthesis of bis-(trimethylsilylmethyl cyclopentadienide)hafnium dichloride,} (Me3SiCH2Cp)2HfCl2. A solid HfCl4 (1.011 g, 3.16 mmol) was slurried in precooled diethyl ether (30 mL) at -25°C, and to this a solid Me₃SiCH₂CpLi (1.0 g, 6.3 mmol) was added over The resulting mixture was stirred overnight at room temperature. All volatiles were removed in vacuo and the crude materials were subsequently extracted into dichloromethane. Solvents were removed under reduced pressure resulted spectroscopically pure (Me₃SiCH₂Cp)₂HfCl₂ as a colorless solid in 1.13 g (70%) yield. ¹H NMR (400 MHz C6D6): ^ -0.11 (18H, s, SiMe3-CH3), 2.18 (4H, s, Me3Si-CH2), 5.68 (8H, s, Cp-CH) ppm. [_{00126] Synthesis of bis-(trimethylsilylmethyl cyclopentadienyl)hafnium dimethyl,} (Me3SiCH2Cp)2HfMe2 (Metallocene Catalyst 1). An ethereal solution of MeLi (2.56 mL, 4.1 mmol) was added drop wise to a precooled diethyl ether solution of (Me₃SiCH₂Cp)₂HfCl₂ (1.12 g, 2.03 mmol) over a period of 3-5 minutes at -25°C. The resulting mixture was stirred overnight at room temperature to ensure completion of the reaction. Insoluble materials were filtered through a pad of celite. Volatiles from the filtrate were removed under vaccum. The crude materials were triturated with pentane and then extracted into pentane, followed by solvent removal afforded a colorless crystalline material of (Me3SiCH2Cp)2HfMe2 in 875 mg (84.2%) yield. ¹H NMR (400 MHz, C₆D₆): ^ -0.23 (6H, s, Hf-CH₃), 0.02 (18H, s, SiMe3-CH3), (8H, m, Cp-CH) ppm. Example Synthesis of Metallocene Catalyst 2 [_{0100] Metallocene Catalyst 2 is (Tetrahydroindenyl)(trimethylsilyl-} methylcyclopentadienyl)hafnium dichloride: . [_{0101] Preparation of hafnium} dichloride, (H4Ind)(Me3SiCH2Cp)HfCl2. To a pale yellow solution of indenyl(trimethylsilylmethylcyclopentadienyl)hafnium dichloride (1.50 g, 2.91 mmol) in dichloromethane (30 mL) was added platinum oxide (0.04 g, 0.18 mmol, 2.7 wt%) to give a brown mixture. 100 psi hydrogen was added to the mixture and the reaction was stirred vigorously for 1 hour. The reaction was vented and filtered to give a colorless solution and black solid. The solution was evaporated under vacuum, leaving white solid title compound (Tetrahydroindenyl)(trimethylsilylmethylcyclopentadienyl)hafnium dichloride, (H4Ind)(Me3SiCH2Cp)HfCl2. Yield 1.43 g (95%). ¹H NMR (CD2Cl2): ^ 6.23 (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). _{[0102] Preparation of Indenyl(trimethylsilylmethylcyclopentadienyl)hafnium dichloride,} Ind(Me₃SiCH₂Cp)HfCl_2. To a white suspension of (trimethylsilylmethylcyclopentadienyl)hafnium trichloride (1,2-dimethoxyethane) (2.50 g, 4.75 mmol, 1.00 eq.) in ether (30 mL) was added lithium indenide (0.57 g, 4.75 mmol, 1.00 eq.) to give a light mixture. The mixture was stirred 21 hours and then evaporated under vacuum, leaving a solid. The solid was extracted with dichloromethane (25 mL, then 3x5 mL) and the extracts filtered to give a light yellow solution and white solid. The solution was evaporated under vacuum, leaving light yellow solid. The solid was washed with pentane (10 mL) and dried under vacuum to provide title compound (Indenyl(trimethylsilylmethylcyclopentadienyl)hafnium dichloride, Ind(Me₃SiCH₂Cp)HfCl₂). Yield 2.27 g (93%) light yellow powder. ¹H NMR (CD2Cl2): ^ 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). _{[0103] Preparation of (Trimethylsilylmethylcyclopentadienyl)hafnium trichloride (1,2-} dimethoxyethane) ((Me₃SiCH₂Cp)HfCl₃(dme)). To a white suspension of hafnium tetrachloride (11.65 dichloromethane (120 mL) at -35°C was added dimethyl sulfide eq.) to give a hazy, pale yellow solution. Tributyl(trimethylsilylmethylcyclopentadienyl)stannane (16.85 g, 38.2 mmol, 1.05 eq.) was added dropwise to the solution to give a hazy, amber solution. The mixture was allowed to warm to room temperature and stirred 3 hours. 1,2-Dimethoxyethane (10.00 g, 109 mmol, 2.99 eq.) was then added to the reaction and the mixture was filtered to give an amber solution and a small amount of white solid. The solution was evaporated under vacuum, leaving a damp, white solid. The solid was washed with pentane (100 mL, then 3x40 mL) and dried under vacuum to provide the title compound (Me₃SiCH₂Cp)HfCl₃(dme)). Yield 18.15 g (95%) white powder. ¹H NMR (CD2Cl2): ^ 6.29 (t, 2H), 4.13 (br s, 4H), 3.91 (3, 6H), 2.33 (s, 2H), -0.01 (s, 9H). _{[0104] Preparation of Tributyl(trimethylsilylmethylcyclopentadienyl)stannane,} Bu₃Sn(Me₃SiCH₂Cp). To a colorless solution of chlorotributylstannane (12.55 g, 38.6 mmol, 1.00 eq.) in ether (60 mL) was added lithium (trimethylsilylmethylcyclopentadienide) (6.10 g, 38.5 mmol, 1.00 eq.) to give a cloudy, light mixture. The reaction was stirred 4 hours and then dried under vacuum, leaving a mixture. The mixture was extracted with pentane (50 mL, then 2x20 mL) and extracts filtered to give a yellow solution and a solid. The solution was evaporated under vacuum, leaving yellow liquid title compound (Bu3Sn(Me3SiCH2Cp)). Yield 16.88 g (99%). ¹H NMR (C6D6): ^ 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). Example Synthesis of Iron Catalyst 1 _{[00127] Iron Catalyst 1 is:} 2-chloro-4, 6-dimethyl chloride and formic acid (95-97%) were purchased from Sigma- as The ¹H NMR measurements were recorded on a 400 MHz Bruker spectrometer. _{[00128] 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, a solid 2-chloro-4, 6-dimethyl aniline (9.537 g, 62 mmol) and formic acid (0.5 mL) were added. The resulting mixture was stirred at room temperature for 48 hours, and a colorless solid precipitated out during the course of reaction. Colorless crystalline solids were filtered out and washed with cold methanol. Crude materials ¹H NMR spectrum showed that three are 1:1 ratio of title precursor compound and starting material 2-chloro-4,6-dimethyl aniline. The desired compound was purified by column chromatography with a mixture of hexane/ethyl