Biphenylphenol polymerization catalyst

Abstract

An embodiment is directed to the use of a supported biphenylphenol polymerization catalyst to produce a polymer via a slurry phase polymerization process, the supported biphenylphenol polymerization catalyst being prepared from a biphenylphenol polymerization pre-catalyst of Formula I.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to biphenylphenol polymerization catalysts, and more specifically, to biphenylphenol polymerization catalysts that can be used for producing polymers via a slurry phase polymerization reaction process.

Background Art

[0002] Polymers can be used in many products, examples of which include films, fibers, nonwoven fabrics and / or woven fabrics, extruded articles, and / or molded articles, among others. Polymers can be produced by reacting one or more monomers in a polymerization reaction in the presence of a polymerization catalyst.

Summary of Invention

[0003] The present disclosure provides various embodiments including the following. There is provided use of a supported biphenylphenol polymerization catalyst for producing a polymer via a slurry phase polymerization process, wherein the supported biphenylphenol polymerization catalyst has Formula I:

[0004]

Chemical Formula

[0005] A supported biphenylphenol polymerization catalyst that can be used to produce polymers via a slurry phase polymerization process is given by formula I:

[0006] [ka] (In the formula, R 5 , R 7 , R 8 , and R 10 Each of these is independent of (C1~C 20 ) Alkyl, aryl, aralkyl, halogen, or hydrogen, R4 and R 11 Each of them is independently a halogen or hydrogen, and R 2 and R 13 Each of these is independent of (C1~C 20 ) Alkyl, aryl, or aralkyl, or hydrogen, R 15 and R 16 Each of them is independently a 2,7-disubstituted carbazole-9-yl or a 3,6-disubstituted carbazole-9-yl, L is a C3 alkylene or C4 alkylene that forms a bridge between the two oxygen atoms to which L is covalently bonded, and R 1 , R 3 , R 12 , and R 14 Each of them is independently a (C1-C8) alkyl, halogen, or hydrogen, and R 6 and R 9 Each of them is hydrogen, (C1-C8) alkyl, or halogen, and R is optionally selected. 6 R 7 It can be connected to R 8 R 9 They can be linked together to form a ring structure, and each X can independently be a halogen, hydrogen, (C1~C 20 ) Alkyl, (C7~C 20 ) Aralkyl, (C1~C6) alkyl substitution (C6~C 12 )aryl, or (C1~C6) alkyl-substituted benzyl, -CH2Si(R C )3(However, R C (C1~C 12 It is produced from a biphenylphenol polymerization precatalyst (which is a hydrocarbon and M is either Zr or Hf).

[0007] As described herein, a biphenylphenol polymerization precatalyst represented by formula I (i.e., a biphenylphenol polymerization precatalyst) can be used to produce a biphenylphenol polymerization catalyst. For example, a biphenylphenol polymerization precatalyst represented by formula I can be contacted with an activator under activation conditions to activate the biphenylphenol polymerization precatalyst represented by formula I, thereby producing a biphenylphenol polymerization catalyst.

[0008] As mentioned above, R as shown in Equation I 5 , R 7 , R 8 , and R 10 Each of these is independent of (C1~C 20 ) may be alkyl, aryl, aralkyl, halogen, or hydrogen. One or more embodiments are R 5 , R 7 , R 8 , and R 10 The condition is that at least one of them is a halogen such as fluorine. One or more embodiments are R 5 , R 7 , R 8 , and R 10 Each of these is provided to be a halogen such as fluorine. One or more embodiments are R 5 and R 10 Each of these is provided to be a halogen such as fluorine. One or more embodiments are R 5 and R 10 Each of these is required to be chlorine. One or more embodiments are R 5 and R 10 Each of them is provided to be methyl. One or more embodiments are R 5 and R 10 The condition is that at least one of them is an alkyl or aryl-substituted silyl. One or more embodiments are R 5 and R 10 Each of these is provided to be a dialkyl or trialkyl-substituted silyl. One or more embodiments are R 5 and R 10with the proviso that each is octyldimethylsilyl.

[0009] One or more embodiments provide that R 7 and R 8 each are independently hydrogen or methyl. One or more embodiments provide that R 7 and R 8 at least one is hydrogen. One or more embodiments provide that R 7 and R 8 each is hydrogen. One or more embodiments provide that R 7 and R 8 at least one is C1 alkyl, for example, methyl. One or more embodiments provide that R 7 and R 8 each is methyl, with the proviso.

[0010] One or more embodiments provide that R 1 , R 3 , R 12 , and R 14 each are independently (C1-C8) alkyl, halogen, or hydrogen. One or more embodiments provide that R 1 , R 3 , R 12 , and R 14 at least one is hydrogen. One or more embodiments provide that R 1 , R 3 , R 12 , and R 14 each is hydrogen, with the proviso.

[0011] One or more embodiments provide that R 6 and R 9 each is hydrogen, (C1-C8) alkyl, or halogen such as fluorine, and optionally, R 6 can be linked to R 7 and R 8 can be linked to R 9 to form a cyclic structure, with the proviso. One or more embodiments provide that R 6 and R9 Each of these is either hydrogen or a halogen such as fluorine. One or more embodiments are R 6 and R 9 Each of these is required to be hydrogen. One or more embodiments are R 6 and R 9 Each of these is provided to be a halogen such as fluorine. One or more embodiments are R 6 However, R 7 It can be connected to R 8 However, R 9 The condition is that it can be connected to form a ring structure.

[0012] As used herein, “alkyl” includes linear, branched, and cyclic paraffinic groups that lack one hydrogen atom. Therefore, for example, CH3 groups ("methyl") and CH3CH2 groups ("ethyl") are examples of alkyl groups.

[0013] As used herein, "aryl" includes phenyl, naphthyl, pyridyl, and other radicals whose molecules have a characteristic ring structure, such as benzene, naphthylene, phenanthrene, and anthracene. "Aryl" is C6-C 20 It is understood that it may also be an aryl group. For example, the C6H5-aromatic structure is "phenyl," and the C6H4-aromatic structure is "phenylene." "Aralkyl," which may also be called "arylalkyl" as used herein, is an alkyl group having an aryl group hanging from it. The "aralkyl" group is C7-C 20 It is understood that it may be an aralkyl group. "Alkylaryl" is an aryl having one or more alkyl groups attached thereto. As used herein, "hydrocarbyl" includes aliphatic, cyclic, olefinic, acetylene, and aromatic radicals (i.e., hydrocarbon radicals) containing one hydrogen-deficient hydrogen and carbon.

[0014] As mentioned above, R as shown in Equation I 4 and R 11Each of these can independently be hydrogen or a halogen such as fluorine. For example, one or more embodiments are R 4 and R 11 Each of these is required to be hydrogen. One or more embodiments are R 4 and R 11 Each of these is required to be fluorine.

[0015] As mentioned above, R as shown in Equation I 2 and R 13 Each of these is independent of (C1~C 20 ) may be alkyl, aryl, or aralkyl, or hydrogen. One or more embodiments are R 2 and R 13 Each of these is provided to be a (C3-C4) alkyl such as n-butyl, t-butyl, or 2-methylpentyl. One or more embodiments are R 2 and R 13 Each of these is provided to be 1,1,3,3-tetramethylbutyl. One or more embodiments are R 2 and R 13 Each of these is required to be (C1) alkyl, i.e., methyl.

[0016] As mentioned above, R as shown in Equation I 15 and R 16 Each of these may be 2,7-disubstituted carbazole-9-yl or 3,6-disubstituted carbazole-9-yl. For example, one or more embodiments are R 15 and R 16 Each of these is a 2,7-disubstituted carbazole-9-yl selected from the group consisting of 2,7-di-t-butylcarbazole-9-yl, 2,7-diethylcarbazole-9-yl, 2,7-dimethylcarbazole-9-yl, and 2,7-bis(diisopropyl(n-octyl)silyl)-carbazole-9-yl. One or more embodiments are R 15 and R 16Each of these is a 3,6-disubstituted carbazole-9-yl selected from the group consisting of 3,6-di-t-butylcarbazole-9-yl, 3,6-diethylcarbazole-9-yl, 3,6-dimethylcarbazole-9-yl, and 3,6-bis(diisopropyl(n-octyl)silyl)-carbazole-9-yl.

[0017] As described above, L as shown in Formula I may be a C3 alkylene or C4 alkylene that forms a bridge between the two oxygen atoms to which L is covalently bonded. For example, in one or more embodiments, L may be a saturated (C3-C4) alkyl that forms a 3-carbon or 4-carbon bridge between the two oxygen atoms to which L is bonded. For example, one or more embodiments may be conditional on L being a saturated (C3) alkyl that forms a bridge between the two oxygen atoms to which L is bonded. The term "saturated" means the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double or triple bonds. For example, one or more embodiments may be conditional on L being a saturated (C4) alkyl that forms a bridge between the two oxygen atoms to which L is bonded.

[0018] As mentioned above, each X shown in Equation I is independently a halogen, hydrogen, (C1~C 20 ) Alkyl, (C7~C 20 ) Aralkyl, (C1~C6) alkyl substitution (C6~C 12 )aryl, or (C1~C6) alkyl-substituted benzyl, -CH2Si(R C )3(However, R C (C1~C 12 It may be a hydrocarbon. For example, one or more embodiments are provided that each X is independently (C1)alkyl.

[0019] As described above, M as shown in formula I 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 are conditional on M being zirconium. One or more embodiments are conditional on M being hafnium.

[0020] The R group of formula I as described herein (R 1 ~R 16 Each of ) and X can independently be substituted or unsubstituted. For example, in some embodiments, each of X in formula I can independently be (C1~C6)alkyl-substituted (C6~C 12 )aryl or (C1-C6)alkyl-substituted benzyl. As used herein, “substituted” means that the group following the term has at least one part instead of one or more hydrogens at any position, the part being a halogen radical, hydroxyl group, carbonyl group, carboxyl group, amine group, phosphine group, alkoxy group, phenyl group, naphthyl group, (C1-C 20 ) alkyl groups, (C2~C 10 ) Selected from the group including alkenyl groups and combinations thereof. "Disubstituted" means that there are two or more substituents at any position, and that part is a halogen radical, hydroxyl group, carbonyl group, carboxyl group, amine group, phosphine group, alkoxy group, phenyl group, naphthyl group, (C1~C 20 ) alkyl groups, (C2~C 10 ) Selected from the group including alkenyl groups and combinations thereof.

[0021] The metallocene olefin polymerization catalyst and the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst described herein can be produced using the reactants described herein. The metallocene olefin polymerization catalyst and the biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst described herein can be produced by many processes, for example, using conventional solvents, reaction conditions, reaction times, and isolation procedures that are used to produce known catalysts such as known metallocene olefin polymerization catalysts.

[0022] One or more embodiments provide a biphenylphenol polymerization catalyst produced from a polymerization catalyst, i.e., a biphenylphenol polymerization pre-catalyst of formula I. The biphenylphenol polymerization catalyst is produced by contacting a biphenylphenol polymerization pre-catalyst and an activator under activation conditions, thereby providing a biphenylphenol polymerization catalyst, for example, an activated biphenylphenol polymerization pre-catalyst. The activation conditions are well known in the art.

[0023] As used herein, “activator” refers to any supported or unsupported compound or combination of compounds that can activate a complex or catalyst component, for example, by generating a cationic species of the catalyst component. For example, this may include abstraction of at least one leaving group from the metal center of the complex / catalyst component, for example, the “X” group described herein. As used herein, “leaving group” refers to one or more chemical moieties that are bonded to a metal atom and can be abstracted by the activator to generate a species that is active for olefin polymerization.

[0024] The activator may include Lewis acids or non-coordinating ionic activators or ionizing activators, or any other compounds including Lewis bases, aluminum alkyls, and / or conventional co-catalysts. In addition to the methylaluminoxanes ("MAO") and modified methylaluminoxanes ("MMAO") described above, exemplary activators include, but are not limited to, aluminoxanes or modified aluminoxanes, and / or neutral or ionic ionized compounds, such as dimethylanilinium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(pentafluorophenyl) borate, dimethylanilinium tetrakis(3,5-(CF3)2phenyl) borate, triphenylcarbenium tetrakis(3,5-(CF3)2phenyl) borate, and dimethylanilinium tetrakis(pentafluorophenyl) borate. Examples include borax (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.

