Biphenylphenol polymerization catalyst

Abstract

An embodiment relates to the use of a supported biphenylphenol polymerization catalyst made from a biphenylphenol polymerization pre-catalyst of Formula I via a gas phase or slurry phase polymerization process under gas phase or slurry phase polymerization conditions to make a polymer.

Description

[Technical Field]

[0001] Embodiments of the present disclosure relate to biphenylphenol polymerization catalysts, and more specifically, to supported biphenylphenol polymerization catalysts that can be used to make polymers via a polymerization process in a single gas phase or slurry phase polymerization reactor. [Background technology]

[0002] Polymers can be used in many products such as films, fibers, nonwoven and / or woven fabrics, extruded articles, and / or molded articles, among others. Polymers can be made by reacting one or more 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] 1. Use of a supported biphenylphenol polymerization catalyst to make a polymer via a gas phase polymerization process or a slurry phase polymerization process, wherein the supported biphenylphenol polymerization catalyst is made from a biphenylphenol polymerization pre-catalyst of Formula I: [ka] In the formula, R 7 and R 8 each is independently C alkyl, halogen, or hydrogen; R 5 and R 10 Each of C1 to C 20 alkyl, aryl, aralkyl, halogen, or hydrogen; R 4 and R 11 each is independently halogen or hydrogen; R 2 and R 13 Each of C1 to C 20 alkyl, aryl, or aralkyl, or hydrogen; R 15 and R 16 each is independently 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted carbazol-9-yl; L is a C3 or C4 alkylene that forms a three-carbon or four-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; R 1 , R 3 , R 12 , and R 14 each is hydrogen; R 6 and R 9 each is hydrogen or C1-C8 alkyl, and optionally, R 6 is R 7 and R 8 is R 9 can be linked to form a cyclic structure, Each X is independently selected from 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 R C is C1~C 12 is a hydrocarbon, M is Zr or Hf.

[0005] A method of making a supported biphenylphenol polymerization catalyst, the method comprising: disposing a biphenylphenol polymerization pre-catalyst of Formula I on a support to obtain a supported biphenylphenol polymerization pre-catalyst; and contacting the supported biphenylphenol polymerization pre-catalyst of Formula I with an activator under activating conditions to activate the supported biphenylphenol polymerization pre-catalyst of Formula I, thereby making the supported biphenylphenol polymerization catalyst.

[0006] A process for making a polyethylene composition, the process comprising polymerizing ethylene in the presence of a supported biphenylphenol polymerization catalyst in each single gas phase polymerization reactor under gas phase polymerization conditions to make a polyethylene composition without the aid of any other polymerization catalyst.

[0007] A method for making a polyethylene composition, the method comprising polymerizing ethylene in the presence of a supported biphenylphenol polymerization catalyst in a single slurry phase polymerization reactor under slurry phase polymerization conditions to make the polyethylene composition without the aid of any other polymerization catalyst.

[0008] A biphenylphenol polymerization pre-catalyst selected from the group consisting of structures (i), (ii), (iii), (viii), and (v) as detailed herein. DETAILED DESCRIPTION OF THE INVENTION

[0009] The biphenylphenol polymerization pre-catalyst herein can be represented by Formula I: [ka]

[0010] In the formula, R 7 and R 8 each is independently C alkyl, halogen, or hydrogen;

[0011] R 5 and R 10 Each of C1 to C 20 alkyl, aryl, aralkyl, halogen, or hydrogen;

[0012] R 4 and R 11 each is independently halogen or hydrogen;

[0013] R 2 and R 13 Each of C1 to C20 alkyl, aryl, or aralkyl, or hydrogen;

[0014] R 15 and R 16 each is independently 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted carbazol-9-yl;

[0015] L is a C3 or C4 alkylene that forms a three-carbon or four-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded;

[0016] R 1 , R 3 , R 12 , and R 14 each is hydrogen;

[0017] R 6 and R 9 each is hydrogen or C1-C8 alkyl, and optionally, R 6 is R 7 and R 8 is R 9 can be linked to form a cyclic structure,

[0018] Each X is independently selected from halogen, hydrogen, (C1-C 20 ) Alkyl, (C7-C 20 ) aralkyl, (C1-C6) alkyl substituted (C 6~C12) Aryl or (C1-C6) alkyl substituted benzyl, -CH2Si(R C )3 and R C is C1~C 12 is a hydrocarbon,

[0019] M is Zr or Hf.

[0020] In various embodiments, the polymerization catalyst of Formula I can be used to produce a polymer composition without the aid of any other polymerization catalyst. As used herein, "without the aid of any other polymerization catalyst" refers to the presence of less than 1 weight percent of another polymerization catalyst, or zero weight percent of another polymerization catalyst, based on the total weight of the components in the catalyst system employed to make a polymer, such as a bimodal polymer as detailed herein. As used herein, the term "other" or "separate" polymerization catalyst refers to any catalyst typically employed to produce a polymer that is not the polymerization catalyst of Formula I. As used herein, "polymerization catalyst" can include any compound capable of catalyzing the polymerization or oligomerization of olefins when activated, wherein the catalyst compound contains at least one Group 3-12 atom and, optionally, at least one leaving group attached thereto. Examples of such "other" / "alternative" polymerization catalysts include, other than the biphenylphenol polymerization pre-catalyst of Formula I or an activated product of the biphenylphenol polymerization pre-catalyst of Formula I, Ziegler-Natta catalysts, chromium-based catalysts (e.g., so-called Phillips catalysts), metallocene catalysts with or without indenyl rings (e.g., metallocene catalysts containing unsubstituted and / or alkyl-substituted cyclopentadienyl rings), Group 15 metal-containing catalyst compounds described in paragraphs

[0041] to

[0046] of WO2018 / 064038A1, or biphenylphenol-based catalyst compounds described in paragraphs

[0036] to

[0080] of US20180002464A1.

[0021] The biphenylphenol polymerization pre-catalyst of Formula I (i.e., biphenylphenol polymerization pre-catalyst) can be used to prepare a biphenylphenol polymerization catalyst. For example, the biphenylphenol polymerization pre-catalyst can be contacted with an activator under activating conditions to activate the biphenylphenol polymerization pre-catalyst, thereby preparing a polymerization catalyst. Embodiments provide methods for preparing supported biphenylphenol polymerization catalysts, as detailed herein. The supported biphenylphenol polymerization catalysts herein prepared solely from biphenylphenol polymerization pre-catalysts are useful for preparing polyolefin polymers characterized by a multimodal distribution, such as a bimodal molecular weight distribution.

[0022] As previously mentioned, R as shown in Formula I 7 and R 8 Each of R may independently be C alkyl, halogen, or hydrogen. 7 is fluorine and R 8 is C alkyl, e.g., methyl. One or more embodiments provide 7 and R 8 is C alkyl, e.g., methyl. One or more embodiments provide 7 and R 8 is hydrogen. One or more embodiments may be 7 and R 8 is a halogen such as fluorine.

[0023] As used herein, "alkyl" includes linear, branched, and cyclic paraffinic groups deficient by one hydrogen. Alkyl typically includes branched or unbranched saturated hydrocarbon groups, although they need not necessarily contain from 1 to about 50 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, and cycloalkyls such as cyclopentyl and cyclohexyl. Generally, although again not necessarily, alkyl herein can contain from 1 to about 12 carbon atoms. Thus, for example, the group CH ("methyl") and the group CHCH ("ethyl") are examples of alkyl.

[0024] As previously mentioned, R as shown in Formula I 5 and R 10 Each of R can independently be alkyl, aryl, aralkyl, halogen, or hydrogen. For example, one or more embodiments may include R 5 and R 10 is a halogen, such as fluorine. 5 and R 10 is hydrogen. One or more embodiments may be 5 and R 10 is hydrogen or R 5 and R 10 is fluorine.

[0025] As used herein, "aryl" includes phenyl, naphthyl, pyridyl, and other radicals whose molecules have ring structures characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. "Aryl" refers to any radical having a C6-C 20 It is understood that the aromatic group can be an aryl. For example, a C6H5-aromatic structure is "phenyl" and a -C6H4-aromatic structure is "phenylene." As used herein, an "aralkyl," which may also be called an "arylalkyl," is an alkyl having an aryl pendant therefrom. An "aralkyl" is an alkyl having a C7-C 20It is understood that it may be aralkyl. An "alkylaryl" is an aryl having one or more alkyl groups pending therefrom. As used herein, "hydrocarbyl" includes aliphatic, cyclic, olefinic, acetylenic, and aromatic radicals (i.e., hydrocarbon radicals) containing hydrogen and carbon deficient by one hydrogen.