acetate (8:2 ratio) as eluent and solvent removal resulted in colorless crystalline solid (2,6-bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine) in 2.5 g (18.6 %) yield. ¹H NMR (400 MHz, CD₂Cl₂): ^ 2.06 (6H, s, CH₃ side arms), 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. _{[00129] Synthesis of 2,6-bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron} dichloride (Iron Catalyst 1). A solid pro-ligand, 2,6-Bis-[1-(2-chloro-4,6- dimethylphenylimino)ethyl]pyridine, was dissolved in THF (40 mL) and cooled to -25°C, to this a solid pre-dried iron chloride was added. The resulting mixture was stirred overnight at room temperature. The resulting mixture color turned from brown to blue during the course of the reaction and the desired iron complex was precipitated out as blue solids. The blue iron compound was filtered out and washed with hexane. The crude materials were further re-dissolved in dichloromethane to remove any insoluble iron containing impurities and ionic compounds formed during the course of the reaction, which could not be identified by ¹H NMR measurements because of their faster relaxation rate (paramagnetic nature) on NMR timescale. Solvent removal under reduced pressure resulted in blue crystalline solid of the bis-[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron dichloride in 1.89 g (81.9 %) yield. ¹H NMR (400 MHz, CD₂Cl₂): ^ -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. Supported mixed catalyst preparations: Metallocene Catalyst 2:Iron Catalyst 160:40 Prep 2, 22 umol _{[00130] To a stirred vessel 1800 g of toluene (Sigma Aldrich) was added along with 894g} of methylaluminoxane (30 wt % in toluene, Albemarle). To this solution 741 g of ES70 (Ineos)– 875 ^oC calcined silica was added. The mixture was stirred for three hours at 80 ^oC after which the temperature was reduced and the reaction was allowed to cool to ambient temperature. (Tetrahydroindenyl)(trimethylylsilylmethylcyclopentadienyl)hafnium dichloride (6.86 g, 13.2 mmol) and 2,6-Bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride (4.97 g, 8.80 mmol) were then dissolved in toluene (250 g) and added to the vessel, which was stirred for one hour. The mixing speed was then reduced and stirred slowly while drying under vacuum for 65 hours, after which 984 g silica supported catalyst was obtained. Metallocene Catalyst 2:Iron Catalyst 180:20 Prep 2, 22 umol _{[00131] To a stirred vessel 1800 g of toluene (Sigma Aldrich) was added along with 894g} of methylaluminoxane (30 wt % in toluene, Albemarle). To this solution 741 g of ES70 (Ineos)– 875 ^oC calcined silica was added. The mixture was stirred for three hours at 80 ^oC after which the temperature was reduced and the reaction was allowed to cool to ambient temperature. (Tetrahydroindenyl)(trimethylylsilylmethylcyclopentadienyl)hafnium dichloride (9.15 g, 17.6 mmol) and 2,6-Bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride (2.49 g, 4.40 mmol) were then dissolved in toluene (250 g) and added to the vessel, which was stirred for one hour. The mixing speed was then reduced and stirred slowly while drying under vacuum for 65 hours, after which 992 g silica supported catalyst was obtained. Metallocene Catalyst 1:Iron Catalyst 180:20 Prep 2, 30 umol _{[00132] To a stirred vessel 1668 g of toluene (Sigma Aldrich) was added along with 925 g} of methylaluminoxane (30 wt % in toluene, Albemarle). To this solution 734 g of ES70 (Ineos)– 875 ^oC calcined silica was added. The mixture was stirred for three hours at 80 ^oC after which the temperature was reduced and the reaction was allowed to cool to ambient temperature. bis(trimethylsilylmethyl-cyclopentadienide)hafnium dimethyl (12.27 g, 24.00 mmol) and 2,6-Bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride (3.39 g, 6.00 mmol) were then dissolved in toluene (250 g) and added to the vessel, which was stirred for one hour. The mixing speed was then reduced and stirred slowly while drying under vacuum for 65 hours, after which 1036 g silica supported catalyst was obtained. Process Summary _{[00133] Polymerization was performed in an 18.5 foot tall gas-phase fluidized bed reactor} with a 10 foot body and an 8.5 foot expanded section. Cycle and feed gases were fed into the reactor body through a perforated distributor plate, and the reactor was controlled at 290 psig and 67 mol% ethylene. The reactor temperature was controlled by manipulating the temperature of the cycle gas loop. Continuity aid (CA-300, from Univation) was co-fed into the reactor by a second carrier nozzle to reactor bed, and the feed rate of continuity aid was adjusted to maintain a weight concentration in the bed of between 20 ppm and 40 ppm. _{[00134] Good reactor operability was observed with a wide range of conditions, including} the utilization of trim technology to adjust catalyst ratio. Typically, inclusion of continuity aid results in increasing reactor operability at the expense of catalyst activity. For these catalysts, high activity was observed with CA-300 at 30 ppm while maintaining high settled resin bulk density. Trim was also used in one instance in order to adjust catalyst ratio. _{[00135] Activity appeared to increase while MIR decreased from a C6/C2 ratio increase} (runs 1 and 2), suggesting a higher contribution from Met. Cat. 2 at lower density. Changing catalyst ratio from 60:40 to 80:20 (cf. Runs 2 and 5) resulted in lower MIR as well, though with much less C6 present in the reactor for a higher density. _{[00136] The catalyst system of Met. Cat. 1:Iron Cat. 1 overall seemed to have a lower} molecular weight capability (higher MI at lower H2/C2 ratio) and somewhat less hexene incorporation than the catalyst system of Met. Cat. 2:Iron Cat. 1 at the same catalyst ratio (runs 5, 6). However, the catalyst system of Met. Cat. 1:Iron Cat. 1 had very high catalyst activity, good operability, and high bulk density.

