Bimodal catalyst system

Abstract

An embodiment provides a bimodal polymerization catalyst system comprising a metallocene olefin polymerization catalyst prepared from a biphenylphenol polymerization pre-catalyst of Formula I and a biphenylphenol polymerization catalyst.

Description

Technical Field

[0001] Embodiments of the present disclosure are directed to bimodal catalyst systems, and more particularly, bimodal catalyst systems that can be utilized to produce bimodal polyethylene compositions containing high molecular weight polyethylene components and low molecular weight polyethylene components in a single gas phase reactor.

Background Art

[0002] Polymers can be used in many products, particularly films, fibers, non-woven and / or woven fabrics, extruded articles, and / or molded articles. Polymers can be produced by reacting one or more types of monomers in a polymerization reaction in the presence of a polymerization catalyst.

Summary of the Invention

[0003] The present disclosure provides various embodiments including the following.

[0004] A metallocene olefin polymerization catalyst and Formula I:

Chemical Formula

[0005] A process for producing a bimodal polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, wherein the high molecular weight and low molecular weight polyethylene components are produced together in a single gas phase reactor via a polymerization process using a bimodal polymerization catalyst system, and the bimodal polyethylene composition has a value of weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) greater than 5.00, a value of z average molecular weight (Mz) to weight average molecular weight (Mw) ratio (Mz / Mw) less than Mw / Mn, or both a Mw / Mn greater than 5.00 and a Mz / Mw less than Mw / Mn; and A process for producing a bimodal polymerization catalyst system, comprising producing a biphenylphenol polymerization catalyst by contacting a biphenylphenol polymerization precatalyst of formula I with an activator under activation conditions, as detailed herein.

DETAILED DESCRIPTION OF THE INVENTION

[0006] A metallocene olefin polymerization catalyst and a biphenylphenol polymerization catalyst prepared from a biphenylphenol prepolymer catalyst of formula I: [Chemical formula] (wherein each of R 7 and R 8 is independently C1-C 20 alkyl, aryl or aralkyl, halogen, or hydrogen, and wherein each of R 5 and R 10 is independently C1-C 20 alkyl, aryl, aralkyl, halogen, alkyl- or aryl-substituted silyl, or hydrogen, and wherein each of R 2 and R 13 is independently C1-C 20 alkyl, aryl or aralkyl, or hydrogen, and wherein each of R 15 and R 16 is independently 2,7-disubstituted carbazol-9-yl, and wherein L is saturated C2-C3 alkyl and forms a 2-carbon or 3-carbon bridge between the two oxygen atoms to which L is attached, and wherein each X is independently halogen, hydrogen, (C1-C 20 )alkyl, (C7-C 20 )aralkyl, (C1-C6)alkyl-substituted (C6-C 12 )aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R C )3, and wherein R C is C1-C 12 hydrocarbon, and wherein each of R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 is independently hydrogen, and wherein M is a heteroatom selected from the group consisting of Zr and Hf).

[0007] The biphenylphenol polymerization pre-catalyst represented by Formula I (i.e., the biphenylphenol polymerization pre-catalyst) can be utilized to produce a biphenylphenol polymerization catalyst as described herein. For example, the biphenylphenol polymerization pre-catalyst represented by Formula I can be contacted with an activator to activate the biphenylphenol polymerization pre-catalyst represented by Formula I under activation conditions, thereby producing a biphenylphenol polymerization catalyst.

[0008] As described above, R as shown in Formula I 7 and R 8 each independently is C1-C 20 alkyl, aryl or aralkyl, halogen, or hydrogen. One or more embodiments provide that each of R 7 and R 8 is C1 alkyl, such as methyl.

[0009] As used herein, "alkyl" includes linear, branched, and cyclic paraffin groups lacking one hydrogen. Thus, for example, the CH3 group ("methyl") and the CH3CH2 group ("ethyl") are examples of alkyl.

[0010] As used herein, "aryl" includes phenyl, naphthyl, pyridyl, and other groups having a ring structure characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. It is understood that "aryl" may be C6-C 20 aryl. For example, the C6H5-aromatic structure is "phenyl" and the C6H4-aromatic structure is "phenylene". As used herein, "aralkyl", which may also be referred to as "arylalkyl" in some cases, is an alkyl having an aryl pendant therefrom. "Aralkyl" is C7-C 20It is understood that it may be aralkyl. "Alkylaryl" is an aryl having one or more alkyls hanging therefrom. As used herein, "hydrocarbyl" includes aliphatic, cyclic, olefinic, acetylenic and aromatic groups (i.e., hydrocarbon groups) containing hydrogen and carbon lacking one hydrogen.

[0011] As described above, each of R as shown in Formula I 5 and R 10 can each independently be C1-C 20 alkyl, aryl, aralkyl, halogen, alkyl- or aryl-substituted silyl, or hydrogen. For example, in one or more embodiments, R 5 and R 10 are provided as being dialkyl- or trialkyl-substituted silyl. In one or more embodiments, each of R 5 and R 10 is provided as being octyldimethylsilyl.

[0012] As described above, each of R as shown in Formula I 4 and R 11 can each independently be hydrogen or a halide such as fluorine. For example, in one or more embodiments, each of R 4 and R 11 is provided as being hydrogen.

[0013] As described above, each of R as shown in Formula I 2 and R 13 can each independently be C1-C 20 alkyl, aryl or aralkyl, or hydrogen. In one or more embodiments, each of R 2 and R 13 is provided as being C3-C4 alkyl such as n-butyl, t-butyl, or 2-methyl-pentyl. In one or more embodiments, each of R 2 and R 13 is provided as being 1,1,3,3-tetramethylbutyl.

[0014] As described above, each of R as shown in Formula I 15 and R 16 can each be 2,7-disubstituted carbazol-9-yl. For example, in one or more embodiments, each of R 15 and R 16 is provided to be 2,7-disubstituted carbazol-9-yl selected from the group consisting of 2,7-di-t-butylcarbazol-9-yl, 2,7-diethylcarbazol-9-yl, 2,7-dimethylcarbazol-9-yl, and 2,7-bis(diisopropyl(n-octyl)silyl)-carbazol-9-yl.

[0015] As described above, as shown in Formula I, L is saturated C2-C3 alkyl and forms a 2-carbon or 3-carbon bridge between the two oxygen atoms to which L is attached. For example, in one or more embodiments, L is provided to be saturated C3 alkyl that forms a bridge between the two oxygen atoms to which L is attached. The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double or triple bonds.

[0016] As described above, as shown in Formula I, each X is independently halogen, hydrogen, (C1-C 20 )alkyl, (C7-C 20 )aralkyl, (C1-C6)alkyl-substituted (C6-C 12 )aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R C )3, where R C is C1-C 12 hydrocarbon. For example, in one or more embodiments, each X is provided to be independently C1 alkyl.

[0017] As described above, as shown in Formula I, M is a heteroatom such as a metal atom. In some embodiments, M can be selected from the group consisting of Zr and Hf. One or more embodiments provide that M is zirconium. One or more embodiments provide that M is hafnium.

[0018] As described herein, each of the R groups (R 1 ~R 16 ) and X of Formula I can each be independently substituted or unsubstituted. For example, in some embodiments, each of the Xs of Formula I can independently be (C1-C6)alkyl-substituted(C6-C 12 )aryl, or (C1-C6)alkyl-substituted benzyl. As used herein, "substituted" indicates that the group following the term has at least one moiety in place of one or more hydrogens at any position, and the moiety is selected from groups such as halogen radicals, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1-C 20 alkyl groups, C2-C 10 alkenyl groups, and combinations thereof. "Disubstituted" refers to the presence of two or more substituents at any position, and the moiety is selected from groups such as halogen radicals, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl, C1-C 20 alkyl groups, C2-C 10 alkenyl groups, and combinations thereof.