[0026] As previously mentioned, R as shown in Formula I 4 and R 11 Each of R can independently be hydrogen or a halogen atom such as fluorine. For example, one or more embodiments may include R 5 and R 10 is hydrogen. One or more embodiments may be 4 and R 11 is fluorine. 4 and R 11 is hydrogen or R 4 and R 11 is fluorine.

[0027] As previously mentioned, R as shown in Formula I 2 and R 13 Each of C1 to C 20 It can be alkyl, aryl, or aralkyl, or hydrogen. For example, one or more embodiments may include R 2 and R 13 is C alkyl. One or more embodiments provide 2 and R 13 is a C4 alkyl, such as n-butyl, t-butyl, or 2-methyl-pentyl. As noted above, in various embodiments, R 1 , R 3 , R 12 , and R 14 Each of is hydrogen.

[0028] As previously mentioned, R as shown in Formula I 15 and R 16may independently be a 2,7-disubstituted carbazol-9-yl or a 3,6-disubstituted carbazol-9-yl. For example, one or more embodiments may include 15 and R 16 is a 2,7-disubstituted carbazol-9-yl selected from the group consisting of 2,7-di-t-butylcarbazol-9-yl, 2,7-di-ethylcarbazol-9-yl, 2,7-di-methylcarbazol-9-yl, and 2,7-di-n-octyl-di-isopropyl-silylcarbazol-9-yl. For example, the 2,7-disubstituted carbazol-9-yl may be selected from the group consisting of biphenylphenol polymerization pre-catalysts of structures (i), (ii), (iii), and (viii) as detailed herein. In some embodiments, R 15 and R 16 is a 2,7-disubstituted carbazol-9-yl selected from the group consisting of 2,7-di-t-butylcarbazol-9-yl, 2,7-di-ethylcarbazol-9-yl, and 2,7-di-methylcarbazol-9-yl. 15 and R 16 is a 3,6-disubstituted carbazol-9-yl, such as 3,6-di-t-butylcarbazol-9-yl.

[0029] As previously mentioned, L as shown in Formula I can be a C3 or C4 alkylene that forms a three-carbon or four-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded. For example, one or more embodiments provide that L is a C3 alkylene. One or more embodiments provide that L is a C4 alkylene.

[0030] As previously mentioned, each X as shown in Formula I is independently selected from 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 RC is C1~C 12 For example, one or more embodiments provide that each X is independently C alkyl. One or more embodiments provide that each X is hydrogen.

[0031] As previously mentioned, M as shown in Formula I can be zirconium (Zr) or hafnium (Hf). In various embodiments, M can be selected from the group consisting of zirconium and hafnium. One or more embodiments provide that M is zirconium. One or more embodiments provide that M is hafnium.

[0032] One or more embodiments may comprise R 7 and R 8 is C1 alkyl, fluorine, or hydrogen, and R 5 , R 6 , R 9 , and R 10 One or more embodiments provide that at least two of R 7 and R 8 is C1 alkyl, fluorine, or hydrogen, and R 5 , R 6 , R 9 , and R 10 One or more embodiments may be provided where two of R 7 and R 8 is C1 alkyl, fluorine, or hydrogen, and R 5 , R 6 , R 9 , and R 10 is fluorine.

[0033] As described herein, the R group (R 1 ~R 16 Each of X and X can be independently substituted or unsubstituted. For example, in some embodiments, each of X in formula I can be independently selected from halogen, hydrogen, (C1-C 20 ) Alkyl, (C7-C 20 ) aralkyl, (C1-C6) alkyl substituted (C6-C12 )aryl, or (C1-C6) alkyl-substituted benzyl, -CH2Si(R C )3, and R C is C1~C 12 As used herein, "substituted" indicates that the group following the term possesses at least one moiety in place of one or more hydrogens at any position, and the moiety may be a halogen radical, a hydroxyl group, a carbonyl group, a carboxyl group, an amine group, a phosphine group, an alkoxy group, a phenyl group, a naphthyl group, a C1-C6 20 Alkyl, C2-C 10 "Disubstituted" refers to the presence of two or more substituents at any position, and the moiety may be selected from halogen radicals, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1-C6 alkyl groups, and combinations thereof. 20 Alkyl, C2-C 10 alkenyl groups, and combinations thereof.

[0034] The biphenylphenol polymerization precatalyst may be made using the reactants described herein.

[0035] One or more embodiments provide a biphenylphenol polymerization catalyst, i.e., a supported biphenylphenol polymerization catalyst. The supported biphenylphenol polymerization catalyst can be made by contacting a biphenylphenol polymerization precatalyst and an activator under activating conditions to provide an activated biphenylphenol polymerization catalyst, e.g., an activated biphenylphenol polymerization precatalyst. Activation conditions are well known in the art.

[0036] As used herein, "activator" refers to any compound or combination of compounds, supported or unsupported, that can activate a complex or catalyst component, e.g., by generating a cationic species of the catalyst component. For example, this can involve abstraction of at least one leaving group, e.g., an "X" group as 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 can be bound to a metal atom and abstracted by an activator, thus generating a species active for olefin polymerization.

[0037] Activators can include Lewis acids or non-coordinating ionic activators or ionizing activators, or any other compounds, including Lewis bases, aluminum alkyls, and / or conventional cocatalysts. In addition to the methylaluminoxane ("MAO") and modified methylaluminoxane ("MMAO") mentioned above, exemplary activators include, but are not limited to, aluminoxanes or modified aluminoxanes, and / or ionizing compounds, 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(perfluoronaphthalene)borate, dimethylanilinium tetrakis(pentafluorophenyl ... triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, dimethylanilinium tetrakis(pentafluoronaphthyl)aluminate, triphenylcarbenium tetrakis(pentafluoronaphthyl)aluminate, dimethylanilinium tetrakis(perfluoronaphthyl)aluminate, triphenylcarbenium tetrakis(perfluoronaphthyl)aluminate, tris(perfluorophenyl)boron, tris(perfluoronaphthyl)boron, tris(perfluorophenyl)aluminum, tris(perfluoronaphthyl)aluminum, or any combination thereof.

[0038] Aluminoxanes can be described as oligomeric aluminum compounds having -A(R)-O- subunits (where R is an alkyl group). Examples of aluminoxanes include, but are not limited to, methylaluminoxane ("MAO"), modified methylaluminoxane ("MMAO"), ethylaluminoxane, isobutylaluminoxane, or combinations thereof. Aluminoxanes can be produced by hydrolysis of the respective trialkylaluminum compounds. MMAO can be produced by hydrolysis of trimethylaluminum and higher trialkylaluminums, such as triisobutylaluminum. There are various known methods for preparing aluminoxanes and modified aluminoxanes. Aluminoxanes can include modified methylaluminoxane ("MMAO") Type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane Type 3A, discussed in U.S. Pat. No. 5,041,584). The MAO source can be, for example, a solution having about 1% to about 50% by weight of MAO. Commercially available MAO solutions include 10% and 30% by weight MAO solutions available from Albemarle Corporation of Baton Rouge, La.

[0039] One or more organoaluminum compounds, such as one or more alkylaluminum compounds, can be used in combination with the 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.

[0040] The supported biphenylphenol polymerization catalyst made from the biphenylphenol polymerization pre-catalyst can be used to make a polymer. For example, the supported biphenylphenol polymerization catalyst and an olefin can be contacted under polymerization conditions to make a polymer, e.g., a polyolefin polymer.

[0041] As used herein, a "polymer" has two or more of the same or different polymer units derived from one or more different monomers, e.g., homopolymers, copolymers, terpolymers, etc. A "homopolymer" is a polymer having the same polymer units. A "copolymer" is a polymer having two or more polymer units that are different from one another. A "terpolymer" is a polymer having three polymer units that are different from one another. When referring to polymer units, "different" indicates that the polymer units differ from one another by at least one atom or are isomerically different. Thus, the definition of a copolymer as used herein includes terpolymers, etc. As used herein, a "polymerization process" is a process used to make a polymer. For example, the polymerization process can be a gas-phase or slurry-phase polymerization process. In some embodiments, the polymerization process comprises a gas-phase polymerization process. In some embodiments, the polymerization process comprises a slurry-phase polymerization process.

[0042] The embodiment provides that the polymer may be a polyolefin polymer. As used herein, "olefin," which may be referred to as "alkene," refers to a linear, 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 comprise (e.g., be made from) an olefin, the olefin present in such a polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 75% to 85% by weight, it is understood that the polymer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present in an amount of 75% to 85% by weight, based on the total weight of the polymer. Higher α-olefin refers to an α-olefin having three or more carbon atoms.