Run 1 2 3 4 5 6 Catalyst Met. Cat. Met. Cat. Met. Cat. Met. Cat. Met. Cat. Met. Cat. at. 0) [_{00137] Overall, methods of the present disclosure can include producing LLDPE} compositions at high catalyst activity and good bulk density, while maintaining useful LLDPE properties such as processability, stiffness, and toughness, each of which can be important for film and other applications. Addition of a continuity aid (such as aluminum distearate) to polymerizations having mixed catalyst systems of the present disclosure provides benefits such as good bulk density even at high catalyst activity. LLDPEs of the present disclosure can also have broad orthogonal composition distribution (“BOCD”), which provides for improved processability and sufficient stiffness and toughness for end use applications. Catalyst systems for processes of the present disclosure include a mixed catalyst system of a metallocene catalyst, such as a Group 4 cyclopentadienyl metallocene catalyst, and a 2,6-bis(imino)pyridyl iron complex. For example, a Group 4 cyclopentadienyl metallocene can be an unbridged hafnocene catalyst having one or more cyclopentadienyl ring having one or more alkylsilyl substitution. _{[00138] All documents described herein are incorporated by reference herein, including} any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of”, “consisting of”, “selected from the group of consisting of”, or “is” preceding the recitation of the composition, element, or elements and vice versa. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