[0019] The biphenylphenol polymerization catalyst produced from the metallocene olefin polymerization catalyst and the biphenylphenol polymerization pre-catalyst herein can be produced using the reactants described herein. The biphenylphenol polymerization catalyst produced from the metallocene olefin polymerization catalyst and the biphenylphenol polymerization pre-catalyst herein can be produced by many processes, for example, using conventional solvents, reaction conditions, reaction times, and isolation procedures, and is utilized for producing known catalysts such as known metallocene olefin polymerization catalysts.

[0020] One or more embodiments provide a polymerization catalyst, i.e., a biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization pre-catalyst of formula I. The biphenylphenol polymerization catalyst is produced by contacting the biphenylphenol polymerization pre-catalyst and an activator under activation conditions, and can provide a biphenylphenol polymerization catalyst, e.g., an activated biphenylphenol polymerization pre-catalyst. Activation conditions are well known in the art.

[0021] As used herein, "activator" refers to any supported or unsupported compound or combination of compounds that can activate a complex or catalyst component, e.g., by generating a cationic species of the catalyst component. For example, this can include the abstraction of at least one leaving group, e.g., the "X" group described herein, from the metal center of the complex / catalyst component, e.g., a metal complex of formula I. As used herein, "leaving group" refers to one or more chemical moieties that are bonded to a metal atom and can be removed by an activator, thus generating a species that is active towards olefin polymerization.

[0022] The activator can include a Lewis acid or a non-coordinating ionic activator or an ionizing activator, or a Lewis base, an aluminum alkyl, and / or any other compound including a conventional co-catalyst. In addition to the above-mentioned methylaluminoxane ("MAO") and modified methylaluminoxane ("MMAO"), exemplary activators include, but are not limited to, an aluminoxane or a modified aluminoxane, and / or an ionizing compound, neutral or ionic, such as dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(3,5-(CF3)2phenyl)borate, triphenylcarbenium tetrakis(3,5-(CF3)2phenyl)borate, dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, dimethylanilinium tetrakis(pentafluoronaphthyl)aluminate, triphenylcarbenium tetrakis(pentafluoronaphthyl)aluminate, dimethylanilinium tetrakis(perfluoronaphthyl)aluminate, triphenylcarbenium tetrakis(perfluoronaphthyl)aluminate, tris(pentafluorophenyl)boron, tris(perfluoronaphthyl)boron, tris(pentafluorophenyl)aluminum, tris(perfluoronaphthyl)aluminum or any combination thereof.

[0023] Aluminoxane can be described as an oligomeric aluminum compound having -A1(R)-O- subunits (where R is an alkyl group). Examples of aluminoxane include, but are not limited to, methylaluminoxane ("MAO"), modified methylaluminoxane ("MMAO"), ethylaluminoxane, isobutylaluminoxane, or combinations thereof. Aluminoxane can be produced by hydrolysis of each trialkylaluminum compound. MMAO can be produced by hydrolysis of higher trialkylaluminums such as trimethylaluminum and triisobutylaluminum. There are various known methods for preparing aluminoxane and modified aluminoxane. Aluminoxane can include modified methylaluminoxane ("MMAO") type 3A (the trade name of modified methylaluminoxane type 3A described in U.S. Patent No. 5,041,584 and commercially available from Akzo Chemicals, Inc.). The MAO source can be, for example, a solution having about 1 wt% to about 50 wt% MAO. Commercially available MAO solutions include 10 wt% and 30 wt% MAO solutions available from Albemarle Corporation (Baton Rouge, La).

[0024] One or more organoaluminum compounds, such as one or more alkylaluminum compounds, can be used in combination with aluminoxane. Examples of alkylaluminum compounds include, but are not limited to, diethylaluminum ethoxide, diethylaluminum chloride, diisobutylaluminum hydride, and combinations thereof. Examples of other alkylaluminum compounds, such as trialkylaluminum compounds, include, but are not limited to, trimethylaluminum, triethylaluminum ("TEAL"), triisobutylaluminum ("TiBAl"), tri-n-hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, and combinations thereof.

[0025] The metallocene olefin polymerization catalyst can be any metallocene olefin polymerization catalyst. In one or more embodiments, the metallocene olefin polymerization catalyst is selected from the group consisting of (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, Me2Si(indenyl)2MX2, Me2Si(tetrahydroindenyl)2MX2, (n-propylcyclopentadienyl)2MX2, (n-butylcyclopentadienyl)2MX2, (1-methyl,3-butylcyclopentadienyl)2MX2, HN(CH2CH2N(2,4,6-Me3phenyl))2MX2, HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2, (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2, (butylcyclopentadienyl)2MX2, (propylcyclopentadienyl)2MX2, and mixtures thereof (where M is Zr or Hf and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1-C5 alkyl or alkenyl). In one or more embodiments, the metallocene olefin polymerization catalyst is selected from the group consisting of bis(indenyl)zirconium dichloride, (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride, or (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride.

[0026] A bimodal polymerization catalyst system comprising a metallocene olefin polymerization catalyst and a biphenylphenol polymerization precatalyst produced from a biphenylphenol polymerization precatalyst can be used to produce a polymer. For example, a bimodal polymerization catalyst system and an olefin can be contacted under polymerization conditions to produce a polymer, such as a polyolefin polymer.

[0027] As used herein, "polymer" has two or more identical or different polymer units derived from one or more different monomers, such as homopolymers, copolymers, terpolymers, etc. A "homopolymer" is a polymer having the same polymer units. A "copolymer" is a polymer having two or more different polymer units that are different from each other. A "terpolymer" is a polymer having three different polymer units that are different from each other. When referring to polymer units, "different" indicates that the polymer units differ from each other by at least one atom or are isomerically different. Thus, the definition of copolymer used herein includes terpolymers and the like. As used herein, "polymerization process" is a process used to produce a polymer.

[0028] Embodiments provide that the polymer can be a polyolefin polymer. As used herein, "olefin", which may be referred to as "alkene", refers to a straight-chain, branched, or cyclic compound containing carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer is said to contain an olefin (e.g., be made from an olefin), the olefin present in such a polymer or copolymer is in a polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 1 wt% to 99 wt%, it is understood that the polymer units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present at 1 wt% to 99 wt% based on the total weight of the polymer. Higher α-olefins refer to α-olefins having three or more carbon atoms.

[0029] Examples of polyolefins include polymers made from olefin monomers such as ethylene, i.e., polyethylene, and linear or branched higher α-olefin monomers containing 3 to 20 carbon atoms. Examples of higher α-olefin monomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-1-hexene. Examples of polyolefins include, in particular, ethylene-based polymers having at least 50% by weight of ethylene, such as ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene copolymers. Other olefins that can be used include, for example, ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cyclic olefins. Examples of monomers include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentene. In many embodiments, a copolymer of ethylene is produced, where ethylene and a comonomer having at least one α-olefin having 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably 4 to 8 carbon atoms can be polymerized, for example, in a gas phase polymerization process. In another embodiment, ethylene and / or propylene can be polymerized with at least two different comonomers (optionally, one of which can be a diene) to produce a terpolymer.

[0030] One or more embodiments provide that the polymer can include units derived from 1 to 100% by weight of ethylene, based on the total weight of the polymer. All individual values and subranges of 1 to 100% by weight are included. For example, the polymer can include units derived from ethylene with a lower limit of 1, 5, 10, or 50% by weight to units derived from ethylene with an upper limit of 100, 95, 90, 85, or 75% by weight, based on the total weight of the polymer.