[0043] 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 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 may include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrenes, ethylidene norbornene, dicyclopentadiene, and cyclopentene. In some embodiments, copolymers of ethylene may be produced, in which case 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, is polymerized, for example, in a gas-phase / slurry-phase polymerization process. In another embodiment, ethylene and / or propylene may be polymerized with at least two different comonomers (optionally, one of which may be a diene) to produce a terpolymer. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and the description includes both cases where the event or circumstance occurs.

[0044] One or more embodiments provide that the polymer can comprise 50 to 95 weight percent ethylene-derived units, based on the total weight of the polymer. All individual values ​​and subranges from 50 to 95 weight percent are included, for example, the polymer can comprise from a lower limit of 50, 60, or 70 weight percent ethylene-derived units to an upper limit of 95, 90, or 85 weight percent ethylene-derived units, based on the total weight of the polymer. The polymer can comprise 5 to 50 weight percent comonomer-derived units, based on the total weight of the polymer.

[0045] As described above, surprisingly, a supported biphenylphenol polymerization catalyst prepared from a biphenylphenol polymerization precatalyst can assist in providing a polymer through a polymerization process in a single gas-phase or slurry-phase (not liquid-phase) polymerization reactor without the aid of any other polymerization catalyst. For example, the resulting polymer can have an improved, i.e., higher, polydispersity index (PDI), as detailed herein, compared to polymers prepared with other (non-invention) polymerization catalysts under similar polymerization conditions. In some applications, an increased PDI is desirable. Similarly, the resulting polymer can have at least a high-molecular-weight polyethylene component and a low-molecular-weight polyethylene component, as detailed herein. Having a high-molecular-weight polyethylene component and a low-molecular-weight polyethylene component is desirable in some applications.

[0046] Embodiments provide that the polymer may have an Mn (number average molecular weight) of 3,000 to 105,000. All individual values ​​and subranges from 3,000 to 105,000 are included, for example, the polymer may have an Mn of 3,000, 4,000, 5,000, 6,000, 7,000, 7,500, 8,000, or 8,500, or an Mn of 105,000, 103,000, 75,000, 65,000, 55,000, 45,000, 35,000, 25,000, 24,000, 23,000, or 22,000. Mn is known in the art and can be determined by gel permeation chromatography (GPC), as described below. For example, in some embodiments, polymers made via homogeneous polymerization may have an Mn of 5,000 to 80,000. In some embodiments, polymers produced using a gas phase polymerization reactor may have an Mn of 4,000 to 103,000.

[0047] Embodiments provide that the polymer may have a Mw (weight average molecular weight) of 25,000 to 1,600,000. All individual values ​​and subranges from 25,000 to 1,600,000 are included, for example, the polymer may have a Mw from lower limits of 25,000, 60,000, 80,000, or 100,000, 120,000, 145,000, 160,000, or 200,000 to upper limits of 1,600,000, 1,500,000, 1,110,000, 500,000, 400,000, or 300,000. Mw can be determined by GPC, as described below. For example, in some embodiments, polymers produced using a gas-phase polymerization reactor may have a Mw of 160,000 to 1,500,000. In some embodiments, polymers made using a gas phase polymerization reactor may have a Mw of 25,000 to 400,000.

[0048] Embodiments provide that the polymer may have a polydispersity index (PDI) (determined as Mw / Mn) of 3.00 to 40.00. All individual values ​​and subranges between 3.00 and 40.00 are included. For example, the polymer may have an Mw / Mn ranging from lower limits of 3.00, 3.50, 4.00, 4.50, or 5.00 to upper limits of 40.00, 36.00, 18.00, 15.00, 8.00, 7.50, 7.00, or 6.50. Mw / Mn can be determined by GPC analysis, as described below. In one or more embodiments, the polymer may have a PDI ranging from 3 to 40, 5 to 40, or 7 to 40. For example, in some embodiments, polymers made using a gas-phase polymerization reactor may have a PDI of 5.56 to 36.36. In some embodiments, polymers made using a gas phase polymerization reactor may have a PDI of 3.6 to 7.5. In some embodiments, the polymers may have a PDI of at least 5.00. For example, in some embodiments, the PDI may range from 5.00 to 36.00 or from 5.00 to 40.00.

[0049] An embodiment provides that the polymer made using a gas phase polymerization reactor may have a melting temperature (Tm) of 118 to 132°C (°C). All individual values ​​and subranges between 118 and 132°C are included, for example, the polymer may have a melting temperature from a lower limit of 118, 119, or 120 to an upper limit of 132, 130, or 128°C.

[0050] Polymers made using a slurry phase polymerization reactor may have the same or similar Mn, Mw, PDI, and / or Tm as polymers made using a gas phase polymerization reactor.

[0051] Gel Permeation Chromatography (GPC) Test Method: Weight-average molecular weight test method: Using a chromatogram obtained with a high-temperature gel permeation chromatography instrument (HTGPC, Polymer Laboratories), M w , number average molecular weight (M n ), and M w / Mn The HTGPC is equipped with a transfer line, a differential refractive index detector (DRI), and three Polymer Laboratories PLgel 10 μm Mixed-B columns, all housed in an oven maintained at 160 °C. The method uses a solvent composed of BHT-treated TCB at a base flow rate of 1.0 milliliters per minute (mL / min) and a base 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. The solvent is degassed with an in-line degasser before entering the HTGPC instrument. The column is calibrated using a series of monodisperse polystyrene (PS) standards. Separately, prepare a known concentration of test polymer dissolved in a solvent by heating a known amount of test polymer in a known volume of solvent at 160 °C for 2 hours with continuous shaking to obtain a solution. (All quantities are measured gravimetrically.) The target solution concentration, c, of the test polymer is 0.5 to 2.0 milligrams of polymer per milliliter of solution (mg / mL), with lower concentrations, c, being used for higher molecular weight polymers. Before running each sample, purge the DRI detector. Then, increase the flow rate in the instrument to 1.0 mL / min and allow the DRI detector to stabilize for 8 hours before injecting the first sample. Using the general calibration relationship for column calibration, calculate the M w and M n Calculate the following formula:

number

[0334] -

[0341] . A GPC chromatogram is obtained by plotting dW / dLog(MW) on the y-axis and Log(MW) on the x-axis, where Log(MW) and dW / dLog(MW) are as defined above.

[0052] The polymers may be used in many articles such as films, fibers, nonwoven and / or woven fabrics, extruded articles, and / or molded articles, among others.

[0053] The biphenylphenol polymerization pre-catalyst and / or biphenylphenol polymerization catalyst as detailed herein, as well as other components discussed herein, such as activators, may be used with a support. "Support," which may also be referred to as "carrier," refers to any support material, including porous support materials such as talc, inorganic oxides, and inorganic chlorides.

[0054] The biphenylphenol polymerization pre-catalyst and / or biphenylphenol polymerization catalyst, as well as other components discussed herein, may be supported on the same or different supports, or one or more of the components may be used in an unsupported form. The use of a support may 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 may be functionalized.

[0055] The support may be a porous support material such as talc, an inorganic oxide, or an inorganic chloride. Other support materials include resinous support materials, functionalized or crosslinked organic supports such as polystyrene, polystyrene divinylbenzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material, or mixtures thereof.

[0056] Support materials include inorganic oxides, including Group 2, 3, 4, 5, 13, or 14 metal oxides. Some preferred supports include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicates, zeolites, talc, clay, and the like. Combinations of these support materials, such as silica-chromium, silica-alumina, silica-titania, and the like, can also be used. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads.

[0057] An example of a support is fumed silica available under the trade name Cabosil™ TS-610, or other TS or TG series supports available from Cabot Corporation. Fumed silica is typically silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyl dichloride so that most of the surface hydroxyl groups are capped.

[0058] The support material has a surface area ranging from about 10 to about 700 m / g, and a surface area ranging from 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 / g and the pore volume is in the range of 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 / g, and the pore volume is about 0.8 to about 3.0 g / cm. 3 The average particle size is about 5 to about 100 μm. The average pore diameter of the carrier is typically in the range of 10 to 1000 Å, preferably 50 to about 500 Å, and most preferably 75 to about 350 Å.

[0059] The biphenylphenol polymerization pre-catalyst and / or the biphenylphenol polymerization pre-catalyst and other components discussed herein, such as an activator, can be slurried. Slurries are well known in the art. The slurry can include, for example, the biphenylphenol polymerization pre-catalyst, an activator, and a carrier.

[0060] The molar ratio of metal in the activator to metal in the biphenylphenol polymerization precatalyst in the slurry can be 1000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. One or more diluents, e.g., fluids, can be used to facilitate the combination of any two or more components in the slurry. For example, the biphenylphenol polymerization precatalyst and 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. A support, either dried or mixed with toluene, can then be added to the mixture, or the metal-ligand complex / activator can be added to the support. The slurry can be fed to a reactor for the polymerization process, and / or the slurry can be dried (e.g., spray-dried) before being fed to a reactor for the polymerization process.