Claims

CLAIMS: What is claimed is: 1. A process for producing a polyethylene composition, comprising: introducing, under polymerization conditions, ethylene and a C₃-C₄₀ alpha-olefin with a catalyst system and a continuity aid in a reactor, the catalyst system comprising an activator, an iron catalyst compound, and an unbridged Group 4 metallocene catalyst compound having one or more alkyl silyl substitutions; and forming a polyethylene composition.

2. The process of claim 1, wherein: the catalyst system has a catalyst activity of about 10,000 gP/gcat to about 20,000 gP/gcat, and the polyethylene composition has a bulk density of about 0.45 g/cm³ to about 0.52 g/cm³.

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

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

5. The process of claim 4, wherein the continuity aid is present in the reactor in an amount of about 20 ppm to about 40 ppm.

6. The process of claim 1 or any one of claims 2-5, wherein the continuity aid is aluminum stearate, aluminum distearate, aluminum oleate, oxol aluminum stearate, or combinations thereof.

7. The process of claim 1 or any one of claims 2-5, wherein the continuity aid is an alkoxylated amine, a carboxylic acid salt, or combination thereof.

8. The process of claim 1 or any one of claims 2-7, wherein the C3-C40 alpha-olefin is 1- hexene.

9. The process of claim 1 or any one of claims 2-8, wherein the iron catalyst compound is represented by Formula (IIa) or Formula (IIb): each of R^6a, R^10a, R^11a, and R^15a are independently halogen, -CF3, or C1-C22-alkyl, or –OR'; each of R^1a and R^2a is independently hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22- aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S, wherein each of R^1a and R^2a is optionally substituted by halogen, -NR'₂, -OR' or –SiR''3, wherein R^1a optionally bonds with R^3a, and R^2a optionally bonds with R^5a, in each case to independently form a five-, six- or seven-membered ring; each of R^3a, R^4a, R^5a, R^7a, R^8a, R^9a, R^12a, R^13a, and R^14a is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, halogen, -NR'2, -OR', -SiR''3 or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S; and each of X^1a, X^2a, and X^3a is independently hydrogen, halogen, C1-C20-alkyl, C₂-C₁₀-alkenyl, C₆-C₂₀-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR'2, -OR', -SR', -SO3R', -OC(O)R', -CN, -SCN, ^-diketonate, -CO, -BF₄ ⁻, -PF₆ ⁻ or bulky non-coordinating anion, or X^1a and X^2a optionally bond to form a five- or six-membered ring.