[0031] As described above, surprisingly, a bimodal polymerization catalyst system comprising a biphenylphenol polymerization catalyst prepared from the biphenylphenol polymerization pre-catalyst of Formula I can assist in providing a polymer by a polymerization process in a single gas-phase reactor. In one or more embodiments, the resulting polymer can have at least a high molecular weight polyethylene component and a low molecular weight polyethylene component, as detailed herein. In one or more embodiments, the resulting polymer can be a bimodal polymer, such as a bimodal polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, and the high molecular weight and low molecular weight polyethylene components are formed together by a polymerization process using a bimodal polymerization catalyst system in a single gas-phase reactor. Having a high molecular weight polyethylene component and a low molecular weight polyethylene component is desirable in some applications.

[0032] Surprisingly, the bimodal polymerization catalyst system comprising a biphenylphenol polymerization catalyst prepared from the biphenylphenol polymerization pre-catalyst of Formula I of the present disclosure can produce a bimodal polymer comprising a high molecular weight polyethylene component having a smaller molecular weight compared to the high molecular weight component in a bimodal polymer formed with other (non-inventive) polymerization catalysts under similar polymerization conditions, as detailed herein. In some applications, a high molecular weight polyethylene component having a lower molecular weight than other high molecular weight polyethylene components is desirable.

[0033] Embodiments provide that the polymer can have an overall Mn (number average molecular weight) of from 8,000 to 50,000. All individual values and subranges from 8,000 to 50,000 are included, for example, the polymer can have an overall Mn from a lower limit of 8,000, 10,000, or 12,000 to an upper limit of 50,000, 40,000, or 35,000. In some embodiments, the overall Mn can be in the range of 12,170 to 30,958.

[0034] Embodiments provide that the polymer can have an overall Mw (weight average molecular weight) of 50,000 to 1,000,000. All individual values and sub-ranges from 100,000 to 1,000,000 are included. For example, the polymer can have an overall Mw from a lower limit of 50,000, 100,000, or 200,000 to an upper limit of 1,000,000, 800,000, or 600,000. In some embodiments, the overall Mw can be in the range of 218,937 to 529,748.

[0035] Embodiments provide that the polymer can have an overall Mz (z average molecular weight) of 200,000 to 10,000,000. All individual values and sub-ranges from 200,000 to 10,000,000 are included. For example, the polymer can have an overall Mz from a lower limit of 200,000, 700,000, or 900,000 to an upper limit of 10,000,000, 5,000,000, or 3,000,000. In some embodiments, the overall Mz can be in the range of 945,368 to 2,645,720.

[0036] Embodiments provide that the polymer can have an overall Mz to Mw ratio in the range of 2.00 to 20.00. All individual values and sub-ranges from 2.00 to 20.00 are included. For example, the polymer can have an overall Mz to Mw ratio from a lower limit of 2.00, 3.00, or 4.00 to an upper limit of 20.00, 15.00, or 10.00. In some embodiments, the polymer can have an overall Mz to Mw ratio of 4.32 to 8.21.

[0037] In some embodiments, the polymer can have a value of the Mw to Mn ratio greater than 5.00. For example, an embodiment provides that the polymer can have an overall Mw to Mn ratio in the range of 5.00 to 75.00. All individual values and sub-ranges from 5.00 to 75.00 are included. For example, the polymer can have an Mw to Mn ratio with a lower limit of 5.00, 6.00, or 7.00 and an upper limit of 75.00, 60.00, or 50.00. In some embodiments, the polymer can have an overall Mw to Mn ratio of 8.95 to 43.53.

[0038] An embodiment provides that the polymer can have an overall Mz to Mw ratio that is less than the overall Mw to Mn ratio of the polymer.

[0039] An embodiment provides that the polymer can have a melt index (I 21 ) in the range of 0.001 dg / min to 1000 dg / min, as measured by ASTM D1238 (at 190 °C and a load of 21 kg). All individual values and sub-ranges from 0.001 dg / min to 1000 dg / min are included. For example, the polymer can have a melt index (I 21 ) of 1.49 dg / min to 7.93 dg / min.

[0040] An embodiment provides that the polymer can have a density of 0.890 g / cm 3 to 0.970 g / cm 3 . All individual values and sub-ranges from 0.890 to 0.970 g / cm 3 are included. For example, the polymer can have a lower limit of 0.890, 0.900, 0.910, 0.920, or 0.940 g / cm 3 and an upper limit of 0.970, 0.960, or 0.950 g / cm 3can have a density up to the upper limit. The density can be determined according to ASTM D - 792 - 13, Standard Test Method for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, e.g., liquid 2 - propanol). The result is reported in units of grams per cubic centimeter (g / cm 3 ).

[0041] Gel Permeation Chromatography (GPC) Test Method: Weight - average Molecular Weight Test Method: Using the chromatogram obtained with a high - temperature gel permeation chromatography instrument (HTGPC, Polymer Laboratories), M w , number - average molecular weight (M n ), and M w / M nis determined. The HTGPC is equipped with a transfer line, a differential refractive index detector (DRI), and three Polymer Laboratories PLgel 10μm Mixed - B columns, all contained in an oven maintained at 160 °C. The method uses a solvent consisting of TCB treated with BHT at a nominal flow rate of 1.0 milliliter per minute (mL / min.) and a nominal injection volume of 300 microliters (μL). The solvent is prepared by dissolving 6 grams of butylated hydroxytoluene (BHT, an antioxidant) in 4 liters (L) of reagent - grade 1,2,4 - trichlorobenzene (TCB), and filtering the resulting solution through a 0.1 micrometer (μm) Teflon filter to obtain the solvent. Before the solvent enters the HTGPC instrument, it is degassed with an in - line degasser. The columns are calibrated using a series of monodisperse polystyrene (PS) standards. Separately, a test polymer of a known concentration dissolved in the solvent is prepared by heating a known amount in the known amount of solvent with continuous shaking at 160 °C for 2 hours. (All amounts are measured by weight.) The target solution concentration c of the test polymer is 0.5 to 2.0 milligrams of polymer per milliliter of solution (mg / mL), and a lower concentration of c is used for high - molecular - weight polymers. Before running each sample, the DRI detector is purged. Next, the flow rate within the apparatus is increased to 1.0 mL / min, and the DRI detector is stabilized for 8 hours before injecting the first sample. Using the general calibration relationship for column calibration, M w and M n are calculated. Using the following equations

Equation

[0334] -

[0341] of US2006 / 0173123. The GPC chromatogram is obtained by plotting dW / dLog(MW) on the y-axis against Log(MW) on the x-axis (Log(MW) and dW / dLog(MW) are as defined above).

[0042] The polymer can be used in many articles, particularly films, fibers, non-woven fabrics and / or woven fabrics, extruded articles, and / or molded articles, etc.

[0043] Provided is a metallocene olefin polymerization catalyst and a compound of formula I: [Chemical formula] (wherein each of R 7 and R 8 is independently C1 - C 20 alkyl, aryl or aralkyl, halogen, or hydrogen, and wherein each of R 5 and R 10 is independently C1 - C 20 alkyl, aryl, aralkyl, halogen, alkyl or aryl substituted silyl, or hydrogen, and wherein each of R 2 and R 13Each of them is independently C1 to C 20 alkyl, aryl or aralkyl, or hydrogen, wherein R 15 and R 16 each of which is independently 2,7-disubstituted carbazol-9-yl, wherein L is saturated C2-C3 alkyl, and a 2-carbon bridge or 3-carbon bridge is formed between two oxygen atoms to which L is bonded, wherein each X is independently halogen, hydrogen, (C1-C 20 )alkyl, (C7-C 20 )aralkyl, (C1-C6)alkyl-substituted (C6-C 12 )aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R C )3, wherein R C is C1-C 12 hydrocarbon, wherein R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 each of which is independently hydrogen, wherein M is a heteroatom selected from the group consisting of Zr and Hf) a biphenylphenol polymerization catalyst prepared from a biphenylphenol polymerization precatalyst, and, a bimodal polymerization catalyst system.