[0061] The polymerization process may be a slurry phase polymerization process and / or a gas phase polymerization process. The polymerization process may be used using known equipment and reaction conditions, e.g., known polymerization conditions. The polymerization process is not limited to any particular type of polymerization system. By way of example, the polymerization temperature may range from about 0°C to about 300°C at atmospheric, subatmospheric, or superatmospheric pressure. In particular, slurry or solution polymerization systems may use subatmospheric or superatmospheric pressures and temperatures ranging from about 40°C to about 300°C. Embodiments provide a method for making a polyolefin polymer, the method comprising contacting an olefin with a biphenylphenol polymerization catalyst under polymerization conditions, as described herein, to polymerize the olefin and thereby produce a polyolefin polymer.

[0062] One or more embodiments provide that the polymer may be formed via a gas phase polymerization system at superatmospheric pressures ranging from 0.07 to 68.9 bar, 3.45 to 27.6 bar, or 6.89 to 24.1 bar, and temperatures ranging from 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 may be less than 112° C. Stirred and / or fluidized bed gas phase polymerization systems may be used.

[0063] Generally, conventional gas-phase fluidized-bed polymerization processes can be carried out by continuously passing a stream containing one or more olefin monomers through a fluidized-bed reactor at a rate sufficient to maintain a bed of solid particles in suspension under reactive conditions and in the presence of a catalyst composition, such as a composition containing a biphenylphenol polymerization precatalyst and an activator. A stream containing unreacted monomers can be continuously withdrawn from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled to the reactor. The product, i.e., polymer, can be removed from the reactor, and a replacement 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 reactors in series.

[0064] The feed stream for the polymerization process may include olefin monomers, non-olefin gases such as nitrogen and / or hydrogen, and may further include one or more non-reactive alkanes that are condensable in the polymerization process and can be used to remove 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 may enter the reactor at a single or multiple different locations.

[0065] For the polymerization process, a biphenylphenol polymerization catalyst, such as a supported biphenylphenol polymerization catalyst, can be continuously fed to a reactor. A gas inert to the polymerization catalyst, such as nitrogen or argon, can be used to carry the biphenylphenol polymerization catalyst to the reactor bed. In one embodiment, the biphenylphenol 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 other C3-C8 alkanes.

[0066] For the polymerization process, hydrogen may be used at a gas molar ratio of hydrogen to ethylene in the reactor that may range from about 0.0 to 2.5, 0.0 to 2.0, 0.0 to 1.5, 0.0 to 1.0, 0.01 to 0.7, 0.03 to 0.5, 0.005 to 0.3, or 0.0017 to 0.0068. Many embodiments use hydrogen gas.

[0067] Some aspects of the present disclosure are provided as follows.

[0068] Embodiment 1 provides the use of a supported biphenylphenol polymerization catalyst to make a polymer via a gas phase polymerization process or a slurry phase polymerization process, the supported biphenylphenol polymerization catalyst being made from a biphenylphenol polymerization pre-catalyst of Formula I: [ka] In the formula, R 7 and R 8 each is independently C alkyl, halogen, or hydrogen; R 5 and R 10 Each of C1 to C 20 alkyl, aryl, aralkyl, halide, or hydrogen; R 4 and R11 each is independently halogen or hydrogen; R 2 and R 13 Each of C1 to C 20 alkyl, aryl, or aralkyl, or hydrogen; R 15 and R 16 each is independently 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted carbazol-9-yl; L is a C3 or C4 alkylene that forms a three-carbon or four-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; R 1 , R 3 , R 12 , and R 14 each is hydrogen; R 6 and R 9 each is hydrogen or C1-C8 alkyl, and optionally, R 6 is R 7 and R 8 is R 9 can be linked to form a cyclic structure, Each X is independently selected from halogen, hydrogen, (C1-C 20 ) Alkyl, (C7-C 20 ) ralkyl, (C1-C6) alkyl substituted (C6-C 12 )aryl, or (C1-C6) alkyl-substituted benzyl, -CH2Si(R C )3 and 、 R C is C1~C 12 is a hydrocarbon, M is Zr or Hf.

[0069] Aspect 2 is the use of aspect 1, wherein R 7 and R 8 is C1 alkyl, fluorine, or hydrogen, and R 5 , R 6 , R 9 , and R 10 At least two of the groups are fluorine.

[0070] Aspect 3 is the use of aspect 1, wherein R 15 and R 16 is a 2,7-disubstituted carbazol-9-yl selected from the group consisting of 2,7-di-t-butylcarbazol-9-yl, 2,7-di-ethylcarbazol-9-yl, and 2,7-di-methylcarbazol-9-yl.

[0071] Embodiment 4 provides the use of embodiment 3, wherein the biphenylphenol polymerization pre-catalyst of formula I is selected from the group consisting of structures (i), (ii), (iii), and (viii) as described herein.

[0072] Embodiment 5 provides the use of embodiment 1 or 2, wherein R 15 and R 16 Each of is 3,6-di-t-butylcarbazol-9-yl.

[0073] Embodiment 6 provides the use of embodiment 5, wherein the biphenylphenol polymerization pre-catalyst of formula I is selected from the group consisting of structures (iv) and (v) as detailed herein.

[0074] Embodiment 7 provides the use of embodiment 1, wherein each X is a C1 alkyl.

[0075] Embodiment 8 provides a method of making a supported biphenylphenol polymerization catalyst, the method including disposing a biphenylphenol polymerization pre-catalyst of Formula I on a support to obtain a supported biphenylphenol polymerization pre-catalyst; and contacting the supported biphenylphenol polymerization pre-catalyst of Formula I with an activator under activating conditions to activate the supported biphenylphenol polymerization pre-catalyst of Formula I, thereby making the supported biphenylphenol polymerization catalyst.

[0076] Example 9 provides a method of making a polyethylene composition, the method comprising polymerizing ethylene in the presence of a supported biphenylphenol polymerization catalyst made by the method of Example 8 in a single gas phase polymerization reactor under gas phase polymerization conditions to make a polyethylene composition without the aid of any other polymerization catalyst, wherein the polyethylene composition comprises a high molecular weight polyethylene component and a low molecular weight polyethylene component.

[0077] Example 10 provides the method of example 9, wherein the polyethylene composition has a polydispersity index (PDI) in the range of 5-40 or 7-40.

[0078] Example 11 provides the method of example 9 or example 10, wherein the polyethylene composition is bimodal.

[0079] Example 12 provides a method of making a polyethylene composition, the method comprising polymerizing ethylene in the presence of a supported biphenylphenol polymerization catalyst made by the method of Example 8 in a single slurry-phase polymerization reactor under slurry-phase polymerization conditions to make a polyethylene composition without the aid of any other polymerization catalyst, wherein the polyethylene composition has a polydispersity index (PDI) in the range of 5 to 40, or 7 to 40.

[0080] Embodiment 13 provides a biphenylphenol polymerization pre-catalyst selected from the group consisting of structures (i), (ii), (iii), and (v) as detailed herein.

[0081] Example 14 provides a supported biphenylphenol polymerization catalyst made by the method of Example 8, wherein the biphenylphenol polymerization pre-catalyst of Formula I is selected from a biphenylphenol polymerization pre-catalyst of any of structures (i), (ii), (iii), (viii), or (v), as detailed herein. [Example]

[0082] A biphenylphenol polymerization precatalyst of formula I,

[0083] [ka]

[0084] In the formula, R 7 and R 8 each is independently C alkyl, halogen, or hydrogen;

[0085] R 5 and R 10 Each of C1 to C 20 alkyl, aryl, aralkyl, halogen, or hydrogen;

[0086] R 4 and R 11 each is independently halogen or hydrogen;

[0087] R 2 and R 13 Each of C1 to C 20 alkyl, aryl, or aralkyl, or hydrogen;

[0088] R 15 and R 16 each is independently 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted carbazol-9-yl;

[0089] L is a C3 or C4 alkylene that forms a three-carbon or four-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded;

[0090] R 1 , R 3 , R 12 , and R 14 each is hydrogen;

[0091] R 6 and R 9 each is hydrogen or C1-C8 alkyl, and optionally, R 6 is R 7 and R8 is R 9 can be linked to form a cyclic structure,

[0092] Each X is independently selected from halogen, hydrogen, (C1-C 20 ) Alkyl, (C7-C 20 ) aralkyl, (C1-C6) alkyl substituted (C6- C12 )aryl, or (C1-C6) alkyl-substituted benzyl, -CH2Si(R C )3 and R C is C1~C 12 is a hydrocarbon,

[0093] M is Zr or Hf and is prepared as follows:

[0094] A biphenylphenol polymerization precatalyst of structure (i) was prepared as follows: To a suspension of ZrCl4 (102 mg, 0.44 mmol) in toluene (20 mL) at −28° C. was added a 3.22 M solution of methylmagnesium bromide (0.57 mL, 1.83 mmol). The solution was stirred for 2 minutes, during which a deep red color formed. Next, the ligand of formula A (3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-2'-(3-((3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2'-hydroxy-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propoxy)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) (550 mg, 0.44 mmol) was added in one portion as a solution in toluene (10 mL). The ligand of formula A was prepared as described in 20160108156A1, the entire contents of which are incorporated herein by reference. The solution was allowed to warm to room temperature and stirred for a total of 4 hours. Hexane (30 mL) was added and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure. The crude solid was then taken up in hot toluene (20 mL) and filtered. The filtrate was evaporated under reduced pressure to give 562 mg (93%) of a pale yellow solid. The presence of the biphenylphenol polymerization precatalyst of structure (i) was 1 This was confirmed by 1 H NMR analysis. 11H NMR (400 MHz, C6D6, 298 K) δ 8.19 (d, J = 8.0 Hz, 1H), 8.15 (d, J = 8.0 Hz, 2H), 7.73 (s, 1H), 7.66 (s, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.49 - 7.39 (m, 4H), 7.30 (d, J = 8.0 Hz, 1H), 7.20 (s, 1H), d (J = 8.0 Hz, 1H), 7.06 - 7.00 (m, 3H), 6.63 (d, J = 8.0 Hz, 1H), 6.22 (dd, J = 8.0 Hz and 4.0 Hz, 1H), 5.75 (td, J = 8.0 Hz and 4.0 Hz, 1H), 3.62 (t, J = 8.0 Hz, 1H), 3.30 (m, 2H), 3.16 (m, 1H), 1.61 (s, 12H), 1.47 (s, 12H), 1.26 (s, 18H), 1.25 (s, 18H), 0.93 (s, 12H), 0.84 (s, 12H), 0.52 (d, 12.0 Hz, 3H), -0.56 (s, 3H), -0.98 (s, 3H).

[0095]

Chem.

[0096] A biphenylphenol polymerization precatalyst of structure (ii) was prepared as follows: To a suspension of ZrCl4 (63 mg, 0.27 mmol) in toluene (20 mL) at -28 °C was added a 3.22 M solution of methylmagnesium bromide (0.37 mL, 1.18 mmol). The solution was stirred for 2 minutes, during which a deep red color formed. Next, ligand B [2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-bis(diisopropyl(octyl)silyl)-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpent-2-yl)-[1,1'-biphenyl]-2-ol))] (520 mg, 0.27 mmol) was added in one portion as a solution in toluene (10 mL). The ligand of formula B was prepared as described in 2018026504(A1), the entire contents of which are incorporated herein by reference. The solution was warmed to room temperature and stirred for a total of 3 hours. Hexane (30 mL) was added, and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure. The crude solid was then taken up in hot toluene (20 mL) and filtered. The filtrate was evaporated under reduced pressure to give 457 mg (83%) of a pale yellow solid. The presence of a biphenylphenol polymerization precatalyst of structure (ii) 1 This was confirmed by 1 H NMR analysis. 1 H NMR(400MHz,C6D6,298K)δ8.26(d,J=8.0Hz,2H),8.13(d,J=8.0Hz,2H),8. 05(s,2H),7.97(s,2H),7.68(s,2H),7.64(d,J=8.0Hz,2H),7.54(d,J=8.0H z,2H),7.36(s,2H),7.02(d,J=4.0Hz,2H),6.21(dd,J=8.0 and 4.0Hz,2H),3 .72(m,2H),3.52(m,2H),1.65-0.91(m,152H),0.80(s,12H),-0.46(s,6H). [ka] [ka]

[0097] A biphenylphenol polymerization precatalyst of structure (iii) was prepared as follows: To a suspension of ZrCl4 (69 mg, 0.30 mmol) in toluene (20 mL) at -28 °C was added a 3.22 M solution of methylmagnesium bromide (0.40 mL, 1.30 mmol). The solution was stirred for 2 minutes, during which a deep red color formed. Next, ligand C (2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-bis(diisopropyl(octyl)silyl)-9H-carbazol-9-yl)-5'-fluoro-3',5-dimethyl-[1,1'-biphenyl]-2-ol)) (513 mg, 0.30 mmol) was added in one portion as a solution in toluene (10 mL). The ligand of formula C was prepared as described in WO2017058981A1, the entire contents of which are incorporated herein by reference. The solution was warmed to room temperature and stirred for a total of 3 hours. Hexane (30 mL) was added and the solution was filtered to remove insoluble salts. The filtrate was dried under reduced pressure to yield 495 mg (90%) of a pale yellow solid. The presence of the biphenylphenol polymerization precatalyst of structure (iii) was 1 This was confirmed by 1 H NMR analysis. 1 H NMR(400MHz,C6D6,298K)δ8.27(d,J=8.0Hz,2H),8.16(d,J=8.0Hz,2H),8.05(s,2H),7. 96(s,2H),7.63(d,J=8.0Hz,2H),7.56(d,J=8.0Hz,2H),6.92(d,J=4.0Hz,2H),6.79(d,J =4.0Hz,2H),6.77(d,J=4.0Hz,2H),6.13(d,J=4.0Hz,1H),6.11(d,J=4.0Hz,1H),3.54( q,J=4.0Hz,2H),3.30(q,J=4.0Hz,2H),2.13(s,6H),1.66-0.89(m,130H),-0.42(s,6H). [ka] [ka]

[0098] The biphenylphenol polymerization precatalyst of structure (iv) was prepared as described in US9000108B2, the entire contents of which are incorporated herein by reference. [ka]

[0099] A biphenylphenol polymerization precatalyst of structure (v) was prepared using a ligand of formula J (i.e., ligand 5 as described and illustrated below). The ligand of formula J was prepared as described below.

[0100] [ka]

[0101] Step 1: Synthesis of (2) A solution of t-butylamine (21.9 g, 0.30 mol) in toluene (200 mL) was prepared in a 1 L two-neck round-bottom flask. Bromine (24.6 g, 0.15 mol) was slowly added to the mixture at -30 °C, and the resulting solution was stirred at this temperature for 15 minutes. 2,3-Difluorophenol (1) (20 g, 0.15 mol) in methylene chloride (CHCl) (200 mL) was added to the mixture at -78 °C. The resulting mixture was stirred at -78 °C for 4 hours. The reaction mixture was quenched at the same temperature using sodium thiosulfate solution (40 mL). The mixture was diluted with CHCl (100 mL) and then washed with water (50 mL), 1 N aqueous hydrochloric acid (HCl) (50 mL), and saturated aqueous sodium chloride solution (brine) (75 mL). The organic layer was isolated using a separatory funnel, and the volatiles were then removed under reduced pressure. Purification of the crude material by silica gel column chromatography gave 14 g of intermediate 2 with 95% purity by GCMS (yield=44%). 1 H-NMR (400MHz, CDCl3): δ[ppm]5.76(br s,1H),6.69-6.75(m,1H),7.21-7.25(m,1H). 19F-NMR(376.5MHz,CDCl3):δ[ppm]-156.4(d,J=22.6Hz,1F),-136.2(d,J=18.8Hz,1F).LCMS:209(M+1)&211(M+3).

[0102] Step 2: Synthesis of (3). Intermediate (2) (11 g, 0.053 mol) and 1,3-dibromopropane (5.3 g, 0.026 mol) were dissolved in acetone (200 mL) in a 500 mL two-neck round-bottom flask. Potassium carbonate (K2CO3) (22 g, 0.16 mol) was added to the suspension, which was then stirred at 65 °C for 24 h. The mixture was cooled and then filtered. The filtrate was concentrated under vacuum to provide a crude residue, which was dissolved in C2Cl2 (200 mL), transferred to a separatory funnel, and then washed with 3 N aqueous KOH (50 mL), followed by saturated aqueous K2CO3 (50 mL x 2). The organic layer was dried over magnesium sulfate (MgSO4) and then concentrated to dryness to give the crude product. Purification of the crude product by silica gel column chromatography (twice) afforded 8.5 g of 3 with a purity of 97% by GCMS (yield = 71%). 1 H-NMR (400MHz, CDCl3): δ[ppm]2.34(quin,J=6.0Hz,2H),4.46(t,J=6.0Hz,4H),6.81-6.88(m,2H),7.27-7.29(m,2H). 19 F-NMR (376.5MHz, CDCl3): δ[ppm]-150.2(d,J=18.8Hz,1F),-136.1(d,J=18.8Hz,1F). 13 C-NMR(100MHz,CDCl3):δ[ppm]30.8,70.9,71.0,111.7,112.3,112.4,126.7,126.8,126.8, 126.8,143.7,143.8,145.7,145.8,146.2,146.3,149.6,149.7,152.1,152.2.GCMS:458(M). [ka]