[0025] Aluminoxanes may be described as oligomeric aluminum compounds having an -Al(R)-O- subunit (wherein 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 their respective trialkylaluminum compounds. MMAO can be produced by hydrolysis of trimethylaluminum with higher trialkylaluminum such as triisobutylaluminum. There are various known methods for preparing aluminoxanes and modified aluminoxanes. Aluminoxanes may include modified methylaluminoxane ("MMAO") type 3A (commercially available from Akzo Chemicals, Inc. under the trade name "Modified Methylaluminoxane Type 3A," as described in U.S. Patent No. 5,041,584). The MAO source may be, for example, a solution containing approximately 1% to 50% by weight of MAO. Examples of commercially available MAO solutions include 10% and 30% by weight MAO solutions available from Albemarle Corporation (Baton Rouge, Louisiana).

[0026] One or more organoaluminum compounds, such as one or more alkylaluminum compounds, can be used in combination with aluminoxanes. 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.

[0027] The metallocene olefin polymerization catalyst can be any metallocene olefin polymerization catalyst. In one or more embodiments, the metallocene olefin polymerization catalyst is (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 The following are selected from the group consisting of (nyl)2MX2, HN(CH2CH2N(2,4,6-Me3C6H2))2MX2, HN(CH2CH2N(2,3,4,5,6-Me5C6))2MX2, (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2, (butylcyclopentadienyl)2MX2, (propylcyclopentadienyl)2MX2, and mixtures thereof (wherein 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.

[0028] Polymers can be produced using a polymerization catalyst system that includes a biphenylphenol polymerization catalyst produced from a metalloceneolefin polymerization catalyst and a biphenylphenol polymerization pre-catalyst. For example, a polymer, such as a polyolefin polymer, can be produced by contacting the polymerization catalyst system with an olefin under polymerization conditions in a slurry phase polymerization reactor.

[0029] As used herein, “polymer” refers to a polymer having two or more identical or different polymer units derived from one or more different monomers, such as homopolymers, copolymers, and terpolymers. A “homopolymer” is a polymer having identical polymer units. A “copolymer” is a polymer having two or more polymer units that are different from each other. A “terpolymer” is a polymer having three polymer units that are different from each other. When referring to polymer units, “different” means that the polymer units differ from each other by at least one atom or are isomerically different. Therefore, the definition of copolymer as used herein includes terpolymers, etc. As used herein, “polymerization process” is a process used to produce a polymer.

[0030] The embodiments are subject to the condition 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 contain an olefin (e.g., produced from an olefin), the olefin present in such a polymer or copolymer is a polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 1% to 99% 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 1% to 99% by weight based on the total weight of the polymer. Higher α-olefin means an α-olefin having three or more carbon atoms.

[0031] Examples of polyolefins include polymers produced 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 containing 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 unconjugated 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, copolymers of ethylene are produced, where ethylene and a comonomer 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 slurry polymerization process. In another embodiment, ethylene and / or propylene can be polymerized with at least two different comonomers to produce a terpolymer, one of which may optionally be a diene.

[0032] One or more embodiments are provided that the polymer may contain 1 to 100% by weight of ethylene-derived units, based on the total weight of the polymer. This includes all individual values ​​and subranges of 1 to 100% by weight, but for example, the polymer may contain ethylene-derived units ranging from 1, 5, 10, or 50% by weight as the lower limit, to 100, 95, 90, 85, or 75% by weight as the upper limit, based on the total weight of the polymer.

[0033] A polymerization catalyst system comprising a biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization pre-catalyst of formula I can help provide a polymer through a polymerization process in a single slurry phase reactor. In one or more embodiments, the resulting polymer may 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 may be a multimodal polymer, such as a bimodal polyethylene composition containing a high molecular weight polyethylene component and a low molecular weight polyethylene component, where the high molecular weight polyethylene component and the low molecular weight polyethylene component are formed together in a single slurry phase reactor through a polymerization process using the polymerization catalyst system. Having high molecular weight polyethylene components and low molecular weight polyethylene components is desirable in some applications.

[0034] Surprisingly, a polymerization catalyst system comprising a biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization precatalyst of formula I of this disclosure can produce polymers containing high molecular weight polyethylene components having lower molecular weights compared to high molecular weight components in polymers formed using other (non-inventive) polymerization catalysts under similar polymerization conditions, as detailed herein. In some applications, high molecular weight polyethylene components having lower molecular weights than other high molecular weight polyethylene components are desirable.

[0035] The embodiments are provided that the polymer may have a number-average molecular weight (Mn) of 8,000 to 400,000. This includes all individual values ​​and subranges within the range of 8,000 to 400,000. For example, the polymer may have Mn ranging from a lower limit of 8,000, 10,000, 12,000, 40,000, or 84,000 to an upper limit of 400,000, 300,000, 250,000, 200,000, 150,000, or 100,000. In some embodiments, Mn may be in the range of 40,300 to 207,200.

[0036] The embodiments are provided that the polymer may have a weight-average molecular weight (Mw) of about 150,000 to about 800,000 under condition B and / or a molecular weight of less than about 500,000 Daltons under condition K. This includes all individual values ​​and subranges of 150,000 to 800,000, for example, the polymer may have an Mw from about 50,000, about 100,000, about 150,000, or about 200,000 as the lower limit, to about 800,000, about 700,000, or about 600,000 under condition K as the upper limit. Some embodiments are provided that the polymer may have a weight-average molecular weight (Mw) of 150,000 to 800,000 under condition K and / or a molecular weight of less than 500,000 Daltons under condition K. This includes all individual values ​​and subranges from 150,000 to 800,000. For example, a polymer can have Mw from 150,000 or 200,000 as a lower limit to 800,000, 700,000, or 600,000 as an upper limit under K conditions. In some examples, a polymer can have Mw from 50,000 to 500,000 under K conditions, or from 100,000 to 500,000 under K conditions. As used herein, B conditions are as follows: temperature is 100°C, ethylene is 100 pounds / square inch (psi), H2 / C2 is 0.0017, and C6 / C2 is 0.4. When used herein, the K conditions are as follows: temperature is 100°C, ethylene is 100 psi, H2 / C2 is 0.0068, and C6 / C2 is 0.4.

[0037] The embodiment is provided that the polymer may have a z-average molecular weight (Mz) between 200,000 and 10,000,000. This includes all individual values ​​and subranges between 200,000 and 10,000,000. For example, the polymer may have an 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.

[0038] The embodiment is provided that the polymer can have an Mz to Mw ratio in the range of 2.00 to 20.00. This includes all individual values ​​and subranges within 2.00 to 20.00, for example, the polymer can have an 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.

[0039] In some embodiments, the polymer may have an Mw-to-Mn ratio value greater than 2.00, greater than 3.00, greater than 4.00, or greater than 5.00. Some embodiments are conditional on the polymer having an Mw-to-Mn ratio in the range of 5.00 to 75.00. This includes all individual values ​​and subranges of 5.00 to 75.00, for example, the polymer may have an Mw-to-Mn ratio from a lower limit of 2.00, 3.00, 4.00, 5.00, 6.00, or 7.00 to an upper limit of 75.00, 60.00, 50.00, or 20.00.

[0040] The embodiment is provided that the polymer can have an Mz to Mw ratio smaller than the Mw to Mn ratio of the polymer.

[0041] The embodiment shows that when the polymer is measured according to ASTM D1238 (at 190°C and a 21kg load), the melt index (I) is in the range of 0.001 dg / min to 1000 dg / min. 21 This is subject to the condition that it can have ) all individual values ​​and subranges from 0.001 dg / min to 1000 dg / min.

[0042] The embodiments are provided that the polymer produced using a gas-phase polymerization reactor may have a melting temperature (Tm) of 110–135 degrees Celsius (°C). This includes all individual values ​​and subranges of 118–135°C, for example, the polymer may have a Tm ranging from a lower limit of 110, 113, 118, 119, or 120°C to an upper limit of 135, 133, 132, 130, or 128°C. The melting temperature (i.e., Tm) can be determined by differential scanning calorimetry according to ASTM D3418-08. For example, a scan rate of 10°C / min is used for a 10 mg sample, and a second heating cycle is used.

[0043] In this embodiment, the polymer is 0.890 g / cm³ 3 ~0.970g / cm 3 The condition is that it can have a density of 0.890~0.970 g / cm³. 3 This includes all individual values ​​and subranges, for example, polymers with lower limits of 0.890, 0.900, 0.910, 0.920, or 0.940 g / cm³. 3 Therefore, the upper limit is 0.970, 0.960, or 0.950 g / cm³. 3 It can have a density up to [a certain value]. The density can be determined according to ASTM D-792-13, Standard Test Method for Density and Specific Gravity (Relative Density) of Plastics Due to Displacement, Method B (Method for Testing Solid Plastics in Liquids Other Than Water, e.g., Liquid 2-Propanol). The result is expressed in grams per cubic centimeter (g / cm³). 3 Report in units of ).

[0044] 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, manufactured by Polymer Laboratories), M w , number average molecular weight (M n ), and M w / M nThe 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 involves using a solvent composed of BHT-treated TCB at a standard flow rate of 1.0 ml / min (mL) and a standard injection volume of 300 microliters (μL). The solvent is prepared by dissolving 6 grams of butylated hydroxytoluene (BHT, 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. The solvent is degassed using an in-line degasser before it enters the HTGPC instrument. The columns are calibrated using a series of monodisperse polystyrene (PS) standards. Separately, a known concentration of the test polymer dissolved in a solvent is prepared by heating a known amount of the test polymer in a known volume of solvent at 160°C for 2 hours with continuous shaking to obtain a solution. (All amounts are measured by gravimetric method.) The target solution concentration c of the test polymer is 0.5 to 2.0 milligrams (mg / mL) per milliliter of solution, with lower concentrations c used for high molecular weight polymers. The DRI detector is purged before performing measurements on each sample. Next, the flow rate in the instrument is increased to 1.0 mL / min, and the DRI detector is stabilized for 8 hours before injecting the first sample. Using the relationship between column calibration and universal calibration, M w and M n Calculate the formula:

[0045]

number

[0334] to

[0341] on pages 24-25 of U.S. Patent Application Publication No. 2006 / 0173123. dW / dLog(M W ), Log(M) on the x-axis W Plot the graph to obtain a GPC chromatogram. Note that Log(M W ) and dW / dLog(M W ) is as defined above.

[0046] Polymers can be used in many articles, particularly films, fibers, nonwovens and / or woven fabrics, extruded articles, and / or molded articles.

[0047] A polymerization catalyst system is provided for producing polymers via a slurry phase polymerization process, the polymerization catalyst system comprising a metallocene olefin polymerization catalyst and a supported biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization pre-catalyst of formula I, as detailed herein.

[0048] Biphenylphenol polymerization catalysts prepared from metallocene olefin polymerization catalysts and / or biphenylphenol polymerization pre-catalysts of formula I, as well as other components discussed herein, such as activators, may be used together with a carrier. The "carrier," which may also be referred to as "carrier," refers to any carrier material, including porous carrier materials such as talc, inorganic oxides, and inorganic chlorides.

[0049] Biphenylphenol polymerization catalysts produced from metallocene olefin polymerization catalysts and / or biphenylphenol polymerization pre-catalysts of formula I, as well as other components discussed herein, may be supported on the same or separate carriers, or one or more of the components may be used in an unsupported form. The use of carriers can be achieved by any technique used in the art. One or more embodiments are provided that a spray drying process is used. Spray drying processes are well known in the art. The carriers may be functionalized.

[0050] The carrier may be a porous carrier material, such as talc, an inorganic oxide, or an inorganic chloride. Other carrier materials include resin carrier materials, such as functionalized or crosslinked organic carriers like polystyrene, polystyrene-divinylbenzene polyolefin, or polymer compounds, zeolites, clays, or any other organic or inorganic carrier materials, or mixtures thereof.