[0044] A metallocene olefin polymerization catalyst and / or a biphenylphenol polymerization catalyst prepared from a biphenylphenol polymerization precatalyst of formula I, and other components discussed herein such as activators can be utilized with a support. The "support", also referred to as a carrier, refers to any support material including porous support materials such as talc, inorganic oxides, and inorganic chlorides.

[0045] A metallocene olefin polymerization catalyst and / or a biphenylphenol polymerization precatalyst of formula I, and other components discussed herein, can be supported on the same or different supports, or one or more of the components can be used in an unsupported form. Using a support can be achieved by any technique used in the art. One or more embodiments provide that a spray drying process is used. Spray drying processes are well known in the art. The support can be functionalized.

[0046] The support can be a porous support material, such as talc, inorganic oxide, or inorganic chloride. Other support materials include resin support materials, such as functionalized or crosslinked organic supports like polystyrene, polystyrene divinylbenzene polyolefin, or polymer compounds, zeolites, clays, or any other organic or inorganic support material, or mixtures thereof.

[0047] Support materials include inorganic oxides containing metal oxides of Groups 2, 3, 4, 5, 13, or 14. Some preferred supports include silica, fumed silica, alumina, silica - alumina, and mixtures thereof. Some other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicates, zeolites, talc, clays, etc. Combinations of these support materials, such as silica - chromium, silica - alumina, silica - titania, etc., can also be used. Additional support materials include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads.

[0048] An example of the support is fumed silica available under the trade name Cabosil (trademark) TS-610, or other supports of the TS or TG series available from Cabot Corporation. Fumed silica is typically silica having particles with dimensions of 7 to 30 nanometers that have been treated with dimethylsilyl dichloride such that most of the surface hydroxyl groups are capped. That is, in some cases, the silica support can support a metallocene olefin polymerization catalyst, a biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of formula I, or a combination of a metallocene olefin polymerization catalyst and a biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of formula I. The silica support can be present in conventional amounts as described in WO2019 / 190897.

[0049] The support material can have a surface area in the range of about 10 to about 700 m 2 / g, a pore volume in the range of about 0.1 to about 4.0 g / cm 3 , and an average particle size in the range of about 5 to about 500 μm. More preferably, the surface area of the support material is in the range of about 50 to about 500 m 2 / g, the pore volume is about 0.5 to about 3.5 g / cm 3 , and the average particle size is about 10 to about 200 μm. Most preferably, the surface area of the support material is in the range of about 100 to about 400 m 2 / g, the pore volume is about 0.8 to about 3.0 g / cm 3 , and the average particle size is about 5 to about 100 μm. The average pore diameter of the carrier typically has a pore diameter in the range of 10 to 1000 Å, preferably 50 to about 500 Å, most preferably 75 to about 350 Å.

[0050] The metallocene olefin polymerization catalyst and / or the biphenylphenol polymerization precatalyst of formula I, and other components discussed herein such as activators, may be slurried. Slurries are well known in the art. The slurry may include, for example, a metallocene olefin polymerization catalyst and / or a biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization precatalyst of formula I, an activator, and a support.

[0051] The molar ratio of the metal in the activator to the metal in the metallocene olefin polymerization catalyst or the metal in the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization precatalyst of formula I in the slurry can be from 1000:1 to 0.5:1, from 300:1 to 1:1, or from 150:1 to 1:1. One or more diluents, such as fluids, can be used to facilitate the combination of any two or more components in the slurry. For example, the metallocene olefin polymerization catalyst and / or the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization precatalyst of formula I, and the activator can be combined together in the presence of toluene or another non-reactive hydrocarbon or hydrocarbon mixture. In addition to toluene, other suitable diluents can include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. Next, a dried or toluene-mixed support can be added to the mixture, or the metal-ligand complex / activator can be added to the support. The slurry may be fed to a reactor for the polymerization process, and / or the slurry may be dried (e.g., spray dried) before being fed to the reactor for the polymerization process.

[0052] The polymerization process can be a suspension polymerization process and / or a gas phase polymerization process. The polymerization process can be carried out using known apparatus and reaction conditions, such as known polymerization conditions. The polymerization process is not limited to any particular type of polymerization system. As an example, the polymerization temperature can range from about 0 °C to about 300 °C at atmospheric pressure, a pressure lower than atmospheric pressure, or a pressure higher than atmospheric pressure. In particular, slurry or solution polymerization systems can use a pressure lower than atmospheric pressure or a pressure higher than atmospheric pressure, and a temperature in the range of about 40 °C to about 300 °C. Embodiments provide a method of manufacturing a polyolefin polymer, which includes contacting an olefin with the bimodal polymerization catalyst system described herein under polymerization conditions to polymerize the olefin, thereby producing a polyolefin polymer.

[0053] One or more embodiments provide that the polymer can be formed via a gas phase polymerization system at a pressure higher than atmospheric pressure in the range of 0.07 to 68.9 bar, 3.45 to 27.6 bar, or 6.89 to 24.1 bar, and a temperature in the range of 30 to 130 °C, 65 to 110 °C, 75 to 120 °C, or 80 to 120 °C. In one or more embodiments, the operating temperature can be less than 112 °C. Stirred and / or fluidized bed gas phase polymerization systems can be used.

[0054] Generally, a conventional gas-phase fluidized bed polymerization process can be carried out by continuously passing a stream containing one or more olefin monomers under reaction conditions in the presence of a catalyst composition, such as a bimodal polymerization catalyst system (a metallocene olefin polymerization catalyst and a biphenylphenol polymerization catalyst prepared from a biphenylphenol prepolymer catalyst of formula I) and an activator, at a rate sufficient to maintain a bed of solid particles in a suspended state in a fluidized bed reactor. A stream containing unreacted monomer can be continuously withdrawn from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled to the reactor. The product, i.e., the polymer, can be removed from the reactor and a substituted monomer can be added to the recycle stream. A gas inert to the catalyst composition and reactants can also be present in the gas stream. The polymerization system can include, for example, a single reactor or two or more consecutive reactors.

[0055] The feed stream to the polymerization process can contain an olefin monomer, a non-olefin gas such as nitrogen and / or hydrogen, and further can contain one or more non-reactive alkanes that are condensable in the polymerization process and can be used to remove the heat of reaction. Exemplary non-reactive alkanes include, but are not limited to, propane, butane, isobutane, pentane, isopentane, hexane, their isomers, and their derivatives. The feed can be introduced into the reactor at a single or multiple different locations.

[0056] For the polymerization process, a polymerization catalyst (a metallocene olefin polymerization catalyst and / or a biphenylphenol polymerization catalyst prepared from a biphenylphenol prepolymerization catalyst of formula I) can be continuously supplied to the reactor. A gas inert to the polymerization catalyst, such as nitrogen or argon, can be used to carry the polymerization catalyst to the reactor bed. In one embodiment, the polymerization catalyst can be provided as a slurry in mineral oil or a liquid hydrocarbon or mixture such as propane, butane, isopentane, hexane, heptane, or octane. The slurry can be delivered to the reactor with a carrier fluid such as nitrogen or argon, or a liquid such as isopentane or another C3 - C8 alkane.

[0057] For the polymerization process, hydrogen can be utilized in the reactor at a gas molar ratio of hydrogen to ethylene, which can be in the range of about 0.0 - 1.0, 0.01 - 0.7, 0.03 - 0.5, 0.005 - 0.3, or 0.0017 - 0.0068. Many embodiments use hydrogen gas.

[0058] Some aspects of the present disclosure are provided as follows.

[0059] Aspect 1 is a metallocene olefin polymerization catalyst and a compound of formula I:

Chemical formula

[0060] Aspect 2 provides the bimodal polymerization catalyst system of Aspect 1, wherein each of R 7 and R 8 is C1 alkyl.