[0103] Step 3: Synthesis of Ligand (5). Degassed THF (10 mL) and degassed water (3 mL) were added to a 40 mL vial charged with boronic ester 4 (preparation of 4 is provided in US8609794B2) (0.87 g, 1.25 mmol), dibromide 3 (0.26 g, 0.57 mmol), solid NaOH (0.11 g, 2.84 mmol), and Pd-Amphos (0.01 g, 0.02 mmol). The reaction was warmed to 55 °C and maintained at this temperature for 18 h. After this time, the reaction was cooled to room temperature. The mixture was transferred to a separatory funnel, diethyl ether (EtO) (25 mL) and water (10 mL) were added, and the layers were separated. The organics were washed with brine (10 mL), dried (NaSO), and filtered. To the above filtrate, MeOH (10 mL) was added along with concentrated HCl (8 drops from a glass pipette). The solution was stirred at room temperature for 18 h. The solution was concentrated to dryness under reduced pressure. The residue was dry-loaded onto a CELITE pre-cartridge and then directly purified using reverse-phase flash chromatography (50 g C18, 40 mL / min, 0% THF to 50% THF in CH3CN over 15 min) to afford 0.55 g (77%) of 5 as a white solid. 1 H NMR(400MHz,CDCl3)δ8.13(dd,J=2.0,0.6Hz,4H),7.42-7.34(m,6H),7.30(d,J=2.4Hz,2H),7.09(ddd,J=8.1,5.8,1.9Hz,2H),7.0 6-6.92(m,6H),5.37(s,2H),4.02(t,J=6.0Hz,4H),1.86(p,J=6.0Hz,2H),1.69(s,4H),1.43(s,36H),1.33(s,12H),0.77(s,18H); 19 F NMR(376MHz,CDCl3)δ-136.39(d,J=20.3Hz),-153.30(d,J=20.1Hz).LCMS(ES / APCIMS m / z 1264[(M+H)+]. [ka] Step 4: Synthesis Precatalyst of Structure (v). A biphenylphenol polymerization precatalyst of structure (v) was prepared as follows: 3 M MeMgBr in EtO (0.25 mL) was added to a −30° C. solution of HfCl (0.06 g, 0.18 mmol) in toluene (6 mL). After stirring for 5 minutes, ligand 5 (i.e., ligand J below) (2′,2′′′-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3′,4′-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)) (0.23 g, 0.18 mmol) in toluene (1 mL) was added. The mixture was stirred for 18 hours, and then the solvent was removed under vacuum. A mixture of hexane and toluene (5:1, 12 mL) was added to the residue, the solution was shaken at room temperature for several minutes, and then the material was passed through a fritted funnel packed with a plug of CELITE. The frit was extracted with a mixture of hexane and toluene (5:1, 12 mL). The combined extracts were concentrated to dryness under reduced pressure to give 0.2 g (76%) of the product as a tan solid. The presence of the biphenylphenol polymerization precatalyst of structure (v) was confirmed by NMR. 1 H NMR(400MHz,C6D6)δ8.63-8.57(m,2H),8.35-8.30(m,2H),7.93-7.82(m,6H),7.61-7.54(m,2H),7 .35(dd,J=8.8,1.9Hz,2H),7.19(d,J=2.5Hz,2H),6.69-6.58(m,2H),6.39-6.29(m,2H),3.99(app dt,J=10.7,5.9Hz,2H),3.17-3.06(m,2H),1.69(s,22H),1.29(s,24H),1.24(s,6H),1.17-1.08(m,2H),0.87(s,18H),-0.87(s,6H); 19 F NMR(376MHz,C6D6)δ-135.70(d,J=20.5Hz),-148.58(d,J=20.4Hz). [ka]

[0104] A comparative polymerization pre-catalyst of structure (vi) was prepared as described in US20150291713A1, the entire contents of which are incorporated herein by reference. [ka]

[0105] A comparative polymerization pre-catalyst of structure (vii) was prepared as described in US20160108156A1, the entire contents of which are incorporated herein by reference. [ka]

[0106] Example 1 (EX1), an activated, supported biphenylphenol polymerization catalyst of Formula I, was prepared as follows: In a nitrogen-purged glovebox, an oven-dried glass bottle was charged with 2.65 grams (g) of treated fumed silica (CABOSIL TS-610, available from W.R. Grace) slurried with 75 g of toluene (available from Aldrich) and a stir bar, and stirred until well dispersed. 22 g of a 10 wt% solution of methylaluminoxane (MAO) (available from W.R. Grace as 10 wt% in toluene) was added to the bottle to form a mixture. The mixture was magnetically stirred for 15 minutes, and then 0.303 g of a biphenylphenol polymerization precatalyst of Structure i was added, and the mixture was stirred for 30-60 minutes. The mixture was spray-dried using a Buchi Mini Spray Dryer B-290 with the following parameters to obtain the dried, supported, activated biphenylphenol polymerization catalyst of Example 1: Set temperature - 185°C, outlet temperature - 100°C (min), aspirator - 95, and pump speed - 150 rpm.

[0107] Example 2 (EX2) was prepared in the same manner as Example 1, with the modification that the catalyst of Example 2 was used, as shown in Table 1.

[0108] Example 3 (EX3) was prepared identically to Example 1, with the modification that the catalyst of Example 3 was used, as shown in Table 1.

[0109] Example 4 (EX4) was prepared in the same manner as Example 1, with the modification that the catalyst of Example 4 was used, as shown in Table 1.

[0110] Example 5 (EX5) was prepared identically to Example 1, with the modification that the catalyst of Example 5 was used, as shown in Table 1.

[0111] Example 6 (EX6) was prepared in the same manner as Example 1, with the modification that Example 6 was carried out under the conditions as shown in Table 1 for Example 6.

[0112] Example 7 (EX7) was prepared in the same manner as Example 2, with the modification that Example 7 was carried out under the conditions as shown in Table 1 for Example 7.

[0113] Example 8 (EX8) was prepared in the same manner as Example 3, with the modification that Example 8 was carried out under the conditions as shown in Table 1 for Example 8.

[0114] Example 9 (EX9) was prepared in the same manner as Example 4, with the modification that Example 9 was carried out under the conditions shown in Table 1 for Example 9.

[0115] Comparative Example 1 (CE1) was prepared identically to Example 1, with the modification that the catalyst of Comparative Example 1 was used, as shown in Table 1.

[0116] Comparative Example 2 (CE2) was prepared identically to Example 1, with the modification that the catalyst of Comparative Example 2 was used, as shown in Table 1.

[0117] Ethylene / 1-hexene copolymerizations of EX1-9 and CE1-2 were carried out in the gas phase in a 2 L semi-batch autoclave polymerization reactor equipped with a mechanical stirrer as follows. The reactor was first dried for 1 hour, charged with 200 g of sodium chloride (NaCl), and dried by heating at 100 °C for 30 minutes under nitrogen. After drying, 5 grams of silica-supported methylaluminoxane (SMAO) was introduced under nitrogen pressure as a scavenger. After SMAO addition, the reactor was sealed and the components were stirred. The reactor was then charged with hydrogen (H2 preload, as indicated below for each condition) and hexene (C6 / C2 ratio, as indicated below for each condition) and then pressurized with ethylene (230 psi). Once the system reached steady state, the type and amount of each activated catalyst identified in Tables 1 and 2 for EX1-9 and CE1-2, respectively, was charged to the reactor at 80 °C to initiate polymerization. The reactor temperature was brought to 90 or 100°C and maintained at this temperature for a 1-hour run. Runs were conducted under conditions B or K, as detailed in Table 1 below. At the end of the run, the reactor was cooled, vented, and opened. The resulting product mixture was washed with water and methanol and then dried. The results for EX1-9 and CE1-2 are shown in Table 1.