[0051] Examples of carrier materials include inorganic oxides containing metal oxides of groups 2, 3, 4, 5, 13, or 14. Some preferred carriers include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Other carriers include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolite, talc, and clay. Combinations of these carrier materials, such as silica-chromium, silica-alumina, and silica-titania, can also be used. Further carrier materials include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads.

[0052] Examples of carriers include fumed silica available under the trade name Cabosil® TS-610, or other TS or TG series carriers available from Cabot Corporation. Fumed silica is typically silica having particles of 7 to 30 nanometers in size, treated with dimethylsilyl dichloride so that most of the surface hydroxyl groups are capped.

[0053] The carrier material is approximately 10 to 700 m 2 Surface area within the range of / g, approximately 0.1 to 4.0 g / cm³ 3 It may have a pore volume within the range and an average particle size within the range of about 5 to about 500 μm. More preferably, the surface area of ​​the carrier material is about 50 to about 500 m 2 The range is within / g, and the pore volume is approximately 0.5 to 3.5 g / cm³. 3 The particle size is within the range of approximately 10 to approximately 200 μm. Most preferably, the surface area of ​​the carrier material is approximately 100 to approximately 400 m². 2 The pore volume is within the range of / g, and is approximately 0.8 to 3.0 g / cm³. 3The average particle size is within the range of approximately 5 to approximately 100 μm. The average pore size of the carrier is typically in the range of 10 to 1000 Å, preferably 50 to approximately 500 Å, and most preferably 75 to approximately 350 Å.

[0054] A biphenylphenol polymerization catalyst prepared from a metalloceneolefin polymerization catalyst and / or a biphenylphenol polymerization pre-catalyst of formula I, and other components discussed herein, such as activators, may be slurryed. Slurries are well known in the art. A slurry may, for example, comprise a biphenylphenol polymerization catalyst prepared from a metalloceneolefin polymerization catalyst and / or a biphenylphenol polymerization pre-catalyst of formula I, an activator, and a support.

[0055] The molar ratio of the metal in the activator in the slurry to the metal in the metallocene olefin polymerization catalyst or the metal in the biphenylphenol polymerization catalyst prepared from the biphenylphenol polymerization pre-catalyst of formula I may be 20,000:1 to 0.5:1, 20,000:1 to 2000:1, 20,000:1 to 5,000:1, 20,000:1 to 10,000:1, 1000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. To facilitate the combination of any two or more components in the slurry, one or more diluents, such as fluids, may be used. For example, the biphenylphenol polymerization catalyst prepared from the metallocene olefin polymerization catalyst and / or the biphenylphenol polymerization pre-catalyst 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 may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. Next, a dry or mixed support with toluene may be added to the mixture, or a metal-ligand complex / activator may be added to the support. The slurry may be fed into the reactor for the polymerization process, and / or the slurry may be dried (e.g., spray-dried) before being fed into the reactor for the polymerization process.

[0056] As described above, the polymerization process may be a slurry phase polymerization process via a slurry phase polymerization reactor. The polymerization process may use known apparatus and reaction conditions, for example, known polymerization conditions. For example, the polymerization temperature may be in the range of about 0°C to about 300°C at atmospheric pressure, a pressure lower than atmospheric pressure, or a pressure higher than atmospheric pressure. Embodiments provide a method for producing a polyolefin polymer, comprising polymerizing an olefin by contacting it with a polymerization catalyst system described herein under polymerization conditions.

[0057] One or more embodiments are provided that the polymer can be formed via a slurry phase polymerization system at ultra-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 at temperatures in the range of 30°C to 130°C, 65°C to 110°C, 75°C to 120°C, or 80°C to 120°C. A stirred and / or fluidized bed slurry phase polymerization system may be used.

[0058] Generally, conventional slurry-phase fluidized bed polymerization processes can be carried out by continuously passing a flow containing one or more olefin monomers through a fluidized bed reactor at a rate sufficient to maintain a bed of suspended solid particles under reaction conditions, in the presence of a catalyst composition, for example, a polymerization catalyst system (a biphenylphenol polymerization catalyst produced from a metallocene olefin polymerization catalyst and a biphenylphenol polymerization pre-catalyst of formula I) and an activator. The flow containing unreacted monomers can be continuously withdrawn from the reactor, compressed, cooled, selectively partially or completely condensed, and recycled back into the reactor. The product, i.e., the polymer, can be removed from the reactor, and alternative monomers can be added to the recycled flow. Gases inert to the catalyst composition and reactants may also be present in the gas flow. The polymerization system may include, for example, a single reactor or two or more consecutive reactors.

[0059] The feed stream for the polymerization process may contain olefin monomers, non-olefin gases such as nitrogen and / or hydrogen, and may further contain one or more unreactive alkanes that are condensable in the polymerization process and can be used to remove reaction heat. Examples of unreactive alkanes include, but are not limited to, propane, butane, isobutane, pentane, isopentane, hexane, their isomers and derivatives. The feed can be introduced into the reactor at one or more different locations.

[0060] For the polymerization process, a polymerization catalyst (a metalloceneolefin polymerization catalyst and / or a biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization pre-catalyst of formula I) can be continuously supplied to the reactor.

[0061] For the polymerization process, hydrogen can be utilized in the reactor in a hydrogen-to-ethylene gas molar ratio, which can be in the range of approximately 0.0–3.5, approximately 0.0–1.0, 0.01–0.7, 0.03–0.5, 0.005–0.3, or 0.0017–0.0068. Some embodiments utilize hydrogen gas.

[0062] Several aspects of this disclosure are provided as follows:

[0063] Embodiment 1 provides the use of a supported biphenylphenol polymerization catalyst for producing a polymer via a slurry phase polymerization process, wherein the supported biphenylphenol polymerization catalyst is of formula I:

[0064] [ka] (In the formula, R 5 , R 7 , R 8 , and R 10 Each of these is independent of (C1~C 20 ) Alkyl, aryl, aralkyl, halogen, or hydrogen, R 4 and R 11Each of them is independently a halogen or hydrogen, and R 2 and R 13 Each of these is independent of (C1~C 20 ) Alkyl, aryl, or aralkyl, or hydrogen, R 15 and R 16 Each of them is independently a 2,7-disubstituted carbazole-9-yl or a 3,6-disubstituted carbazole-9-yl, L is a C3 alkylene or C4 alkylene that forms a bridge between the two oxygen atoms to which L is covalently bonded, and R 1 , R 3 , R 12 , and R 14 Each of them is independently a (C1-C8) alkyl, halogen, or hydrogen, and R 6 and R 9 Each of them is hydrogen, (C1-C8) alkyl, or halogen, and R is optionally selected. 6 R 7 It can be connected to R 8 R 9 They can be linked together to form a ring structure, and each X can independently be a halogen, hydrogen, (C1~C 20 ) Alkyl, (C7~C 20 ) Aralkyl, (C1~C6) alkyl substitution (C6~C 12 )aryl, or (C1~C6) alkyl-substituted benzyl, -CH2Si(R C )3, (however R C (C1~C 12 The biphenylphenol polymerization precatalyst is a hydrocarbon, and M is either zirconium (Zr) or hafnium (Hf).

[0065] Embodiment 2 provides the use of Embodiment 1, wherein the biphenylphenol polymerization precatalyst of formula I is selected from the group consisting of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv), and (xv) as described herein.

[0066] Embodiment 3 provides an embodiment in which a polymer formed under condition B (100°C and 100 pounds / square inch (psi) of ethylene, with H2 / C2 being 0.0017 and C6 / C2 being 0.4) has a molecular weight (Mw) in the range of about 150,000 daltons to about 800,000 daltons.

[0067] Embodiment 4 provides the use of Embodiment 1, wherein the polymer formed under K conditions (100°C and 100 psi, with H2 / C2 being 0.0068 and C6 / C2 being 0.4) has a molecular weight (Mw) of less than about 500,000 daltons. That is, in one or more embodiments, the polymer has a molecular weight in the range of about 150,000 to about 800,000 daltons under B conditions, or less than about 500,000 under K conditions.

[0068] Embodiment 5 provides a polymerization catalyst system for producing a polymer via a slurry phase polymerization process, comprising a metalloceneolefin polymerization catalyst and a supported biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization pre-catalyst of Embodiment 1.

[0069] Embodiment 6 provides a slurry phase polymerization method for producing a polymer, comprising polymerizing an olefin monomer in a slurry phase polymerization reactor in the presence of the polymerization catalyst system of Embodiment 5 to produce a polymer. That is, in various embodiments, part or all of the polymerization catalyst system (e.g., metallocene and / or biphenylphenol polymerization pre-catalyst / catalyst) is provided as a trim solution. For example, part of the metallocene catalyst may be provided as a trim solution. Alternatively, part of the biphenylphenol polymerization pre-catalyst / catalyst may be provided as a trim solution.

[0070] Embodiment 7 is R 15 and R 16 The present invention provides a polymerization catalyst system according to Embodiment 5 or a slurry phase polymerization method according to Embodiment 6, wherein each of the components is 3,6-di-t-butylcarbazole-9-yl.

[0071] Appearance 8 is R 15and R 16 The present invention provides a polymerization catalyst system of Embodiment 5 or a slurry phase polymerization method of Embodiment 6, wherein each of the components is 2,7-di-t-butylcarbazole-9-yl.

[0072] Embodiment 9 describes a metalloceneolefin polymerization catalyst, (Pentamethylcyclopentadienyl)(Propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(Propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, (methylcyclopentadienyl)(1,3-dimethyltetrahydroindenyl)MX2, (cyclopentadienyl)(1,3-dimethyltetrahydroindenyl)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 The present invention provides a polymerization catalyst system of embodiment 5 or a slurry phase polymerization method of embodiment 6, 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 alkyl or alkenyl groups of (C1-C5)).

[0073] Embodiment 10 provides a polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, wherein the high molecular weight polyethylene component and the low molecular weight polyethylene component are produced together in a single slurry phase reactor via a polymerization process using the polymerization catalyst system of Embodiment 5. [Examples]

[0074] A biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization precatalyst of formula (I), a polymerization catalyst system containing the biphenylphenol polymerization catalyst, and a comparative polymerization catalyst (excluding the one produced from the polymerization precatalyst of formula (I)) were prepared as follows.

[0075] A biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization precatalyst of formula (I), and a polymerization catalyst system containing the biphenylphenol polymerization catalyst were prepared as follows.

[0076] The biphenylphenol polymerization precatalyst of structure (i) was prepared as follows.

[0077] [ka]

[0078] Preparation of 4-dodecyl-2-iodo-6-methylphenol: 25 mL of acetonitrile was mixed with 4-dodecyl-2-methylphenol (2.12 g, 7.688 mmol) and p-toluenesulfonic acid monohydrate (1.48 g, 7.78 mmol). The mixture was stirred at 0-10°C (ice bath) for approximately 15 minutes, at which point N-iodosuccinimide (1.73 g, 7.668 mmol) was added. The reaction mixture became a thick slurry, so an additional 25 mL of acetonitrile was added and stirring was resumed. The reaction mixture was heated to room temperature and stirred for 24 hours, at which point approximately 16% of the starting material remained. Therefore, an additional 0.3 equivalents of N-iodosuccinimide (0.52 g, 2.30 mmol) were added to the reactant, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was concentrated to dryness, dissolved in methylene chloride (50 mL), washed with 10 wt% aqueous sodium thiosulfate solution (3 × 50 mL), washed with water, then brine (50 mL each), dried over anhydrous MgSO4, filtered through a silica gel pad, and then concentrated to obtain 2.80 g of the crude compound (purity approximately 95% by GC-MS) as an off-white solid. The product was recrystallized from hexane (8 mL) to obtain 1.79 g (58.0%) of the pure product.

[0079] 1 H NMR (400MHz, CDCl3) δ 7.29(s, 1H), 6.89(s, 1H), 2.46(t, 2H), 2.28(s, 3H), 1.55(br s, 2H), 1.27(br s, 18H), 0.89(t, 3H).