[0061] Aspect 3 provides the bimodal polymerization catalyst system of Aspect 1, wherein each of R 5 and R 10 is a dialkyl- or trialkyl-substituted silyl.

[0062] Aspect 4 provides the bimodal polymerization catalyst system of any one of Aspects 1-3, wherein each R 2 and R 13 is 1,1-dimethylethyl.

[0063] Aspect 5 provides R 15 and R 16Provide any one of the bimodal polymerization catalyst systems of Aspects 1 to 4, each of which is 2,7 - di - t - butylcarbazol - 9 - yl.

[0064] The bimodal polymerization catalyst system of Aspect 6 of any one of Aspects 1 to 5, where L is a saturated C3 alkyl.

[0065] Aspect 7 provides any one of the bimodal polymerization catalyst systems of Aspects 1 to 6, where each X is a C1 alkyl.

[0066] Aspect 8 provides any one of the bimodal polymerization catalyst systems of Aspects 1 to 7, where M is Zr.

[0067] Aspect 9 provides any one of the bimodal polymerization catalyst systems of Aspects 1 to 8, where M is Hf.

[0068] Aspect 10 is such that the metallocene olefin polymerization catalyst is (Pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, (Methylcyclopentadienyl)(1,3 - dimethyl - tetrahydroindenyl)MX2, (Cyclopentadienyl)(1,3 - dimethyl - tetrahydroindenyl)MX2, (Cyclopentadienyl)(4,7 - dimethylindenyl)MX2, (Cyclopentadienyl)(1,5 - dimethylindenyl)MX2, (Cyclopentadienyl)(1,4 - dimethylindenyl)MX2, Me2Si(indenyl)2MX2, Me2Si(tetrahydroindenyl)2MX2, (n - propylcyclopentadienyl)2MX2, (n - butylcyclopentadienyl)2MX2, (1-Methyl, 3-butylcyclopentadienyl)2MX2, HN(CH2CH2N(2,4,6-Me3phenyl))2MX2, HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2, (Butylcyclopentadienyl)2MX2, (Propylcyclopentadienyl)2MX2, and mixtures thereof, produced from a metallocene pre-catalyst selected from the group consisting of, wherein M is Zr or Hf and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1-C5 alkyl or alkenyl, provides a bimodal polymerization catalyst system of any one of aspects 1-9.

[0069] Aspect 11 is a silica support, wherein the silica support further comprises a silica support supporting (a) a metallocene olefin polymerization catalyst not produced from a biphenylphenol polymerization pre-catalyst of formula I, (b) a biphenylphenol polymerization catalyst not produced from a metallocene olefin polymerization catalyst of formula I, or (c) a combination of a metallocene olefin polymerization catalyst and a biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization pre-catalyst of formula I (i.e., (c) is a supported bimodal polymerization catalyst system), providing a bimodal polymerization catalyst system of any one of aspects 1-10.

[0070] Aspect 12 is a method for producing a bimodal polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, wherein the high molecular weight and low molecular weight polyethylene components are produced together in a single gas phase reactor via a polymerization process using the bimodal polymerization catalyst system of Aspect 1, and the bimodal polyethylene composition has a value of weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) greater than 5.00, a value of z average molecular weight (Mz) to weight average molecular weight (Mw) ratio (Mz / Mw) less than Mw / Mn, or both Mw / Mn greater than 5.00 and Mz / Mw less than Mw / Mn.

[0071] Aspect 13 provides a method according to Aspect 12, further comprising forming a trim solution comprising at least a metallocene olefin polymerization catalyst, a biphenylphenol polymerization pre-catalyst of Formula I, or a biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of Formula I, and adding the trim solution to a single reactor to produce at least a portion of the bimodal polymerization catalyst system.

[0072] Aspect 14 provides a method for producing a bimodal polymerization catalyst system according to any one of Aspects 1 to 11, comprising producing a biphenylphenol polymerization catalyst by contacting a biphenylphenol polymerization pre-catalyst of Formula I with an activator under activation conditions.

[0073] Aspect 15 provides a method according to Aspect 14, wherein the activator is spray dried on a silica support, and the method comprises producing a biphenylphenol polymerization catalyst by contacting a biphenylphenol polymerization pre-catalyst of Formula I with the supported spray dried activator under activation conditions.

Examples

[0074] A bimodal polymerization catalyst system comprising a biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of Formula (I), and a comparative bimodal polymerization catalyst system comprising a comparative catalyst (excluding those produced from the bimodal polymerization pre-catalyst of Formula (I)) were prepared as follows.

[0075] The biphenylphenol polymerization pre-catalyst of formula (i) was prepared as follows. Inside a glove box, hafnium chloride [HfCl4] (12.07 g, 37.7 mmol, available from Strem Chemical), toluene (300 mL, available from Fisher Scientific), and a magnetic stir bar were placed into a 16-ounce oven-dried glass jar. The contents of the jar were cooled to a temperature of about -30 °C. Methylmagnesium bromide (56.6 mL of a 2.6 M solution in diethyl ether, 147 mmol, available from Millipore Sigma) was added and the solution was stirred at -30 °C for 15 minutes. The ligand of formula A (56.00 g, 35.9 mmol) was placed into the jar. The ligand of formula A was prepared as described in WO2017 / 058,981, the entire contents of which are incorporated herein by reference. The contents of the vial were stirred for 3 hours while gradually warming the solution to room temperature. The mixture was filtered and the solvent was removed from the filtrate in vacuo to obtain a gray powder (45 g, 71.0% yield). The presence of the biphenylphenol polymerization pre-catalyst of formula (i) was 1 confirmed by 1H NMR analysis. 1 1H NMR (400 MHz, benzene-d6) δ 8.19 (d, 2H), 8.01 (s, 2H), 7.99 (d, 2H), 7.89 (d, 2H), 7.74 (s, 2H), 7.64 (d, 2H), 7.55 (s, 2H), 7.51 (dd, 2H), 7.31 (dd, 2H), 7.06 (m, 2H), 3.68 (m, 2H), 3.42 (m, 2H), 1.79 (d, 2H), 1.67 (d, 2H), 1.60 (s, 18H), 1.47 (s, 6H), 1.42 (s, 6H), 1.35 (s, 6H), 1.33 - 1.25 (m, 26H), 1.25 (s, 18H), 0.93 (t, 6H), 0.92 (s, 18H), 0.59 (m, 4H), 0.10 (s, 6H), 0.07 (s, 6H), -0.82 (s, 6H).

Chemical formula

[0076] As used herein, "Me" refers to methyl, "n-Oct" refers to n-C8H 17 and "n-Pr" refers to n-C3H7.

[0077] The biphenylphenol polymerization pre-catalyst of formula (ii) was prepared using the same components and methodology as the biphenylphenol polymerization pre-catalyst of formula (i), except that zirconium tetrachloride [ZrCl4] (15.0 g, 64.1 mmol) was used instead of hafnium chloride (99.9 g, 92.9% yield). The presence of the biphenylphenol polymerization pre-catalyst of formula (ii) was 1 confirmed by 1H NMR analysis. 1 1H NMR (400 MHz, benzene-d6) δ 8.19 (d, 2H), 8.01 (s, 2H), 7.99 (d, 2H), 7.87 (d, 2H), 7.79 (d, 2H), 7.65 (d, 2H), 7.57 (d, 2H), 7.51 (dd, 2H), 7.30 (dd, 2H), 7.04 (m, 2H), 3.57 (m, 2H), 3.43 (m, 2H), 1.79 (d, 2H), 1.67 (d, 2H), 1.60 (s, 18H), 1.46 (s, 6H), 1.42 (s, 6H), 1.35 (s, 6H), 1.34 - 1.25 (m, 26H), 1.25 (s, 18H), 0.94 (t, 6H), 0.93 (s, 18H), 0.60 (m, 4H), 0.11 (s, 6H), 0.08 (s, 6H), -0.63 (s, 6H). [Chemical formula]

[0078] In various embodiments, a catalyst produced from the pre-catalyst of formula (i) and / or (ii) can be used in the bimodal polymerization catalyst system herein to produce a high molecular weight polyethylene component in a bimodal polyethylene composition.