10. The process of claim 9, wherein the iron catalyst compound is: .

11. The process of any one or Group 4 metallocene catalyst compound is represented by Formula (I): ^^^ ^^^ ^^^ ^^ , wherein: M of Formula (I) is Ti, Hf, or Zr; each of X¹ and X² of Formula (I) is independently C1 to C20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X¹ and X² join together to form a C4 to C62 cyclic or polycyclic ring structure; each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ of Formula (I) is independently selected from hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements or one or more of R¹ and R², R² and R³, R³ and R⁴, R⁵ and R⁶, R⁶ and R⁷, R⁷ and R⁸ are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring, such as a substituted or unsubstituted C4 to C62 cyclic or polycyclic ring; and each of R⁹, R¹⁰, R¹⁰, R¹¹, R¹², and R¹³ of Formula (I) is independently selected from hydrogen, C1-C40 hydrocarbyl, or substituted C1-C40 hydrocarbyl.

12. The process of claim 11, wherein the unbridged Group 4 metallocene catalyst compound is: ^^ ^ _{^ ^ ^ ^^} ^^ _^ . 13. The process of any one of claims 9 or 10, wherein the unbridged Group 4 metallocene catalyst compound is represented by Formula (III): , wherein: M of Formula (III) is Ti, Hf, or Zr; each of X¹ and X² of Formula (III) is independently C1 to C20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X¹ and X² join together to form a C4 to C62 cyclic or polycyclic ring structure; each of R¹, R², R³, R⁴, R⁵, R⁶, R¹⁴, R¹⁵, and R¹⁶ of Formula (III) is independently selected from hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, -NR’2, -SR’, -OR’, -OSiR’₃, or -PR’₂, wherein each R’ is independently hydrogen, halogen, C₁-C₁₀ alkyl, or C6-C10 aryl, or one or more of R¹ and R², R² and R³, R³ and R⁴, R⁴ and R⁵, R¹ and R⁵, R¹⁴ and R¹⁵, and R¹⁵ and R¹⁶ join together to form a C₄ to C₆₂ cyclic or polycyclic ring structure; each of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ of Formula (III) is independently selected from hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, aryl, substituted aryl, -NR’₂, -SR’, -OR’, -OsiR’₃, or -PR’₂, wherein each R’ is independently hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R⁷ and R⁸, R⁸ and R¹⁰, and R¹⁰ and R¹² are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring. 14. The process of claim 13, wherein the unbridged Group 4 metallocene catalyst compound is . 15. The process of claim 1 or any one of claims 2-14, wherein the reactor is a gas phase fluidized bed reactor. 16. The process of claim 15, wherein the polymerization conditions comprise: 1) a reactor temperature of about 40 °C to about 120 °C; 2) a reactor pressure of about 0.45 MPa to about 6 MPa; 3) presence of an aliphatic hydrocarbon solvent; 4) wherein the activator is an alumoxane activator; 5) the continuity aid is present in an amount of about 20 ppm to about 40 ppm based on the weight of polyethylene composition formed; and 6) a molar ratio of the Group 4 metallocene catalyst compound to the iron catalyst compound is about 1:1 to about 9:1. 17. The process of claim 1 or any one of claims 2-16, further comprising introducing about 0.25 mole to about 5 mole of scavenger per mole water in the continuity aid, as measured prior to addition of the scavenger thereto. 18. The process of claim 1 or any one of claims 2-17, wherein the continuity aid is aluminum distearate. 19. The process of claim 1, wherein the polyethylene composition has a gradient density of about 0.91 g/cm³ to about 0.94 g/cm³.