[0080] [ka]

[0081] Preparation of 1,3-bis(4-dodecyl-2-iodo-6-methylphenoxy)propane: 4-dodecyl-2-iodo-6-methylphenol (1.63 g, 4.05 mmol), K2CO3 (1.19 g, 8.61 mmol), and propane-1,3-diylbis(4-methylbenzenesulfonate) (0.78 g, 2.03 mmol) were added to dimethylformamide (25 mL). The reaction mixture was heated at 100 °C for 30 minutes, cooled thereafter, and concentrated to dryness by rotary evaporation. The residue was dissolved in 1:1 methylene chloride and water (100 mL) and extracted into methylene chloride (three times in 50 mL increments). The combined organic phases were washed with 200 mL each of 2N NaOH, water, and then brine, dried over anhydrous MgSO4, filtered through a small silica gel pad, and concentrated to obtain 1.6 g of the compound as a brownish oily substance. This crude product was recrystallized from hexane (10 mL) to obtain 1.32 g (77.1%) of the product as a white, fluffy powder.

[0082] [ka]

[0083] To 40 mL of dimethyl ether, 2.35 g of 94.2% purity (3.19 mmol) 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (prepared as described in International Publication No. 2017 / 004462A1), 1.274 g (1.508 mmol) of 1,3-bis(4-dodecyl-2-iodo-6-methylphenoxy)propane, and 0.447 g of NaOH (11.2 mmol) were added in 11 mL of water and 15 mL of THF. The reaction mixture was sparged with N2 for approximately 15 minutes, then 112 mg (0.097 mmol) of Pd(PPh3)4 was added, and the mixture was heated at 85°C for 48 hours, followed by cooling. After cooling, a precipitate formed, which was isolated by vacuum filtration and dried under high vacuum for approximately 2 hours. This crude protection product was used directly in the next step. To the crude protection ligand, 150 mL of 1:1 methanol / THF and approximately 100 mg of PTSA were added. The solution was heated at 60°C for 6 hours, cooled, and concentrated. The crude ligand was placed on methylene chloride, washed with brine, dried on anhydrous magnesium sulfate, filtered through a silica gel pad, and then concentrated to obtain the crude ligand. This crude product was placed on hexane and purified by flash chromatography using an ISCO purification system (2% ethyl acetate in hexane, homogeneous concentration) to obtain 2.30 g (97.5%) of pure ligand. To the crude protective ligand, 150 mL of 1:1 methanol / THF and approximately 100 mg of PTSA were added. The solution was heated at 60°C for 6 hours, cooled, and concentrated. The crude ligand was placed on methylene chloride, washed with brine, dried on anhydrous magnesium sulfate, filtered through a silica gel pad, and concentrated to obtain the crude ligand. This crude product was placed on hexane and purified by flash chromatography using an ISCO purification system (2% ethyl acetate in hexane, homogeneous concentration) to obtain 2.30 g (97.5%) of pure ligand.

[0084] 1H NMR (400MHz, CDCl3)δ 8.05(d, 4H), 7.46(dd, 4H), 7.33(dd, 4H), 7.15(d, 4H), 7.10(d, 2H), 6.98(d, 2H), 6.38(br s, 2H), 3.72(t, 4H), 2.63(t, 4H), 2.00(s, 6H), 1.79(br s, 6H), 1.68(quintet, 4H), 1.32(br m, 86H), 0.93(t, 6H), 0.85(s, 18H).

[0085] [ka]

[0086] HfCl4 (0.0516 g, 0.161 mmol) and toluene (10 mL) were added to a jar equipped with a stirring rod in a nitrogen-purged glove box. The resulting slurry was cooled in a glove box freezer at -30°C. Methylmagnesium bromide in diethyl ether (3.0 M, 0.22 mL, 0.66 mmol) was added to the stirred-cooled slurry. The mixture was vigorously stirred for about 4 minutes. The solid dissolved, and the mixture turned pale yellow. Next, the ligand (0.2500 g, 0.161 mmol) was added to the mixture as a solid. The resulting mixture was stirred at ambient temperature for 2 hours. Then, hexane (10 mL) was added to the mixture, and the mixture was filtered the following day. The colorless solid was concentrated under vacuum to obtain 0.2145 g of the structure i product as a white solid (yield was 75.8%).

[0087] 1 H NMR (400MHz, C6D6)δ 8.24(d, 2H), 8.06(d, 2H), 8.01(d, 2H), 7.88(d, 2H), 7.80(d, 2H), 7.58(d, 2H), 7.54(dd, 2H), 7.35(dd, 2H), 7.12(d, 2H), 6.51(d, 2) H), 3.64 (quintet, 2H), 3.40 (quintet, 2H), 2.24 (t, 4H), 1.80 (d, 2H), 1.65 (d, 2H), 1.62 (s, 18H), 1.28 (m, 90H), 0.93 (s, 30H), -0.78 (s, 6H).

[0088] [ka]

[0089] As used herein, "Me" refers to methyl, "Et" refers to ethyl, and "n-Oct" refers to n-C8H 17 "tBu" refers to tert-butyl, and "n-Pr" refers to n-C3H7.

[0090] The biphenylphenol polymerization precatalyst of structure (ii) was prepared as follows.

[0091] The ligand was prepared as described above in the synthesis of structure i.

[0092] [ka]

[0093] ZrCl4 (0.0376 g, 0.161 mmol) and toluene (10 mL) were added to a jar equipped with a stirring rod in a nitrogen-purged glove box. The resulting slurry was cooled in a glove box freezer at -30°C. Methylmagnesium bromide in diethyl ether (3.0 M, 0.23 mL, 0.69 mmol) was added to the stirred-cooled slurry. The mixture was vigorously stirred for about 4 minutes. The solid dissolved, and the mixture turned pale yellow. Next, the ligand (0.2505 g, 0.161 mmol) was added to this mixture as a solid. The resulting mixture was stirred at ambient temperature for 2 hours. Then, hexane (10 mL) was added to the mixture, and the mixture was filtered the following day. The colorless solid was concentrated under vacuum to obtain 0.2640 g of the structure ii product as a white solid (yield was 97.9%).

[0094] 1H NMR (400MHz, C6D6)δ 8.24(d, 2H), 8.05(d, 2H), 8.01(d, 2H), 7.85(d, 2H), 7.58(d, 2H), 7.54(dd, 2H), 7.34(dd, 2H), 7.13(d, 2H), 6.50(d, 2H), 3.55 (quintet, 2H), 3.40 (quintet, 2H), 2.24 (t, 4H), 1.81 (d, 2H), 1.66 (d, 2H), 1.61 (s, 18H), 1.28 (m, 100H), 0.94 (s, 18H), -0.58.

[0095] [ka]

[0096] The biphenylphenol polymerization precatalyst of structure (iii) was prepared as follows.

[0097] [ka]

[0098] Preparation of 4,4'-diethyl-2-nitro-1,1'-biphenyl: A three-necked round-bottom flask was fitted with a magnetic stirring rod, thermowell, addition funnel, and septum. The flask was filled with 4,4'-diethylbiphenyl (15.0089 g, 71.366 mmol) and acetic anhydride (382 mL, 4041 mmol). The solution was cooled using an ice bath (internal temperature 2.9°C). A mixture of nitric acid (12.0 mL, 209.4 mmol) and acetic acid (6.5 mL, 152.7 mmol) was added dropwise over 10 minutes. The internal temperature was monitored to ensure it did not exceed 10°C. The temperature at the end of the addition was 8.6°C, and the maximum temperature reached was 10.0°C. The mixture was sampled by GC / MS after 10 minutes, indicating that the reaction was complete. After 20 minutes, the reaction mixture was poured into a beaker containing approximately 2 L of ice water (mostly ice) and stirred for 1.5 hours. The yellow oily substance was separated from the aqueous phase. The mixture was transferred to a separatory funnel and 285 mL of dichloromethane was added to the mixture. The mixture was thoroughly mixed and separated. The organic phase was separated and washed with 230 mL of water and 230 mL of 1 M aqueous NaOH solution. The yellow solution was dried over anhydrous magnesium sulfate and filtered. The solution was concentrated by rotary evaporation at a bath temperature starting at 35°C and reaching 50°C to obtain a crude yellow oily substance (22.46 g). The oily substance was chromatographed using a 330 g silica gel Grace column in an Isco CombiFlash system with a gradient of 10–20% dichloromethane in hexane until the product eluted. The fractions were analyzed by GC / MS and TLC (5% ethyl acetate in hexane). The pure fractions were combined, concentrated by rotary evaporation, and dried under high vacuum to obtain 15.75 g (86.5%) of the product as a yellow oily substance.

[0099] 1¹H NMR (400 MHz, CDCl₃) δ 7.64 (d, J=1.7 Hz, 1H), 7.40 (dd, J=7.9, 1.8 Hz, 1H), 7.32 (d, J=7.9 Hz, 1H), 7.25-7.20 (m, 4H), 2.73 (q, J=7.6 Hz, 2H), 2.68 (q, J=7.6 Hz, 2H), 1.28 (t, J=7.6 Hz, 3H), 1.26 (t, J=7.6 Hz, 3H). 13 ¹³C NMR (101 MHz, CDCl₃) δ 149.22, 144.50, 143.95, 134.54, 133.42, 131.68, 131.64, 128.04, 127.73, 123.02, 28.43, 28.04, 15.21, 14.96.

[0100] [[Chem.]]

[0101] Preparation of 2,7-diethyl-9H-carbazole: A three-necked round-bottom flask equipped with a magnetic stirring rod was placed in a glove box under a nitrogen atmosphere. The flask was filled with 4,4'-diethyl-2-nitro-1,1'-biphenyl (20.580 g, 80.608 mmol) and triethyl phosphite (81 mL). The flask was sealed with a septum and transferred to a fume hood equipped with a condenser and nitrogen gas inlet. The yellow solution was heated under reflux (heating mantle temperature 175°C), and samples were taken for GC / MS analysis after 2 and 4 hours of reflux (0.1 mL of sample diluted in dichloromethane). After 4 hours, only trace amounts of the starting material were observed. A major peak with the molecular weight of the desired product was observed. Therefore, the reaction mixture was cooled to room temperature. A white crystalline precipitate was observed. The reaction mixture was stored in the freezer overnight. A white crystalline solid (Crop 1) was collected by vacuum filtration while cold and washed five times with 20 mL of cold ethanol. The solid was dried. The filtrate was placed in the freezer again overnight. The crystalline solid (Crop 2) that precipitated in the mother liquor was collected by vacuum filtration while cold and washed five times with 10 mL of cold ethanol. Both solids were transferred to vials and placed under high vacuum. 8.2640 g of crystalline solid was obtained from Crop 1 and 2.3351 g of crystalline solid was obtained from Crop 2. The total yield of the product was 10.5991 g (58.9%).

[0102] 1 H NMR (400MHz, DMSO-d6)δ 7.93 (d. 13 C NMR (101MHz, DMSO-d6) δ 140.94, 140.27, 120.51, 119.54, 118.75, 109.55, 28.80, 16.15.