[0079] The pre-polymerization catalyst of formula (iii) was prepared according to the method found in Huang, Rubin et al., Macromolecules (Washington, DC, USA), 41(3), 579-590, 2008, and the entire content of Huang, Rubin et al., Macromolecules is incorporated herein by reference.

Chemical formula

[0080] The comparative pre-polymerization catalyst of formula (iv) can be prepared according to the method found in PCT Int. Appl. WO2009 / 064404(A2).

[0081] In various embodiments, the metallocene olefin polymerization pre-catalyst of formula (iii) and / or formula (iv) can be used in the bimodal polymerization catalyst system herein to produce a low molecular weight polyethylene component in the bimodal polyethylene composition.

Chemical formula

[0082] The comparative pre-polymerization catalyst of formula (v) can be prepared according to the method found in PCT Int. Appl. WO2009 / 064404(A2). In various embodiments, the comparative pre-polymerization catalyst of formula (v) can be used in the bimodal polymerization catalyst system to produce a relatively high molecular weight polyethylene component in the comparative bimodal polyethylene composition.

Chemical formula

[0083] The pre-catalysts of formula (i) and (ii) were activated as follows to produce the activated biphenylphenol polymerization catalyst contained in the bimodal polymerization catalyst systems of Examples 1-4 (EX1-4).

[0084] Example 1 uses a bimodal polymerization catalyst system A (including the pre-catalyst of formula (ii) and the pre-catalyst of formula (iii)) prepared as follows.

[0085] The trim solution of the pre-catalyst of formula (ii) was prepared as follows. In a 1 L cylinder, 698 g of the solution of the pre-catalyst of formula (ii) was measured (1.00 weight percent in methylcyclohexane, 539 ppm Zr). The 1 L cylinder was connected to a 3785.41 cubic centimeter (cc) (28 gallon) cylinder and filled with approximately 8.60 kilograms (18.96 pounds) of purified isopentane to produce a final concentration of 0.075 weight percent. The cylinder was pressurized and purged three times with nitrogen. That is, in various embodiments, some or all of the catalyst system (e.g., metallocene and / or biphenylphenol polymerization pre-catalyst) is provided as a trim solution. For example, some of the metallocene catalyst may be provided as a trim solution. Alternatively, some of the biphenylphenol polymerization pre-catalyst may be provided as a trim solution.

[0086] The spray-dried formulation of the pre-catalyst of formula (iii) was prepared as described in WO2019 / 190897 to produce an activated and supported catalyst. The final spray-dried catalyst composition had a zirconium loading of 0.18 weight percent, an aluminum loading of 16.7 weight percent, and a residual toluene of 2.5 weight percent.

[0087] In Example 1, the bimodal polymerization catalyst system A was used at a trim catalyst concentration of 0.075 weight percent based on the total weight of the pre-catalyst of formula (ii), a spray-dried catalyst feed rate of 26.6 cc / hr, a trim catalyst feed rate of 24.9 cc / hr, an ethylene partial pressure of about 4.24 kilograms per square centimeter (60.3 pounds per square inch absolute (PSIA)), a C6 / C2 molar ratio of 0.0028, an H2 / C2 molar ratio of 0.0018, and an isopentane concentration of 12.3 mole percent, using the polymerization procedure described herein. Example 1 produced a bimodal polyethylene composition at a production rate of about 11.89 kilograms per hour (26.2 pounds per hour) and a productivity of the catalyst (2515 pounds of polymer / pound of catalyst) of about 2515 kilograms of polymer / kilogram.

[0088] Example 2 was prepared using the same method as the bimodal catalyst system A, but with a zirconium loading of 0.11 wt%, an aluminum loading of 16.9 wt%, and a residual toluene of 2.1 wt%, a spray-dried catalyst feed rate of 65.9 cc / hr, a trim catalyst feed rate of 21.2 cc / hr, an ethylene partial pressure of 61.1 PSIA, a C6 / C2 molar ratio of 0.0017, an H2 / C2 molar ratio of 0.0018, and an isopentane concentration of 12.5 mole percent, using a spray-dried blend of the pre-catalyst of formula (iii) for the bimodal polymerization catalyst system B (including the pre-catalyst of formula (ii) and the pre-catalyst of formula (iii)). Example 2 produced a bimodal polyethylene composition at a production rate of about 8.84 kilograms per hour (19.5 pounds per hour) and a productivity of the catalyst (6667 pounds of polymer / pound of catalyst) of about 6667 kilograms of polymer / kilogram.

[0089] Example 3 used a bimodal polymerization catalyst system C (including the pre-catalyst of formula (iii) and the spray-dried catalyst of the mixture of formula (ii) and formula (iii)) present in the ratios of Table 1 prepared as follows.

[0090] The trim solution of the pre-catalyst of formula (iii) was prepared using the same method as the trim solution of Example 1, but using the pre-catalyst of formula (iii) instead of the pre-catalyst of formula (ii) to produce a final concentration of 0.04 weight percent.

[0091] The spray-dried catalysts produced from the pre-catalyst of formula (iii) and the pre-catalyst of formula (ii) were formed as described in WO2019 / 190897 to produce activated spray-dried catalysts. In the formulation, the pre-catalyst of formula (ii) and the pre-catalyst of formula (iii) are present at a molar ratio of 0.7:20, respectively. The final spray-dried catalyst composition had a zirconium loading of 0.19 weight percent, an aluminum loading of 16.7 weight percent, and a residual toluene of 3.2 weight percent.

[0092] The bimodal polymerization catalyst system C was used as described herein at a trim catalyst concentration of 0.04 weight percent, a spray-dried catalyst feed rate of 38.0 cc / hour, a trim catalyst feed rate of 106.0 cc / hour, an ethylene partial pressure of 35.0 PSIA, a C6 / C2 molar ratio of 0.00097, an H2 / C2 molar ratio of 0.00174, and an isopentane concentration of 13.9 mole percent. Example 3 produced a bimodal polyethylene composition at a production rate of about 7.71 kilograms / hour (17.0 pounds / hour) and a productivity of the catalyst (1296 pounds of polymer / pound of catalyst) of about 1296 kilograms of polymer / kilogram.

[0093] Example 4 used a bimodal polymerization catalyst system D (comprising the pre-catalyst of formula (i) and the pre-catalyst of formula (iii)) prepared as follows.

[0094] The trim solution of the pre-catalyst of formula (i) was prepared as follows. In a 1L cylinder, 350 g of a solution of the pre-catalyst of formula (i) was measured (1.01 weight percent in methylcyclohexane, 1008 ppm Hf). The 1L cylinder was connected to a 3785.41 cc (28 gallon) cylinder and filled with approximately 8.39 kilograms (18.5 pounds) of purified isopentane to produce a final concentration of 0.04 weight percent. The cylinder was pressurized and purged three times with nitrogen.

[0095] The spray-dried formulation of the pre-catalyst of formula (iii) was prepared as described in WO2019 / 190897 to produce an activated catalyst. The final spray-dried catalyst composition had a zirconium loading of 0.18 wt%, an aluminum loading of 16.7 wt%, and a residual toluene of 2.5 wt%.