[0118] The slurry phase biphenylphenol polymerization precatalyst of structure (viii) was prepared as described in WO2017004456, the entire contents of WO2017058981A1 being incorporated herein by reference. [ka]

[0119] Example 10 (EX10) was prepared in an inert atmosphere glove box under nitrogen. Isopar E, ethylene, and hydrogen were purified by passing them through two columns: one containing A2 alumina and the second containing the Q5 reactant. 48 parallel pressure reactor (PPR)-A reactor cells were prepared the following weekday prior to the actual PPR run. A tared library of glass tubes was manually inserted into the reactor wells, the agitator paddle attached to the module head, and the module head attached to the module body. The reactor was heated to 150°C, purged with nitrogen for 10 hours, and cooled to 50°C. On the day of the experiment, the reactor was purged twice with ethylene, fully evacuated, and the lines purged. The reactor was then heated to 50°C, and the agitator was turned on at 400 rpm. Using a robotic needle, the reactor was filled with Isopar-E to the appropriate solvent level to obtain a final reaction volume of 5 mL. Solvent injection into modules 1-3 was performed using the left robotic arm, while solvent injection into modules 4-6 was performed using the right robotic arm, with both arms operating simultaneously. Following solvent injection, the reactor was heated to the final desired temperature, and agitation was increased to the setpoint programmed in the Library Studio design. When the reactor reached the temperature setpoint, which required approximately 10-30 minutes depending on the desired temperature, the cells were pressurized to the desired setpoint with either pure ethylene or a mixture of ethylene and hydrogen from the gas accumulator until the solvent was saturated (as observed by gas uptake). When an ethylene-hydrogen mixture was used, once the solvent was saturated in all cells, the gas supply line was switched from the ethylene-hydrogen mixture to pure ethylene for the remainder of the run. The robotic synthesis protocol was then initiated, whereby the comonomer solution (1-hexene) was injected first, followed by the scavenger solution (SMAO), and finally the catalyst solution in Isopar-E. All injections into modules 1-3 were performed using the left robotic arm, while injections into modules 4-6 were performed using the right robotic arm, with both arms actuated simultaneously. All three injections for a given cell were completed before the robot began injecting the next cell in the sequence.Each reagent addition was followed by 500 μl of Isopar-E solvent to ensure complete injection of the reagent. After each reagent addition, the inside and outside of the needle were rinsed with Isopar-E. The reaction timer was started the moment the catalyst was injected into each individual cell. The polymerization reaction proceeded for 60–180 min or until the set ethylene uptake of 60–180 psi, whichever occurred first, and then quenched by adding 40 psi overpressure of 10% (v / v) CO2 in argon. Data collection continued for 5 min after quenching each cell. The reactor was cooled to 50 °C, evacuated, and the PPR tubing was removed from the module block. The PPR library was removed from the drybox, and volatiles were then removed using a Genevac rotary evaporator to yield the polymer of Example 10.

[0120] Example 11 (EX11) was prepared in the same manner as Example 10, with the modification that Example 11 was carried out under the conditions as shown in Table 2 for Example 11. The results for EX10 and EX11 are shown in Table 2 below.

[0121] Catalyst Preparation Procedure - Supported Reaction of Structure VIII to SMAO: All work was performed in the nitrogen-purged box of the Core Module 3 (CM3) high-throughput unit. Prior to starting the experiment, a solution of Structure VIII was prepared to the desired concentration in toluene. The desired amount of SMAO was manually weighed into each reaction vial to reach 45 μmol of catalyst per gram of SMAO (approximately a 1:108 equivalent ratio) and added along with a tumble stir disk. Toluene was dispensed via CM3, followed by the desired amount of the stock solution of Structure VIII. After all reaction components were added, the vials were capped, stirred at 300 rpm, and heated to 50 °C. After 30 min, the vials were cooled to room temperature, uncapped, and the reaction plate was placed on the CM3 vortex deck. The reaction vials were mixed by vortexing at 800 rpm for 3 min to form a uniform slurry. The desired amount of each supported catalyst slurry was then dispensed into an 8 mL vial and diluted with Isopar E. If multiple daughter samples were required, a new PDT chip was used for each subsequent daughtering step. The reaction was daughtered to the desired concentration of PPR.

[0122] In various embodiments, the biphenylphenol polymerization pre-catalyst is selected from the group consisting of one or more of structures (i), (ii), (iii), (viii), (iv), and / or (v), as detailed herein. In various embodiments, the biphenylphenol polymerization pre-catalyst is selected from the group consisting of one or more of structures (i), (ii), (iii), (iv), and / or (v), as detailed herein. In various embodiments, the biphenylphenol polymerization pre-catalyst is selected from the group consisting of one or more of structures (i), (ii), (iii), (viii), (iv), and (v), as detailed herein. In various embodiments, the biphenylphenol polymerization pre-catalyst is selected from the group consisting of one or more of structures (i), (ii), (iii), (iv), and (v), as detailed herein.

[0123] B—Conditions are as follows: Temperature = 100°C, Ethylene = 220 pounds per square inch (psi), H2 / C2 = 0.0017, C6 / C2 = 0.004. スラリー The conditions were as follows: temperature = 100°C, ethylene = 100 pounds per square inch (psi), H2 / C2 = 0.012.

[0124] The K conditions were as follows: temperature = 100°C, ethylene = 220 psi, H2 / C2 = 0.0068, C6 / C2 = 0.004. スラリー The conditions were as follows: temperature = 100°C, ethylene = 100 pounds per square inch (psi), H2 / C2 = 0.05.

[0125] Bimodal GPC plot (yes / no): By plotting dWf / dLogM (mass detector response) on the y-axis and LogM on the x-axis to obtain a GPC chromatogram curve containing the maximum log(MW) values ​​of the peaks of LMW and HMW polyethylene components, and observing the presence or absence of a minimum between the peak of the LMW polyethylene component and the peak of the HMW polyethylene component, the presence or absence of resolved multimodality such as bimodality can be determined. dWf is the change in weight fraction, and dLogM is also called dLog(MW) and is the change in the logarithm of molecular weight. LogM is also called Log(MW) and is the logarithm of molecular weight.

[0126] Mn (number average molecular weight) and Mw (weight average molecular weight) were determined by gel permeation chromatography (GPC), as known in the art. Values ​​are reported in units of Daltons (Da).

[0127] Polydispersity index (PDI) refers to a measure of the distribution of molecular masses in a given polymer sample. The polydispersity index is calculated by dividing Mw by Mn.

[0128] The melting temperature (i.e., Tm) can be determined by differential scanning calorimetry according to ASTM D3418-08, for example, using a scan rate of 10°C / min on a 10 mg sample and using a second heating cycle. [Table 1] [Table 2]

[0129] As detailed in Table 1, EX1-9 each provide a supported biphenylphenol polymerization catalyst that produces polyethylene with a PDI greater than 5 and a bimodal distribution, as evidenced by GPC plots demonstrating the presence of bimodality, over a wide range of conditions, including H2 / C2 values ​​ranging from 0.0017 to 0.0068. For example, EX1-9 (gas phase, conducted under B / K conditions as detailed in Table 1) each provided polyethylene with a high molecular weight polyethylene component (represented by the second peak in the polyethylene molecular weight distribution plot) and a low molecular weight polyethylene component (represented by the first peak in the polyethylene molecular weight distribution plot). Furthermore, EX1-11 each provided a PDI greater than 5.0 (under both B and K conditions), compared to PDIs for CE1 and CE2, which were less than 3.0 and / or had non-bimodal GPC plots, as shown in Table 1.