[0103] [ka]

[0104] Preparation of 2,7-diethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole: A three-necked round-bottom flask was fitted with a stirring rod and placed in a glove box under a nitrogen atmosphere. The flask was filled with 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (24.48 g, 58.798 mmol), 2,7-diethyl-9H-carbazole (9.595 g, 42.965 mmol), tripotassium phosphate (31.04 g, 146.229 mmol), and dry toluene (114 mL). In a glove box, copper iodide (0.2860 g, 1.502 mmol) was added to a 20 mL vial and diluted with toluene (1 mL). The flask and the vial containing the copper iodide solution were removed from the glove box and placed in a fume hood. A nitrogen gas inlet and condenser were attached to the flask. N,N-dimethylethylenediamine (0.602 mL, 5.593 mmol) was added to the copper iodide solution, and the resulting slurry was added to the reaction mixture. The mixture was heated at 125 °C (heated mantle temperature). After 24 hours, GC analysis showed approximately 84.74% conversion, with 15.26% carbazole remaining. Therefore, an additional anhydrous copper iodide (0.2827 g, 1.484 mmol) slurry and N,N-dimethylethylenediamine (0.602 mL, 5.593 mmol) in dry toluene (1 mL) were added. The reaction mixture was stirred at 125°C for a further 24 hours. After 48 hours, GC analysis showed approximately 97.60% conversion, with 2.40% carbazole remaining. The reaction mixture was cooled to room temperature, filtered through a small silica plug, washed three times with 75 mL of tetrahydrofuran, and concentrated by rotary evaporation to obtain the crude product as a dark brown oil (35.15 g), which eventually solidified. Since the solid did not recrystallize from hexane (75 mL), the solution was concentrated by rotary evaporation to obtain a dark brown oil, which also eventually solidified. This substance was dissolved in hot hexane (25 mL), filtered while hot through cotton using a glass funnel, and recrystallized. The resulting slurry was overly concentrated.The slurry was heated to dissolve the solid, and the resulting solution was concentrated by rotary evaporation to obtain a dark brown oily substance, which eventually turned into a solid. The solid was recrystallized from hexane (50 mL) to obtain light brown crystals. The crystals were recovered by vacuum filtration, washed twice with 10 mL each of cold hexane, and dried under high vacuum to obtain 14.2792 g (64.9%) of the product as light brown crystals.

[0105] 1 H NMR(400MHz, CDCl3+TMS)δ 7.95(d, J=7.9Hz, 2H), 7.47(d, J=2.4Hz, 1H), 7.42(dd, J=8.7, 2.5Hz, 1H), 7.33(d, J=8.6Hz, 1H), 7.06( dt, J=8.0, 1.2Hz, 2H), 7.06~7.00(m, 1H), 6.99~6.93(m, 1H), 5.26(t, J=2.9Hz, 1H), 3.70(td, J=11.1, 2. 9Hz, 1H), 3.46(dt, J=11.2, 3.7Hz, 1H), 2.73(q, J=7.6Hz, 4H), 1.74(s, 2H), 1.45~1.34(m, 2H, overlapping with two singlets at 1.38 and 1.37 ppm), 1.38(s, 3H), 1.37(s, 3H), 1.25(t, J=7.6, Hz, 8H), 1.15~1.09(m, 2H), 0.82(s, 9H). 13 C NMR (101MHz, CDCl3+TMS)δ 151.07, 144.12, 142.07, 142.03, 141.55, 141.53, 127.76, 126.69, 126.30, 121.29, 121.16, 119.61, 119.57, 119.48, 119.41, 116.29, 109.53, 108.95, 96.85, 61.47, 57.07, 38.19, 32.38, 31.85, 31.62, 31.46, 29.99, 29.49, 25.06, 17.66, 16.11, 16.07.

[0106] [ka]

[0107] Preparation of 2,7-diethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole: A three-necked round-bottom flask was fitted with a magnetic stirring rod, septum, and nitrogen gas inlet. The flask was filled with 2,7-diethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (10.0012 g, 19.544 mmol) and dry tetrahydrofuran (130 mL). This solution was cooled to 0-10°C for about 15 minutes using an ice bath, and 2.5 M n-butyllithium in hexane (20,500 mL, 51,250 mmol) was slowly added. The color of the solution changed from clear pale yellow to clear dark yellow. After stirring for 4 hours, 2-iso-propoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10,200 mL, 49.9967 mmol) was slowly added. The solution changed from clear dark yellow to cloudy pale yellow. The mixture was stirred at 0-10°C for 1 hour, then the reactants were warmed to room temperature and stirred overnight. Cold saturated sodium bicarbonate aqueous solution (110 mL) was added to the reaction mixture. The aqueous phase was extracted four times with 75 mL each of dichloromethane. The organic phases were combined, washed with cold saturated sodium bicarbonate aqueous solution (290 mL), washed with brine (290 mL), then dried on anhydrous magnesium sulfate, and filtered by vacuum filtration. The filtrate was concentrated by rotary evaporation and placed under high vacuum to obtain the crude product as a pale yellow foam (13.76 g). The foam was slurryed in acetonitrile (50 mL), then stirred at room temperature for 30 minutes, and the white solid was isolated by vacuum filtration. The solid was washed twice with 20 mL each of cold acetonitrile and dried under high vacuum to obtain 7.8165 g (62.7%) of the product as an off-white solid.

[0108] 11H NMR (400 MHz, CDCl3) δ 7.93 (d, J=7.9 Hz, 2H), 7.93 (d, J=7.9 Hz, 2H), 7.84 (dd, J=2.6, 0.8 Hz, 1H), 7.45 (dd, J=2.5, 0.8 Hz, 1H), 7.06 (d, J=8.0 Hz, 2H), 7.05 (d, J=8.0 Hz, 2H), 7.02 (s, 1H), 7.00 (s, 1H), 5.00~4.96 (m, 1H), 2.81~2.69 (m, 5H), 2.62 (dt, J=11.2, 3.9 Hz, 1H), 1.72 (s, 2H), 1.67~1.62 (m, 1H), 1.42~1.34 (m, 18H), 1.27~1.05 (m, 8H), 1.21~1.06 (m, 1H), 1.04~0.92 (m, 1H), 0.83~0.77 (m, 9H). 13 13C NMR (101 MHz, CDCl3) δ 156.44, 145.68, 142.11, 142.01, 141.71, 141.68, 133.85, 130.95, 129.45, 121.25, 121.01, 119.57, 119.54, 119.23, 119.21, 109.70, 109.51, 101.27, 83.61, 61.20, 56.95, 38.30, 32.37, 31.88, 31.41, 31.36, 30.02, 29.48, 29.45, 25.02, 25.00, 24.75, 18.19, 16.22, 16.16.

[0109]

Chemical

[0110] Preparation of 2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-diethyl-9H-carbazole-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol): A three-necked round-bottom flask was fitted with a magnetic stirring rod, septum, condenser, and nitrogen gas inlet. The flask was filled with 2,7-diethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (3.6936 g, 5.792 mmol), 1,2-dimethoxyethane (72 mL), a solution of NaOH (0.7647 g, 19.118 mmol) in water (21 mL), tetrahydrofuran (24 mL), and 1,3-bis(4-fluoro-2-iodo-6-methylphenoxy)propane (1.5002 g, 2.757 mmol). The mixture was purged with nitrogen for approximately 15 minutes, and then tetrakis(triphenylphosphine)palladium(0) (0.2368 g, 0.2049 mmol) was added. The mixture was heated under reflux at 85°C for 48 hours, and then cooled to room temperature. After cooling, the ligand remained in the solution. The mixture was transferred to a separatory funnel for phase separation. The phases did not completely separate. Water (30 mL) was added to the mixture, but the phases still did not completely separate. Dichloromethane (30 mL) was added to the mixture to separate the four phases. The organic phases were combined. The aqueous phases were combined and extracted with dichloromethane (30 mL). All organic phases were combined, dried on magnesium sulfate, and filtered by vacuum filtration. The flask was washed twice with 15 mL each of dichloromethane and filtered into a filter flask containing the organic phases. The organic solution was concentrated by rotary evaporation to obtain a reddish-brown oily substance (5.66 g) as the crude protective ligand. ligand 1 The reaction was analyzed by 1H NMR. The protected ligand was dissolved in a mixture of tetrahydrofuran (200 mL) and methanol (200 mL), and then heated to 60°C. To the solution, p-toluenesulfonic acid (0.0556 g, 0.2922 mmol) was added, and the reaction mixture was stirred at 60°C for 8 hours, then cooled to room temperature.1 The reaction was analyzed by 1H NMR to determine the completion of the reaction. The ligand was considered to be deprotected. The ligand was concentrated by rotational evaporation to obtain a brown, viscous substance (4.86 g). The ligand did not recrystallize in acetonitrile (10 mL) at room temperature. The ligand was concentrated to obtain a brown, viscous solid, dissolved in a small amount of dichloromethane, and analyzed on an Isco CombiFlash system 220 Grace column using a gradient of 35-40% dichloromethane in hexane until the ligand eluted. The fraction was analyzed by TLC (40% dichloromethane in hexane), and the pure fraction was concentrated by rotational evaporation to obtain 1.59 g of a pale yellow solid. The fraction containing a small amount of impurities was also concentrated by rotational evaporation to obtain 1.16 g of a pale yellow solid. Both solids were... 1 Analysis by 1H NMR revealed that the substance was not deprotected. The solids were combined and deprotection was repeated. The ligand was dissolved in a mixture of tetrahydrofuran (200 mL) and methanol (200 mL), and then heated to 60°C. p-toluenesulfonic acid monohydrate (0.2864 g, 1.506 mmol) was added to the solution until the solution became acidic (pH = 1~3). After 8 hours, the substance was... 1 The deprotection was confirmed by analysis by 1H NMR, and then cooled to room temperature. The substance was concentrated to form a yellow, viscous solid, dissolved in a small amount of dichloromethane, and filtered on an Isco CombiFlash system 120 Grace column using a 35-40% dichloromethane gradient in hexane until the ligands eluted. The pure fraction was concentrated by rotational evaporation to obtain 0.7084 g of a pale yellow crystalline solid. 1 Analysis was performed by 1H NMR. The fraction containing small amounts of impurities was concentrated by rotational evaporation, dissolved in a small amount of dichloromethane, and filtered on an Isco CombiFlash system 220 Grace column using a gradient of 35-40% dichloromethane in hexane. The pure fraction was concentrated by rotational evaporation to obtain 1.3092 g of pale yellow crystalline solid. 1 Analysis was performed by 1H NMR. The total yield was 2.0176 g (64.0%) of the product as a white crystalline solid.

[0111] 1 H NMR (400MHz, CDCl3)δ 7.98(d, J=7.9Hz, 4H), 7.43(d, J=2.4Hz, 2H), 7.41(d, J=2.5Hz, 2H), 7.07(dd, J=8 .0, 1.4Hz, 4H), 6.98(dd, J=8.9, 3.1Hz, 2H), 6.88(s, 4H), 6.81(dd, J=8.6, 3.1Hz, 2 H), 6.56(s, 2H), 3.65(t, J=6.4Hz, 4H), 2.65(q, J=7.6Hz, 8H), 1.94(s, 6H), 1.77( p, J=6.8Hz, 2H), 1.73(s, 4H), 1.37(s, 12H), 1.17(t, J=7.6Hz, 12H), 0.79(s, 18H). 13 ¹³C NMR (10¹ MHz, CDCl3) δ 160.20, 157.78, 149.70, 149.68, 147.86, 143.01, 141.95, 141.85, 133.53, 133.44, 133.01, 132.93, 128.98, 127.92, 126.47, 126.45, 125.47, 121.40, 119.97, 119.79, 117.40, 117.18, 116.20, 115.97, 108.67, 70.80, 57.16, 38.20, 32.43, 31.81, 31.56, 30.62, 29.45, 16.30, 16.28, 16.03. [Multiplicity due to carbon-fluorine bonding was not identified.] 19 F NMR (376MHz, CDCl3) δ-118.04 (t, J=8.8Hz). HRMS(ESI, M+NH4 + ):C 77 H 92 The calculated (m / z) value for F2N3O4 was 1160.705, while the measured value was 1160.704.

[0112] [ka]

[0113] Preparation of structure (iii): A jar was filled with HfCl4 (0.1410 g, 0.4372 mmol) and toluene (27 mL). The slurry was cooled to -25°C for 30 minutes in a glove box freezer. 3.0 M methylmagnesium bromide in diethyl ether (0.60 mL, 1.8 mmol) was added to the cold, stirring slurry. The mixture was stirred vigorously for 2 minutes. The solid turned into a solution, but the reaction solution was cloudy. Ligand (0.5000 g, 0.4372 mmol) was added to this solution as a solid. The vial containing the solid was rinsed with toluene (3.0 mL). The rinsing solvent was added to the reaction mixture. After stirring for 2 hours, the brownish reaction mixture was filtered under vacuum using a frit glass funnel. The cake was washed twice with 5 mL each of toluene. Hexane (20 mL) was added to the filtrate (a clear, pale yellow solution). The resulting turbid solution was filtered and concentrated under high vacuum to obtain 0.5933 g (100.5%) of the product as a pale yellow solid. The excess yield was due to the presence of toluene, which is difficult to remove.