[0096] The bimodal polymerization catalyst system D was used with a trim catalyst concentration of 0.04 weight percent, a spray-dried catalyst feed rate of 24.0 cc / hour, a trim catalyst feed rate of 30.8 cc / hour, an ethylene partial pressure of 100.1 PSIA, a C6 / C2 molar ratio of 0, an H2 / C2 molar ratio of 0.0022, and an isopentane concentration of 9.1 mole percent using the polymerization procedure described herein. Example 4 produced a bimodal polyethylene composition with a production rate of about 12.25 kilograms / hour (27.0 pounds / hour) and a productivity of about 2911 kilograms of polymer / kilogram of catalyst (2911 pounds of polymer / pound of catalyst).

[0097] Comparative Example 1 used a comparative bimodal polymerization catalyst system E (including a catalyst produced from the pre-catalysts of formula (iv) and formula (v)) prepared as follows. The supported formulations of the pre-catalyst of formula (iv) and the pre-catalyst of formula (v) can be prepared according to the method found in PCT Int. Appl. WO2009 / 064404 (A2). The bimodal polymerization catalyst system E was used using the method found in PCT Int. Appl. WO2009 / 064404 (A2).

[0098] Ethylene / 1-hexene copolymerization was carried out for each of Examples 1 to 4 using gas-phase fluidized bed copolymerization of ethylene and 1-hexene to produce an ethylene / 1-hexene copolymer. The gas-phase fluidized bed reactor used was a gas-phase fluidized bed reactor having an inner diameter of 0.35 m and a bed height of 2.3 m, and a fluidized bed composed of polymer granules. The fluidizing gas passed through the bed at a velocity of about 1.7 - 2.1 feet / second. The fluidizing gas exited the top of the reactor, passed through a recycle gas compressor and a heat exchanger, and then re-entered the reactor under the distribution grid. A constant fluidized bed temperature was maintained by continuously adjusting the temperature of the water on the shell side of the multitubular heat exchanger. The gaseous feed streams of ethylene, nitrogen, and hydrogen were introduced into the recycle gas line together with the 1-hexene comonomer. The reactor was operated at an overall pressure of about 2413 kilopascals (kPa) gauge and vented to a flare to control the overall pressure. The individual flow rates of ethylene, nitrogen, hydrogen, and 1-hexene were adjusted to maintain the gas composition target. The ethylene partial pressure, C6 / C2 molar ratio, H2 / C2 molar ratio, and isopentane concentration were set to the values in the examples, respectively. The concentration of all gases was measured using an on-line gas chromatograph. The fluidized bed was maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of formation of the particulate product. The slurry catalyst (spray-dried pre-catalyst / catalyst specified in Table 1) was fed to the catalyst injection pipe where it was contacted in-line with the trim solution (trim pre-catalyst / catalyst specified in Table 1), and then isopentane and nitrogen carrier were sprayed into the fluidized bed. The feed rate of the slurry catalyst was adjusted to maintain the desired production rate, and the feed rate of the trim solution was adjusted to obtain the desired final resin flow index in the resulting bimodal polymer. The product was withdrawn semi-continuously into a fixed-volume chamber via a series of valves. A significant portion of the hydrocarbon taken up and dissolved in the fixed-volume chamber was removed by nitrogen purge. After purging, the product was discharged from the fixed-volume chamber into a fiber pack for collection. The product was further treated with a small flow of humid nitrogen to deactivate trace amounts of residual catalyst and cocatalyst.

[0099] The results of EX1 - 4 and CE1 are shown in Tables 1 and 2 and described herein.

[0100] The number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz) were determined by gel permeation chromatography (GPC) as is known in the art.

[0101] Productivity (kilograms of polymer / kilogram of catalyst) was determined as the ratio of the polymer produced to the amount of catalyst and activator added to the reactor. [Table 1] [Table 2]

[0102] As detailed in Tables 1 and 2, EX1-4 provide a bimodal polymerization catalyst system and a bimodal polymer having suitable properties. For example, the bimodal polymerization catalyst system of the present disclosure provides a bimodal polymer having a high molecular weight component having an improved (i.e., lower) molecular weight than the high molecular weight component of a bimodal polymer produced from a comparative catalyst under similar conditions, as evidenced by a polymer having an improved Mz to Mw ratio (i.e., a value of Mw to Mn ratio greater than 5.00 and a value of Mz to Mw ratio smaller than the value of Mw / Mn ratio). That is, the biphenylphenol polymerization pre-catalyst of formula I (such as the pre-catalyst of formula (i) and / or (ii)) can be used in a bimodal polymerization catalyst system that leads to the production of a desired high molecular weight component having an improved (i.e., lower) molecular weight than a bimodal polymer produced from a comparative catalyst under similar conditions. Without wishing to be bound by theory, it has been suggested that a high molecular weight component with a value of Mw less than 700,000 may improve the resin properties for certain applications. In particular, the improved Mw can be achieved both when the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of formula I is used as a trim catalyst (EX1, EX2, EX4) in a bimodal catalyst system, and when the catalyst produced from the biphenylphenol polymerization pre-catalyst of formula I is used as a spray-dried catalyst (EX3) in a bimodal catalyst system. The present specification includes the following aspects. Item 1. A metallocene olefin polymerization catalyst, and Formula I: [Chemical formula] (wherein each of R 7 and R 8 is independently C1-C 20 alkyl, aryl or aralkyl, halogen, or hydrogen, wherein each of R 5 and R 10 is independently C1-C 20is alkyl, aryl, aralkyl, halogen, alkyl- or aryl-substituted silyl, or hydrogen, wherein R 2 and R 13 each independently is C1-C 20 alkyl, aryl or aralkyl, or hydrogen, wherein R 15 and R 16 each independently is 2,7-disubstituted carbazol-9-yl, wherein L is saturated C2-C3 alkyl, forming a 2-carbon or 3-carbon bridge between the two oxygen atoms to which L is attached, wherein each X independently is halogen, hydrogen, (C1-C 20 )alkyl, (C7-C 20 )aralkyl, (C1-C6)alkyl-substituted (C6-C 12 )aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R C )3, R C is C1-C 12 hydrocarbon, wherein R 1 , R 3 , R 4 , R 6 , R 9 , R 11 , R 12 , and R 14 each independently is hydrogen, wherein M is a heteroatom selected from the group consisting of Zr and Hf) a biphenylphenol polymerization catalyst prepared from a biphenylphenol polymerization pre-catalyst, and a bimodal polymerization catalyst system comprising the same. Item 2. R 7 and R 8 each being C1 alkyl, the bimodal polymerization catalyst system according to Item 1. Item 3. R 5 and R 10 each being dialkyl- or trialkyl-substituted silyl, the bimodal polymerization catalyst system according to Item 1 or 2. Item 4. each R2 and R 13 The bimodal polymerization catalyst system according to any one of items 1 to 3, wherein R is 1,1,3,3 - tetramethylbutyl. Item 5. R 15 and R 16 The bimodal polymerization catalyst system according to any one of items 1 to 4, wherein each of R and R is 2,7 - di - t - butylcarbazol - 9 - yl. Item 6. The bimodal polymerization catalyst system according to any one of items 1 to 5, wherein L is a saturated C3 alkyl. Item 7. The bimodal polymerization catalyst system according to any one of items 1 to 6, wherein each X is a C1 alkyl. Item 8. The bimodal polymerization catalyst system according to any one of items 1 to 7, wherein M is Zr. Item 9. The bimodal polymerization catalyst system according to any one of items 1 to 7, wherein M is Hf. Item 10. The metallocene olefin polymerization catalyst is (Pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, (Methylcyclopentadienyl)(1,3 - dimethyl - tetrahydroindenyl)MX2, (Cyclopentadienyl)(1,3 - dimethyl - tetrahydroindenyl)MX2, (Cyclopentadienyl)(4,7 - dimethylindenyl)MX2, (Cyclopentadienyl)(1,5 - dimethylindenyl)MX2, (Cyclopentadienyl)(1,4 - dimethylindenyl)MX2, Me2Si(indenyl)2MX2, Me2Si(tetrahydroindenyl)2MX2, (n-Propylcyclopentadienyl)2MX2, (n-Butylcyclopentadienyl)2MX2, (1-Methyl,3-butylcyclopentadienyl)2MX2, HN(CH2CH2N(2,4,6-Me3phenyl))2MX2, HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2, (Butylcyclopentadienyl)2MX2, (Propylcyclopentadienyl)2MX2, and mixtures thereof, produced from a metallocene pre-catalyst selected from the group consisting of, wherein M is Zr or Hf and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1-C5 alkyl or alkenyl, the bimodal polymerization catalyst system according to any one of items 1-9. Item 11. A silica support, wherein the silica support further comprises a silica support supporting (a) the metallocene olefin polymerization catalyst, which is not the biphenylphenol polymerization pre-catalyst of formula I, (b) the biphenylphenol polymerization catalyst, which is not the metallocene olefin polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of formula I, or (c) a combination of the metallocene olefin polymerization catalyst and the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of formula I, the bimodal polymerization catalyst system according to any one of items 1-10. Item 12. A method for producing a bimodal polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, wherein the high molecular weight and low molecular weight polyethylene components are produced together in a single gas phase reactor via a polymerization process using the bimodal polymerization catalyst system described in item 1, and the bimodal polyethylene composition has a value of weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) greater than 5.00, a value of z average molecular weight (Mz) to weight average molecular weight (Mw) ratio (Mz / Mw) smaller than the Mw / Mn, or both the Mw / Mn greater than 5.00 and the Mz / Mw smaller than the Mw / Mn. Item 13. Forming a trim solution comprising at least the metallocene olefin polymerization catalyst, the biphenylphenol polymerization pre-catalyst of formula I, or the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of formula I; Adding the trim solution to a single reactor to produce at least a portion of the bimodal polymerization catalyst system, the method according to item 12. Item 14. A method for producing the bimodal polymerization catalyst system according to any one of items 1 to 11, comprising producing the biphenylphenol polymerization catalyst by contacting the biphenylphenol polymerization pre-catalyst of formula I with an activator under activation conditions. Item 15. The activator is spray-dried on a silica support, and the method comprises producing the biphenylphenol polymerization catalyst by contacting the biphenylphenol polymerization pre-catalyst of formula I with the supported spray-dried activator under activation conditions, the method according to item 14.