[0130] In summary, each of EX1-9 demonstrates the presence of bimodality over a wide range of conditions, including H2 / C2 values ​​ranging from 0.0017 to 0.0068, as evidenced by GPC plots demonstrating the presence of bimodality, with PDIs exceeding 5.0. Furthermore, each of EX10-11 provides a PDI exceeding 5.0. Furthermore, the bimodal polymers provided by the supported biphenylphenol polymerization catalysts of EX1-11 are formed in a single reactor gas-phase or slurry-phase polymerization reactor without the aid of any other polymerization catalyst. This contrasts with other approaches that rely on multiple reactors and / or multiple polymerization catalysts to provide bimodal polymers, and with other polymerization catalysts (such as CE1 and CE2) that provide polymers with a monomodal distribution. The present specification includes the following aspects. Section 1. 1. Use of a supported biphenylphenol polymerization catalyst to make a bimodal polyethylene composition via a gas phase polymerization process or a unimodal polyethylene composition via a slurry phase polymerization process, wherein the supported biphenylphenol polymerization catalyst is made from a biphenylphenol polymerization pre-catalyst of Formula I: [ka] In the formula, R 7 and R 8 each is independently C alkyl, halogen, or hydrogen; R 5 and R 10 Each of C1 to C 20 alkyl, aryl, aralkyl, halogen, or hydrogen; R 4 and R 11 each is independently halogen or hydrogen; R 2 and R 13 Each of C1 to C 20 alkyl, aryl, or aralkyl, or hydrogen; R 15 and R 16 each is independently 2,7-disubstituted carbazol-9-yl or 3,6-disubstituted carbazol-9-yl; L is a C3 or C4 alkylene that forms a three-carbon or four-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded; R 1 , R 3 , R 12 , and R 14 each of which is hydrogen; R 6 and R 9 each of which is hydrogen or C1-C8 alkyl, and optionally R 6 But R 7 and R 8 But R 9 can be linked to form a cyclic structure, Each X is independently selected from halogen, hydrogen, (C1-C20 ) Alkyl, (C7-C 20 ) aralkyl, (C1-C6) alkyl substituted (C6-C 12 )aryl, or (C1-C6) alkyl-substituted benzyl, -CH2Si(R C )3 and R C However, C1~C 12 is a hydrocarbon, Use where M is Zr or Hf. Section 2. R 7 and R 8 is C1 alkyl, fluorine, or hydrogen; R 5 , R 6 , R 9 , and R 10 Item 1, wherein at least two of the groups are fluorine. Section 3. R 15 and R 16 Item 3. The use according to item 1 or 2, wherein each of the above is a 2,7-disubstituted carbazol-9-yl selected from the group consisting of 2,7-di-t-butylcarbazol-9-yl, 2,7-di-ethylcarbazol-9-yl, and 2,7-di-methylcarbazol-9-yl. Section 4. Item 4. The use according to item 3, wherein the biphenylphenol polymerization pre-catalyst of formula I is selected from the group consisting of structures (i), (ii), (iii), and (viii). [ka] [ka] [ka] [ka] Section 5. R 15 and R 16 Item 3. The use according to item 1 or 2, wherein each of the above is 3,6-di-t-butylcarbazol-9-yl. Section 6. Item 6. The use according to item 5, wherein the biphenylphenol polymerization pre-catalyst of formula I is selected from the group consisting of structures (iv) and (v). [ka] [ka] Section 7. Item 1, wherein each X is a C1 alkyl. Section 8. 1. A method for making a supported biphenylphenol polymerization catalyst, comprising: disposing the biphenylphenol polymerization pre-catalyst of Formula I on a support to obtain a supported biphenylphenol polymerization pre-catalyst; contacting the supported biphenylphenol polymerization pre-catalyst of Formula I with an activator under activating conditions to activate the supported biphenylphenol polymerization pre-catalyst of Formula I, thereby producing the supported biphenylphenol polymerization catalyst. Section 9. 1. A method of making a bimodal polyethylene composition, comprising: Item 9. A method for producing a bimodal polyethylene composition comprising: polymerizing ethylene in the presence of the supported biphenylphenol polymerization catalyst, prepared by the method described in Item 8, in a single gas phase polymerization reactor under gas phase polymerization conditions to produce the bimodal polyethylene composition without the aid of any other polymerization catalyst, wherein the bimodal polyethylene composition comprises a high molecular weight polyethylene component and a low molecular weight polyethylene component. Section 10. Item 10. The method according to item 9, wherein the bimodal polyethylene composition has a polydispersity index (PDI) in the range of 5 to 40 or 7 to 40. Section 11. 1. A method for making a unimodal polyethylene composition, comprising: Item 9. A method for producing a polyethylene composition without the aid of any other polymerization catalyst, comprising polymerizing ethylene in the presence of the supported biphenylphenol polymerization catalyst prepared by the method of item 8 in a single slurry-phase polymerization reactor under slurry-phase polymerization conditions, wherein the unimodal polyethylene composition has a polydispersity index (PDI) in the range of 5 to 40 or 7 to 40. Section 12. Item 12. The method according to any one of items 9 to 11, wherein the polymerization step comprises using any one of items 1 to 7. Section 13. A biphenylphenol polymerization precatalyst selected from the group consisting of structures (i), (ii), (iii), and (v). [ka] [ka] Section 14. Item 9. A supported biphenylphenol polymerization catalyst made by the method described in item 8, wherein the biphenylphenol polymerization pre-catalyst of formula I is selected from the biphenylphenol polymerization pre-catalysts of any of structures (i), (ii), (iii), (viii), or (v). [ka] [ka]

Claims

Claim 1: Use of a supported biphenylphenol polymerization catalyst for making a bimodal polyethylene composition via a gas phase polymerization process, wherein the supported biphenylphenol polymerization catalyst is made from a biphenylphenol polymerization pre-catalyst of Formula I: 【Chemical 1】 In the formula, R ７ and R ８ Each of the groups independently represents C １ alkyl, halogen, or hydrogen; R ５ and R １０ Each of the groups independently represents C １ ~C ２０ alkyl, aryl, aralkyl, halogen, or hydrogen; R ４ and R １１ each is independently halogen or hydrogen; R ２ and R １３ Each of the groups independently represents C １ ~C ２０ alkyl, aryl, or aralkyl, or hydrogen; R １５ and R １６ each is independently 3,6-di-t-butylcarbazol-9-yl or 2,7-di-n-octyl-di-isopropyl-silylcarbazol-9-yl; L forms a three-carbon bridge or a four-carbon bridge between the two oxygen atoms to which L is covalently bonded, respectively. ３ or C ４ is alkylene, R １ , R ３ , R １２ , and R １４ each of which is hydrogen; R ６ and R ９ Each of １ ~C ８ alkyl, and optionally R ６ is R ７ Connected with R ８ is R ９ can be linked to form a cyclic structure, Each X is independently selected from halogen, hydrogen, (C １ ~C ２０ ) alkyl, (C ７ ~C ２０ ) aralkyl, (C １ ~C ６ ) alkyl-substituted (C ６ ~C １２ ) aryl, (C １ ~C ６ ) alkyl-substituted benzyl, or —CH ２ Si(R Ｃ ) ３ and R Ｃ But C １ ~C １２ is a hydrocarbon, Use wherein M is Zr or Hf.

2. R ７ and R ８ But C １ alkyl, fluorine, or hydrogen; R ５ , R ６ , R ９ , and R １０ The use according to claim 1, wherein at least two of are fluorine.

3. 2. The use of claim 1, wherein the biphenylphenol polymerization precatalyst of formula I is selected from the group consisting of structure (ii) and structure (iii). 【Chemistry 3】 【Chemistry 4】

4. 2. The use of claim 1, wherein the biphenylphenol polymerization precatalyst of formula I is selected from the group consisting of structure (iv) and structure (v). 【Chemistry 6】 【Chemistry 7】

5. Each X is C １ The use according to claim 1, wherein the alkyl is alkyl.

6. 1. A method for making a supported biphenylphenol polymerization catalyst, comprising: disposing the biphenylphenol polymerization pre-catalyst of Formula I on a support to obtain a supported biphenylphenol polymerization pre-catalyst; contacting the supported biphenylphenol polymerization pre-catalyst of Formula I with an activator under activating conditions to activate the supported biphenylphenol polymerization pre-catalyst of Formula I, thereby producing the supported biphenylphenol polymerization catalyst; 【Chemistry 8】 In the formula, R ７ and R ８ Each of the groups independently represents C １ alkyl, halogen, or hydrogen; R ５ and R １０ Each of the groups independently represents C １ ~C ２０ alkyl, aryl, aralkyl, halogen, or hydrogen; R ４ and R １１ each is independently halogen or hydrogen; R ２ and R １３ Each of the groups independently represents C １ ~C ２０ alkyl, aryl, or aralkyl, or hydrogen; R １５ and R １６ each of which is 3,6-di-t-butylcarbazol-9-yl or 2,7-di-n-octyl-di-isopropyl-silylcarbazol-9-yl; L forms a three-carbon bridge or a four-carbon bridge between the two oxygen atoms to which L is covalently bonded, respectively. ３ or C ４ is alkylene, R １ , R ３ , R １２ , and R １４ each of which is hydrogen; R ６ and R ９ Each of １ ~C ８ alkyl, and optionally R ６ is R ７ Connected with R ８ is R ９ can be linked to form a cyclic structure, Each X is independently selected from halogen, hydrogen, (C １ ~C ２０ ) alkyl, (C ７ ~C ２０ ) aralkyl, (C １ ~C ６ ) alkyl-substituted (C ６ ~C １２ ) aryl, (C １ ~C ６ ) alkyl-substituted benzyl, or —CH ２ Si(R Ｃ ) ３， and R Ｃ is C １ ~C １２ is a hydrocarbon, The method wherein M is Zr or Hf.

7. 1. A method of making a bimodal polyethylene composition, comprising:

10. A method of producing a bimodal polyethylene composition comprising: polymerizing ethylene in the presence of the supported biphenylphenol polymerization catalyst made by the method of claim 6 in a single gas phase polymerization reactor under gas phase polymerization conditions to produce the bimodal polyethylene composition without the aid of any other polymerization catalyst, wherein the bimodal polyethylene composition comprises a high molecular weight polyethylene component and a low molecular weight polyethylene component.

8. 8. The method of claim 7, wherein the bimodal polyethylene composition has a polydispersity index (PDI) in the range of 5 to 40 or 7 to 40.

9. The method of claim 7 or 8, comprising the use of any one of claims 1 to 5 in polymerizing the ethylene.

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