[0114] 1 H NMR (400MHz, C6D6)δ 8.17(d, J=7.9Hz, 2H), 8.04(d, J=7.9Hz, 2H), 7.85(d, J=2.5Hz, 2H), 7.76(s, 2H), 7.65(s, 2H), 7.28~7.26(m, 4H), 7 .11(dd, J=8.0, 1.5Hz, 2H), 6.74(dd, J=9.0, 3.2Hz, 2H), 6.08(dd, J=8.2, 3.2Hz, 2H), 3.48(dt, J=9.9, 4.8Hz, 2H), 3. 19(dt, J=10.6, 5.5Hz, 2H), 3.02~2.89(m, 4H), 2.70~2.54(m, 4H), 1.66(d, J=14.6Hz, 2H), 1.61(d, J=14.6Hz, 4H), 1 .44(t, J=7.6Hz, 6H), 1.27(m and s, 8H), 1.22(s, 6H), 1.19(s, 6H), 1.13(t, J=7.6Hz, 6H), 0.86(s, 18H), -0.70(s, 6H). 13C NMR (101MHz, C6D6)δ 161.59, 159.14, 153.64, 149.53, 149.50, 142.81, 142.46, 141.56, 141.32, 140.7 0, 135.72, 135.63, 135.00, 134.92, 130.50, 127.03, 123.94, 121.63, 120.90, 120. 69, 120.44, 119.91, 118.02, 117.79, 117.52, 117.30, 113.22, 110.12, 76.13, 57.65, 49.77, 38.25, 32.66, 31.99, 30.97, 30.41, 30.27, 30.10, 17.14, 16.30, 16.20. [Multiplicity due to carbon-fluorine bonding was not identified]. 19 F NMR (376MHz, C6D6) δ-115.12 (d, J=8.7Hz).

[0115] [ka]

[0116] The biphenylphenol polymerization precatalyst of structure (iv) was prepared as follows.

[0117] [ka]

[0118] Preparation of 4,4'-dimethyl-2-nitro-1,1'-biphenyl: A three-necked round-bottom flask was fitted with a magnetic stirring rod, thermowell, addition funnel, and septum. The flask was placed under a nitrogen atmosphere and filled with 4,4'-dimethylbiphenyl (5.7972 g, 31.806 mmol) and acetic anhydride (170 mL, 1798.4 mmol). The solution was cooled in an ice bath (internal temperature 3.8°C). While monitoring to ensure the internal temperature did not exceed 10°C, a mixture of nitric acid (3.3 mL, 69.8 mmol) and acetic acid (5.3 mL, 92.5 mmol) was added dropwise in succession. After 10 minutes at 0-10°C, a sample was taken by GC / MS. GC / MS showed the conversion of the starting biphenyl to the product, and the reaction was determined to be complete. After 25 minutes, the reaction mixture was poured into a beaker of ice water (mainly ice) (850 mL) and stirred for 1.5 hours. The yellow oily substance was separated from the aqueous phase. The mixture was transferred to a separatory funnel, and dichloromethane (127 mL) was added to separate the phases. The organic phase was washed with water (100 mL) and then with 1 M aqueous sodium hydroxide solution (100 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered by vacuum filtration, and concentrated by rotary evaporation to obtain the product as a crude orange oily substance (10.8926 g). The oily substance was packed into an Isco CombiFlash system and chromatographic chromatography was performed using a 330 g Grace column with a gradient of 15-20% dichloromethane in hexane until the product eluted. The fractions were analyzed by TLC. The pure fractions were combined, concentrated by rotary evaporation, and dried under high vacuum to obtain 5.07 g (70.1%) of the product as a yellow solid.

[0119] 1 H NMR (400MHz, CDCl3+TMS) δ 7.62~7.58(m, 1H), 7.36(ddd, J=7.9, 1.8, 0.8Hz, 1H), 7.28(d, J=7.8Hz, 1H), 7.22~7.15(m, 4H), 2.42(s, 3H), 2.36(s, 3H). 13C NMR (101MHz, CDCl3+TMS) δ 149.10, 138.30, 137.76, 134.33, 133.25, 132.84, 131.59, 129.28, 127.68, 124.19, 21.11, 20.70.

[0120] [ka]

[0121] Preparation of 2,7-dimethyl-9H-carbazole: In a glove box, a three-necked round-bottom flask equipped with a magnetic stirrer and septum was filled with 4,4'-dimethyl-2-nitro-1,1'-biphenyl (4.9855 g, 21.937 mmol) and triethyl phosphite (22 mL, 128 mmol). In a fume hood, a condenser and nitrogen gas inlet were attached to the flask. The yellow slurry was placed under a nitrogen atmosphere, heated under reflux (heating mantle temperature 175°C), and sampled for GC / MS analysis. The yellow slurry eventually changed to a brown solution. After 2 hours, GC / MS showed product formation and residual starting material. After 5 hours, only trace amounts of starting material were observed, and the reaction was determined to be complete. The reactants were then cooled to room temperature. A white crystalline precipitate was observed. The reaction mixture was stored overnight in a freezer. A white crystalline solid (crop 1) was collected by vacuum filtration, washed with cold ethanol (5.5 mL each, 5 times), and dried under high vacuum to obtain 1.62 g of product as a white crystalline solid. The filtrate was placed in a freezer over the weekend. A white crystalline precipitate was observed. A white crystalline solid (crop 2) was collected by vacuum filtration, washed with cold ethanol (5.5 mL each, 5 times), and dried under high vacuum to obtain 0.62 g of product as a white crystalline solid. The total yield obtained was 2.24 g (52.2%) of product as a white crystalline solid.

[0122] 1 H NMR (400MHz, DMSO-d6) δ 10.96(s, 1H), 7.87(d, J=7.9Hz, 2H), 7.25(s, 2H), 6.93(d, J=7.9Hz, 2H), 2.45(s, 6H).13 C NMR (101MHz, DMSO-d6) δ 140.23, 134.33, 120.32, 119.87, 119.47, 110.82, 21.67.

[0123]

change

[0124] Preparation of 2,7-dimethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (13) (201303282-6): A three-necked round-bottom flask was fitted with a magnetic stirring rod and septum. In a glove box, the flask was filled with 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (6.9934 g, 16.797 mmol), 2,7-dimethyl-9H-carbazole (2.2032 g, 10.408 mmol), tripotassium phosphate (7.5577 g, 35.604 mmol), and dry toluene (25 mL). In a glove box, anhydrous copper iodide (0.0676 g, 0.3549 mmol) and N,N-dimethylethylenediamine (0.1456 mL, 1.353 mmol), slurryed in dry toluene (1 mL), were added to the reaction mixture. In a fume hood, a condenser and nitrogen gas inlet were attached to the flask. The reaction mixture was placed under a nitrogen atmosphere and heated at 125°C (heated mantle temperature). After 24 hours, HPLC analysis showed product formation and residual starting carbazole. Therefore, additional anhydrous copper iodide (0.0667 g, 0.3502 mmol) and N,N-dimethylethylenediamine (0.1456 mL, 1.353 mmol), slurryed in dry toluene (1 mL), were added. The reaction mixture was continued to stir at 125°C for another 24 hours. After 48 hours, HPLC analysis showed little change in the consumption of starting carbazole, so the reaction was stopped at this point. Next, the reaction mixture was cooled to room temperature. The reaction mixture was filtered by vacuum filtration through a small silica plug. The plug was washed with tetrahydrofuran (three times with 50 mL each), and the filtrate was concentrated by rotary evaporation to obtain the product as a crude brown oil. The oil was dissolved in chloroform, and silica gel was added. The slurry was concentrated by rotary evaporation to obtain a dry powder mixture. The powder mixture was loaded into an Isco CombiFlash system, and chromatography was performed using a gradient of 15-20% dichloromethane in hexane until the product eluted. The fractions were analyzed by TLC.The pure fractions were combined and concentrated by rotary evaporation to obtain a pale yellow solid, which was then dried under high vacuum to remove the solvent. 1 Analysis by 1H NMR revealed the presence of some of the starting material, 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran. The solid was recrystallized from hexane to obtain a white solid. The solid was collected by vacuum filtration and washed with cold hexane (twice in 10 mL increments). To remove trace amounts of hexane, the solid was dissolved in dichloromethane and concentrated by rotational evaporation to obtain a white crystalline solid (repeated twice). The solid was dried under high vacuum to obtain 2.96 g (58.8%) of the product as a white crystalline solid.

[0125] 1 H NMR (400MHz, CDCl3)δ 8.01(d, J=7.9Hz, 2H), 7.54(d, J=2.4Hz, 1H), 7.50(dd, J=8.7, 2.5Hz, 1H), 7.39(d, J=8. 7Hz, 1H), 7.11(dd, J=7.9, 1.4Hz, 2H), 7.08(dt, J=1.5, 0.8Hz, 1H), 7.01(dt, J=1.6, 0.8 Hz, 1H), 5.35(t, J=2.9Hz, 1H), 3.80(td, J=11.2, 2.9Hz, 1H), 3.57(dt, J=11.1, 3.4Hz, 1 H), 2.52(s, 6H), 1.82(s, 2H), 1.63~1.50(m, 2H), 1.47(s, 3H), 1.45(s, 3H), 0.90(s, 9H). 13 C NMR (101MHz, CDCl3)δ 150.91, 144.07, 141.90, 141.88, 134.94, 134.84, 127.68, 126.71, 126.05, 121.00, 120.85, 120.63, 120.60, 119.39, 119. 30, 116.06, 110.82, 110.18, 96.67, 61.43, 57.00, 38.18, 32.39, 31.85, 31.60, 31.52, 29.95, 25.10, 22.05, 21.96, 17.57.

[0126] [ka]

[0127] Preparation of 2,7-dimethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (16) (201303282-23): A three-necked round-bottom flask was fitted with a magnetic stirring rod, septum, and nitrogen gas inlet. The flask was placed under a nitrogen atmosphere and filled with 2,7-dimethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (2.8580 g, 5.912 mmol) and dry tetrahydrofuran (40 mL). The solution was cooled to 0-10°C for approximately 15 minutes (using an ice bath), and 2.5 M n-butyllithium in hexane (6.2 mL, 15,500 mmol) was slowly added. After stirring at 0-10°C for 4 hours, 2-iso-propoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.1 mL, 15,195 mmol) was slowly added. The mixture was stirred at 0-10°C for 1 hour, then the reaction product was warmed to room temperature and stirred overnight. Cold saturated sodium bicarbonate aqueous solution (40 mL) was added to the reaction mixture. The aqueous phase was extracted with dichloromethane (4 times in 20 mL increments). The organic phases were combined and washed with cold saturated sodium bicarbonate aqueous solution (90 mL), then with brine (90 mL). The organic phase was dried on anhydrous magnesium sulfate, filtered by vacuum filtration, concentrated by rotary evaporation, and then placed under high vacuum to obtain the product as a crude white crystalline solid (3.8902 g). 1The analysis was performed by 1H NMR. The crude product was slurryed in acetonitrile (30 mL), stirred at room temperature for 30 minutes, and then isolated as a white solid by vacuum filtration. The solid was washed with cold acetonitrile (twice with 10 mL each). To remove trace amounts of acetonitrile, the solid was dissolved in dichloromethane and concentrated by rotary evaporation to obtain an off-white crystalline solid (repeat twice). The solid was dried under high vacuum to obtain 2.24 g (62.2%) of the product as an off-white crystalline solid.