Claims

1. A metallocene olefin polymerization catalyst and, Formula I: 【Chemical 1】 (wherein, R ７ and R ８ each independently is C １ - C ２０ alkyl, aryl or aralkyl, halogen, or hydrogen of, wherein, R ５ and R １０ each independently is C １ to C ２０ alkyl, aryl, aralkyl, halogen, alkyl- or aryl-substituted silyl, or hydrogen, In the formula, R ２ and R １３ each independently represents C １ to C ２０ alkyl, aryl or aralkyl, or hydrogen, wherein R １５ and R １６ each independently represents 2,7-disubstituted carbazol-9-yl, In the formula, L is a saturated C ２ ~C ３ alkyl, and a 2-carbon bridge or a 3-carbon bridge is formed between two oxygen atoms to which L is bonded. In the formula, each X independently represents a halogen, hydrogen, (C １ ~C ２０ ), alkyl, (C ７ ~C ２０ ), aralkyl, (C １ ~C ６ ), alkyl-substituted (C ６ ~C １２ ), aryl, or (C １ ~C ６ ), alkyl-substituted benzyl, -CH ２ Si(R Ｃ ), where R ３ is a C Ｃ ~C １ ~C １２ hydrocarbon, In the formula, R １ , R ３ , R ４ , R ６ , R ９ , R １１ , R １２ , and R １４ each independently is hydrogen, In the formula, M is a heteroatom selected from the group consisting of Zr and Hf) a biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization pre-catalyst, a bimodal polymerization catalyst system comprising.

2. R ７ and R ８ each of which is C １ alkyl, the bimodal polymerization catalyst system according to claim 1.

3. R ５ The bimodal polymerization catalyst system according to claim 1 or 2, wherein each of R and R10 is a dialkyl- or trialkyl-substituted silyl.

4. Each R ２ and R １３ is 1,1,3,3 - tetramethylbutyl, the bimodal polymerization catalyst system according to any one of claims 1 to 3.

5. R １５ and R １６ each of which is 2,7-di-t-butylcarbazol-9-yl, the bimodal polymerization catalyst system according to any one of claims 1 to 4.

6. L is saturated C ３ The bimodal polymerization catalyst system according to any one of claims 1 to 5, wherein L is alkyl.

7. Each X is C １ The bimodal polymerization catalyst system according to any one of claims 1 to 6, wherein each X is alkyl.

8. The bimodal polymerization catalyst system according to any one of claims 1 to 7, wherein M is Zr.

9. The bimodal polymerization catalyst system according to any one of claims 1 to 7, wherein M is Hf.

10. The metallocene olefin polymerization catalyst is (Pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX ２ , (Tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX ２ , (Tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX ２ , (Methylcyclopentadienyl)(1,3-dimethyl-tetrahydroindenyl)MX ２ , (Cyclopentadienyl)(1,3-dimethyl-tetrahydroindenyl)MX ２ , (Cyclopentadienyl)(4,7-dimethylindenyl)MX ２ , (Cyclopentadienyl)(1,5-dimethylindenyl)MX ２ , (Cyclopentadienyl)(1,4-dimethylindenyl)MX ２ , Me ２ Si(indenyl) ２ MX ２ , Me ２ Si(Tetrahydroindenyl) ２ MX ２ , (n-Propylcyclopentadienyl) ２ MX ２ , (n-Butylcyclopentadienyl) ２ MX ２ , (1-Methyl, 3-butylcyclopentadienyl) ２ MX ２ , (Butylcyclopentadienyl) ２ MX ２ , (propylcyclopentadienyl) ２ MX ２ and mixtures thereof, produced from a metallocene pre-catalyst selected from the group consisting of: In the formula, M is Zr or Hf, and X is F, Cl, Br, I, Me, benzyl, CH ２ SiMe ３ , and C １ ~C ５ The bimodal polymerization catalyst system according to any one of claims 1 to 9, selected from alkyl or alkenyl of

11. (a) the metallocene olefin polymerization catalyst, (b) the biphenylphenol polymerization catalyst, or (c) a combination of the metallocene olefin polymerization catalyst and the biphenylphenol polymerization catalyst, further comprising a silica support for supporting, the bimodal polymerization catalyst system according to any one of claims 1 to 10.

12. A method for producing a bimodal polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, wherein the high molecular weight and low molecular weight polyethylene components are produced together in a single gas phase reactor via a polymerization process using the bimodal polymerization catalyst system according to claim 1, the bimodal polyethylene composition having a value of weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) greater than 5.00, a value of z average molecular weight (Mz) to weight average molecular weight (Mw) ratio (Mz / Mw) for a weight average molecular weight (Mw) ratio smaller than the Mw / Mn, or both the Mw / Mn greater than 5.00 and the Mz / Mw smaller than the Mw / Mn.

13. Forming a trim solution comprising at least the metallocene olefin polymerization catalyst, the biphenylphenol polymerization pre-catalyst of Formula I, or the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of Formula I; Adding the trim solution to a single reactor to produce at least a portion of the bimodal polymerization catalyst system, further comprising the method according to claim 12.

14. A method for producing the bimodal polymerization catalyst system according to any one of claims 1 to 11, comprising producing the biphenylphenol polymerization catalyst by contacting the biphenylphenol polymerization precatalyst of formula I with an activator under activation conditions.

15. The method according to claim 14, wherein the activator is spray-dried on a silica support, and the method comprises producing the biphenylphenol polymerization catalyst by contacting the biphenylphenol polymerization precatalyst of formula I with the supported spray-dried activator under activation conditions.

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