[0128] 1 H NMR (400MHz, CDCl3)δ 7.96,(d, J=7.9Hz, 1H), 7.95(d, J=7.9Hz, 1H), 7.88(d, J=2.6Hz, 1H), 7.45(d, J=2.6Hz, 1H), 7. 08(dd, J=8.0, 1.4Hz, 1H), 7.07(dd, J=8.0, 1.4Hz, 1H), 7.01(d, J=0.8Hz, 1H), 4.99~4.95(m, 1H) , 2.77(td, J=10.9, 3.0Hz, 1H), 2.61(dt, J=11.3, 4.0Hz, 1H), 2.50(s, 3H), 2.48(s, 3H), 1.76(s, 2H), about 1.73 (m, 1H), 1.43 and 1.42 (overlapping singlets, 15H), 1.40 (s, 3H), 1.40-1.00 (m's, 5H), 0.84 (s, 9H). 13 C NMR (101MHz, CDCl3)δ 156.66, 145.86, 142.08, 141.96, 135.05, 134.09, 131.09, 129.45, 120.95, 120.68, 120.61, 119.15, 119.10, 110.80, 110.71 , 101.55, 83.66, 61.18, 56.87, 38.29, 32.37, 31.87, 31.46, 31.36, 30.02, 25.05, 24.96, 24.72, 24.70, 22.10, 22.07, 18.23.

[0129] [ka]

[0130] Preparation of 2',2'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-dimethyl-9H-carbazole-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol): A three-necked round-bottom flask was fitted with a magnetic stirring rod, septum, condenser, and nitrogen gas inlet. The flask was placed under a nitrogen atmosphere and filled with 2,7-dimethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (2.1304 g, 3.494 mmol), 1,2-dimethoxyethane (44 mL), sodium hydroxide (0.4680 g, 11.700 mmol) in 13 mL of water, tetrahydrofuran (15 mL), and 1,3-bis(4-fluoro-2-iodo-6-methylphenoxy)propane (0.9055 g, 1.664 mmol). The mixture was purged with nitrogen for approximately 15 minutes, and then tetrakis(triphenylphosphine)palladium(0) (0.1373 g, 0.1188 mmol) was added. The mixture was heated under reflux at 85°C for 20 hours, and analyzed by HPLC to determine if the reaction was complete. After 2 hours, HPLC showed the formation of a protected product and the consumption of crosslinks. After 20 hours, there was no change in the HPLC analysis, and the reaction was determined to be complete. The reactants were then cooled to room temperature. After cooling, the protected product remained in the solution. The mixture was transferred to a separatory funnel and phase separation was performed. The phases were separated. The organic phase was dried over magnesium sulfate and filtered by vacuum filtration. The solid was washed with dichloromethane, and the filtrate was concentrated by rotary evaporation to obtain the protected product as a crude, viscous, golden-orange solid (3.3180 g). 1 The reaction was analyzed by 1H NMR. The protected product was dissolved in a mixture of tetrahydrofuran (17.5 mL) and methanol (17.5 mL), and then heated to 60°C. p-toluenesulfonic acid monohydrate (0.0663 g, 0.3485 mmol) was added to the solution. The reaction mixture was stirred overnight at 60°C, and the reaction was checked for completion. 19The reaction was analyzed by 1F NMR. The reaction mixture was then cooled to room temperature. The solution was concentrated by rotational evaporation to obtain the deprotected product as a crude golden-orange viscous solid (2.8889 g). The solid was dissolved in chloroform and silica gel was added. The slurry was concentrated by rotational evaporation to obtain a dry powder mixture. The powder mixture was packed into an Isco CombiFlash system and chromatography was performed using a 330 Grace column and a gradient of 40-50% dichloromethane in hexane until the product eluted. Each fraction was analyzed by TLC. The pure fractions were combined and concentrated by rotational evaporation to obtain an orange crystalline solid. To remove trace amounts of hexane, the solid was dissolved in dichloromethane and concentrated by rotational evaporation to obtain an orange crystalline solid (repeat twice). The solid was dried under high vacuum to obtain 1.35 g (74.9%) of the product as an orange crystalline solid.

[0131] 1 1H NMR (400 MHz, CDCl3) δ 8.04 (d. , J=8.8, 2.9Hz, 2H), 6.73(s, 2H), 3.75(t, J=6.4Hz, 4H), 2.44(s, 12H), 2.0 5(s, 6H), 1.87(p, J=6.3Hz, 2H), 1.82(s, 4H), 1.47(s, 12H), 0.88(s, 18H). 13C NMR (101MHz, CDCl3)δ 160.25, 157.82, 149.58, 149.55, 147.82, 143.12, 141.81, 135.32, 133.52, 133.43, 133.01, 132.92, 128.94, 127.97, 126.49, 125.52 , 121.14, 121.09, 119.70, 117.44, 117.21, 116.21, 115.98, 109.87, 70.77, 57.12, 38.21, 32.42, 31.80, 31.55, 30.56, 22.07, 16.28. [Multiplicity due to carbon-fluorine bonding was not identified.] 19 F NMR (376MHz, CDCl3) δ-118.04 (t, J=8.8Hz).

[0132] [ka]

[0133] Preparation of structure (iv): The reaction setup was carried out in a glove box under a nitrogen atmosphere. A jar was filled with HfCl4 (0.0335 g, 1.046 mmol) and toluene (6 mL). The slurry was cooled to -25°C for 30 minutes in a glove box freezer. 3.0 M methylmagnesium bromide (0.14 mL, 0.42 mmol) in diethyl ether was added to the cold, stirring slurry. The mixture was stirred vigorously for 2 minutes. The solid turned into a solution, but the reaction solution was cloudy. To the solution, a solution of ligand (0.1076 g, 0.0990 mmol) in toluene (2 mL) was added. The vial containing the ligand solution was rinsed with toluene (2.0 mL). The rinsing solvent was added to the reaction mixture. After stirring for 1.5 hours, the brownish reaction mixture was filtered under vacuum using a frit glass funnel. The cake was washed twice with 4 mL each of toluene. To the filtrate (a clear, pale yellow solution), hexane (10 mL) was added. The resulting turbid solution was filtered (using a syringe filter) and concentrated under high vacuum to obtain 0.1097 g (85.7%) of the product.

[0134] 1H NMR (400MHz, C6D6)δ 8.15(d, J=8.0Hz, 2H), 8.00(dt, J=7.9, 0.5Hz, 2H), 7.87(d, J=2.5Hz, 2H), 7.76~7.75(m, 2H), 7.63 (dt, J=1.4, 0.7Hz, 2H)7.29~7.21(m, 4H), 7.05(ddd, J=7.9, 1.4, 0.6Hz, 3H), 6.73(ddd, J=9.0, 3.2, 0.7Hz, 2H), 6.07(ddd, J=8.2, 3.2, 0.8Hz, 2H), 3.49(dt, J=9.9, 4.9Hz, 2H), 3.19(ddd, J=10.6, 6.1 , 5.1Hz, 2H), 2.64(s, 6H), 2.27(s, 6H), 1.67(d, J=14.5Hz, 2H), 1.58(d, J=14.5Hz, 2H), 1.27(broad s, 8H), 1.22(s, 6H), 1.19(t, J=0.7Hz, 6H), 0.85(s, 18H), -0.69(s, 6H). 13 C NMR (101MHz, C6D6)δ 161.49, 159.04, 153.43, 149.47, 149.44, 142.21, 141.32, 140.70, 136.21, 135 .59, 135.50, 134.90, 134.81, 134.47, 130.43, 126.91, 123.66, 121.99, 121.37, 120.55, 119.66, 118.07, 117.84, 117.52, 117.29, 114.42, 111.20, 76.10, 57.48, 49.01, 38.19, 32.57, 31.94, 31.66, 31.29, 30.19, 22.50, 22.13, 16.17, 1.38. [Multiplicity due to carbon-fluorine bonding was not identified.]

[0135] [ka]

[0136] The biphenylphenol polymerization precatalyst of structure (v) was prepared as follows.

[0137] [ka]

[0138] Preparation of meso-pentane-2,4-diyldibenzenesulfonate: A 250 mL three-necked round-bottom flask was fitted with two septums and a stirring bar and placed under nitrogen gas. The flask was filled with 2,4-pentanediol (7.5 mL, 69.1 mmol) and pyridine (110 mL, this pyridine was placed on a 3 Å molecular sieve before use). The colorless solution was cooled to approximately 0°C (using an ice bath). p-toluenesulfonyl chloride (39.5903 g, 0.2077 mol) was added gradually over 10 minutes. The solution turned yellow. The ice bath was removed and the mixture was stirred overnight. After stirring overnight, the reaction mixture was poured into 550 mL of ice water and stirred for 3 hours. The white precipitate was collected by vacuum filtration. The solid was washed twice with 50 mL of water each time. The solid was allowed to stand and air-dried. Crude product 1 ¹H-NMR, based on sextet integrals at 4.57 and 4.70 ppm, showed a meso-isomer:racemic isomer ratio of approximately 1:1. Crude bis-tosylate (23.8423 g) was obtained as a white solid. The solid was transferred to a jar and diethyl ether (50 mL) was added. The mixture was vigorously stirred for 10 minutes. The solid was isolated by vacuum filtration. The cake was washed twice with 10 mL each of diethyl ether. This extraction procedure was repeated at least three more times. The recovered white solid was air-dried. 1 1H-NMR showed that the solid was not concentrated in the meso isomer. Therefore, the solid was suspended in diethyl ether (240 mL) and vigorously stirred overnight. The solid was filtered, and a small amount of sample was taken. 1 Analysis was performed by 1H-NMR. The spectrum showed a meso-to-racemic ratio of approximately 2:1. Therefore, the solid was suspended in diethyl ether (240 mL) and vigorously stirred overnight. This procedure was repeated twice. Then, after vigorous stirring for another 66 hours, the solid was filtered, and a small amount of sample was taken. 1 The analysis was performed by 1H-NMR. The spectrum showed a meso:racemic ratio of approximately 6:1. The solid was left under high vacuum to remove the diethyl ether, and 10.08 g (35.3%) of meso-enriched bistosylate was obtained as a white solid.

[0139] [ka]

[0140] Preparation of 2,2'-(((meso)-pentane-2,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene): A 250 mL round-bottom flask was fitted with a condenser, two septums, a magnetic stirring rod, and a gas inlet at the top of the condenser. The flask was filled with meso-pentane-2,4-diyldibenzenesulfonate (3.0041 g, 7.2823 mmol), 4-fluoro-2-iodo-6-methylphenol (3.6751 g, 14.582 mmol) [prepared as described in U.S. Patent Application Publication No. 2015 / 0291713A1], potassium carbonate (4.0220 g, 29.101 mmol), and N,N-dimethylformamide (55 mL). The reaction mixture was placed under nitrogen and heated to 100 °C. After heating for 2 hours, the brown mixture was sampled for GC / MS analysis. Peaks corresponding to the molecular weight fraction of the product were observed, suggesting that the starting material, phenol, had been consumed. The reaction mixture was cooled to room temperature and concentrated in a rotary evaporator (bath temperature 25-70°C) to obtain a wet brown solid. The solid was partitioned between dichloromethane (50 mL) and water (50 mL). The phases were separated. The aqueous phase was extracted three times with 30 mL each of dichloromethane. The combined organic phase was washed with 1 M sodium hydroxide aqueous solution (60 mL), water (60 mL), and saturated sodium chloride aqueous solution (60 mL). The organic phase was dried on anhydrous magnesium sulfate, filtered, and concentrated under vacuum to obtain 4.02 g of brown oil. The oil was subjected to chromatography using a 120 g Grace column and an automated ISCO apparatus. The column was eluted with a gradient of 0-2% ethyl acetate in hexane. The fraction containing the product was identified by a combination of TLC and GC / MS. The fractions were combined and concentrated under high vacuum to obtain the product (2.2653 g, 54.4%) as a yellow oily substance.

[0141] 1H NMR (400MHz, CDCl3)δ 7.32(m, 2H), 6.86(m, 2H), 4.69(m, 2H), 2.48(m, 1H), 2.28(s, 6H), 2.27(s, 1H), 1.96(m, 1H), 1.31(d, 6H), 1.27(d, 1H).

[0142] [ka]

[0143] Preparation of 2',2'''-(((meso)-pentan-2,4-diyl)bis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol): 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetra) in 1,2-dimethoxyethane (125 mL) (5.20 g, mmol) (described in the synthesis of structure (iv)) (warmed to room temperature), 2,2'-(((meso)-pentan-2,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene) (2.037 g, mmol), a 30 mL aqueous solution of NaOH (0.8994 g, mmol), and THF (70 mL) were added. All were dissolved before the addition of NaOH. The reaction mixture was spurged with N2 for about 15 minutes, then Pd(PPh3)4 was added, and the mixture was heated overnight at 85°C, then cooled. 1919F NMR spectroscopy was used to determine whether the reaction was complete. The reaction solution was concentrated, the residue was taken up in methylene chloride (200 mL), washed with brine (200 mL), dried over anhydrous magnesium sulfate, filtered through a pad of silica gel, and concentrated to obtain a crude protected ligand. To the crude protected ligand were added THF (50 mL), methanol (50 mL), and about 100 mg of PTSA. PTSA was added until the solution became acidic (confirmed by pH test paper). The solution was heated to 60°C overnight, then cooled and concentrated. The crude ligand was taken up in methylene chloride (100 mL), washed with brine (100 mL), dried over anhydrous magnesium sulfate, filtered through a pad of silica gel, and then concentrated to obtain the ligand as a brown crystalline powder. Since this ligand contained trace impurities, chromatography was performed on a 330 g ISCO column using a methylene chloride:hexane gradient, yielding 1.92 g of white crystals. Since there was slight overlap between the impurities and the desired product, the impure fractions were loaded onto an ISCO 330 g column using the same conditions.

[0144] 1 1H NMR (400 MHz, CDCl3) δ 8.01 (dd, 4H), 7.41 (dd, 4H), 7.30 (dd, 4H), 7.04 (dd, 4H), 6.99 (dd, 2H), 6.79 (dd, 2H), 6.49 (br s, 2H), 3.96 (br s, 2H), 1.94 (s, 6H), 1.74 (s, 4H), 1.37 (d, 12H), 1.29 (s, 36H), 0.85 (d, 6H), 0.80 (s, 18H). 19 19F NMR (376 MHz, CDCl3) δ -118.66 (s)

[0145]

Chemical Formula

[0146] ZrCl4 (0.0399 g, 0.171 mmol) and toluene (10 mL) were added to a jar equipped with a stirring rod in a nitrogen-purged glove box. The resulting slurry was cooled in a glove box freezer at -25°C. Methylmagnesium bromide in diethyl ether (3.0 M, 0.25 mL, 0.75 mmol) was added to the stirred-cooled slurry. The mixture was vigorously stirred for about 4 minutes. The solid turned into a solution, and the mixture changed to a light brown color. Next, the ligand (0.2007 g, 0.1561 mmol) was added to this mixture as a solid. The resulting mixture was stirred at ambient temperature for 5 hours. Then, hexane (10 mL) was added to the mixture, and the mixture was filtered. The solution was concentrated under vacuum to obtain 0.2248 g of the product of structure v as a white solid. Some residual solvent remained in the final product.

[0147] [ka]

[0148] The biphenylphenol polymerization precatalyst of formula (vi) was prepared as described in International Publication No. 2017 / 004462A1. The entire contents of International Publication No. 2017 / 004462A1 are incorporated herein by reference.

[0149] [ka]

[0150] The biphenylphenol polymerization precatalyst of structure (vii) was prepared as follows. The ligand was prepared as described in International Publication No. 2017 / 004462A1.

[0151] [ka]

[0152] The reaction setup was carried out in a glove box under a nitrogen atmosphere. ZrCl4 (0.0333 g, 0.1429 mmol) and toluene (10 mL) were packed into a jar. The slurry mixture was cooled to -25°C in the glove box freezer. 3.0 M methylmagnesium bromide (0.22 mL, 0.66 mmol) in diethyl ether was added to the cooled slurry mixture while stirring. The mixture was stirred vigorously for about 4 minutes. The solid dissolved and turned brown. Ligand (0.2002 g, 0.1353 mmol) was added to the mixture as a solid. The resulting mixture was stirred at room temperature for 4 hours. Hexane was then added to the mixture and it was filtered. The solution was concentrated under vacuum to obtain 0.1942 g of the product (theoretical yield is 0.2164 g, 90%) as an off-white solid. The product was further purified. Hexane and then toluene were added to the solid until most of the solid dissolved. The mixture was filtered (using a Whatman 0.45 μL syringe filter), and the solution was concentrated to obtain the product.

[0153] 1 H NMR (400MHz, C6D6)δ 8.10(d, 2H), 7.99(d, 2H), 7.81(br s, 2H), 7.76(br, 4H), 7.41(d, 2H), 7.32(d, 2H), 7.27(d, 2H), 6.85(dd, 2H), 6.08(d d, 2H), 3.38(m, 2H), 3.20(m, 2H), 1.83(d, 2H), 1.56(m, 18H), 1.36(d, 12H), 1.23(br s, 9H), 1.16(s, 12H), 1.05(br m, 6H), 0.93(s, 18H), 0.81(s, 18H), 0.59(s, 18H), -0.55(s, 6H).

[0154] [ka]

[0155] The biphenylphenol polymerization precatalyst of structure (viii) was prepared as described in International Publication No. WO 2017 / 004456 A1. The entire content of International Publication No. WO 2017 / 004456 A1 is incorporated herein by reference.

[0156]

Chemical Formula

[0157] The biphenylphenol polymerization precatalyst of structure (ix) was prepared as follows.

[0158]

Chemical Formula

[0159] 2-Iodo-4-fluorophenol, 1,4-dibromobutane, K₂CO₃, and 100 mL of acetone were charged into a 250 mL flask equipped with a stirring bar and a condenser. The reaction mixture was stirred, refluxed overnight (60°C), and checked by GC and GCMS. Since both analyses indicated completion of the reaction, the mixture was cooled, filtered through a pad of silica gel, and concentrated by rotary evaporation. The residue was recrystallized from hot acetone to give 7.137 g of white crystals. The filtrate was recrystallized to obtain a total mass of 0.6 g, which had a faint orange tint and was 98% pure containing some impurities.

[0160] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.49 (dd, 2H), 7.00 (m, 2H), 6.75 (dd, 2H), 4.07 (m, 4H), 2.09 (m, 4H).

[0161]

Chemical Formula

[0162] Preparation of 6',6'''-(butane-1,4-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazole-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol): 2.69 g (3.58 mmol) of 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5 ,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (prepared as described in U.S. Patent Application Publication No. 2015 / 0291713A1), 0.901 g (1.70 mmol) of 1,4-bis(4-fluoro-2-iodophenoxy)butane, 0.45 g (11.25 mmol) of NaOH, 13 mL of water, and 13 mL of THF were added. The system was sparged with N2, then 130 mg of Pd(Ph3)4 was added, and the mixture was heated at 85°C for 48 hours, then cooled and concentrated. After cooling, the protective ligand precipitated from the solution and was isolated by vacuum filtration. The mixture was further dried under high vacuum for about 1 hour to obtain the crude ligand as a gray powder. This ligand was used directly in the next step. To the crude protective ligand, 100 mL of 1:1 methanol / THF and approximately 100 mg of PTSA were added. The solution was heated at 60°C for 8 hours, then cooled and concentrated. The residue was taken in methylene chloride (200 mL), washed with brine (200 mL), dried on anhydrous magnesium sulfate, filtered through a silica gel pad, and then concentrated to obtain a yellow powder. This compound was purified by flash chromatography using an ISCO purification system with elution in 2% ethyl acetate in hexane to obtain 1.70 g (54.4%) of the pure compound as a white powder.

[0163] [ka]

[0164] HfCl4 (0.0795 g, 0.248 mmol) and toluene (15 mL) were added to a jar equipped with a stirring rod in a nitrogen-purged glove box. The resulting slurry was cooled in a glove box freezer at -25°C. Methylmagnesium bromide in diethyl ether (3.0 M, 0.34 mL, 1.02 mmol) was added to the cooled slurry while stirring. The mixture was vigorously stirred for about 4 minutes. The solid dissolved, and the mixture turned pale yellow. Next, the ligand (0.3007 g, 0.237 mmol) was added to the mixture as a solid. The resulting mixture was stirred at ambient temperature for 2.5 hours. Then, hexane (15 mL) was added to the mixture, and the mixture was filtered. The pale yellow solution was concentrated under vacuum to obtain 0.3866 g of the product as a brown solid. Hexane (10 mL) was added to the solid, and the mixture was stirred at room temperature for 2.5 hours. The solid was then recovered by filtration. The solid was dried under vacuum to obtain 0.3280 g of the product of structure ix as an off-white solid (yield was 93.8%).

[0165] [ka]

[0166] The biphenylphenol polymerization precatalyst of structure (x) was prepared as described in International Publication No. 2017 / 058858. The entire contents of International Publication No. 2017 / 058858 are incorporated herein by reference.

[0167] [ka]

[0168] A biphenylphenol polymerization precatalyst of structure (xi) was prepared as described in International Publication No. 2017 / 058858. The entire contents of International Publication No. 2017 / 058858 are incorporated herein by reference.

[0169] [ka]

[0170] A biphenylphenol polymerization precatalyst of structure (xii) was prepared as described in U.S. Patent No. 8,609,794. The entire contents of U.S. Patent No. 8,609,794 are incorporated herein by reference.

[0171] [ka]

[0172] The biphenylphenol polymerization precatalyst of structure (xiii) was prepared as follows.

[0173] [ka]

[0174] Synthesis of 2-methylbutane-1,4-diol: In a nitrogen-filled glove box, a three-necked round-bottom flask equipped with a stirring bar and septum was filled with 2.0 M lithium aluminum hydride (109 mL, 217.72 mmol) and tetrahydrofuran (240 mL). The flask was sealed and removed from the glove box into a fume hood. The flask was equipped with a nitrogen gas inlet. The solution was cooled to 0°C (using an ice bath). A solution of dimethyl 2-methyl succinate (9.00 g, 56.19 mmol) in tetrahydrofuran (70 mL) was slowly added to the cooled solution via syringe. The resulting mixture was stirred at room temperature for 17 hours. The mixture was cooled to 0°C (using an ice bath), and the excess lithium aluminum hydride was rapidly cooled by successive addition of water (4.1 mL), 10% aqueous sodium hydroxide solution (8.4 mL), and then water (12.6 mL). Next, the mixture was stirred at room temperature for 3 hours and filtered. The solid was washed with diethyl ether. The filtrate was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to obtain a crude yellow oil with precipitate. The oil was dried under high vacuum to obtain 3.41 g (58.3%) of the product as a yellow oil with precipitate.

[0175] 1 H NMR (400MHz, Chroroholm-d) δ 4.69 (p, J=5.1Hz, 1H), 3.70 (dq, J=9.5, 5.0Hz, 0H), 3.60 (tt, J=7.6, 4.3Hz, 0H), 3.48 (dt, J=9.8, 4.6Hz, 0H), 3.37 (ddd, J=10.7, 7.1, 3.6Hz, 0H), 1.76 (septet, J=6.8, 5.0Hz, 0H), 1.62 (dddd, J=14.6, 8.0, 6.6, 5.6Hz, 0H), 1.48 (dtd, J=14.1, 6.0, 5.2Hz, 0H), 0.91 (d, J=6.8Hz, 1H). 13 C NMR (101MHz, クロロホルム-d) δ 67.62, 60.34, 37.00, 33.53, 16.98.

[0176]

change

[0177] Synthesis of 2-methylbutane-1,4-diirbis(4-methylbenzenesulfonate): A three-necked round-bottom flask equipped with a stirring bar, septum, and nitrogen inlet was packed with p-toluenesulfonyl chloride (15.06 g, 78.99 mmol) and anhydrous pyridine (26 mL). The solution was cooled to 0°C (using an ice bath). A solution of 2-methylbutane-1,4-diol (3.41 g, 32.70 mmol) in anhydrous pyridine (6.5 mL) was added dropwise via syringe. The resulting mixture was stirred at 0°C (using an ice bath) for 5 hours. The reaction product was poured into a beaker of stirred ice water (65 mL), and a dark pink oil phase formed at the bottom. The phases were separated. The aqueous phase was extracted with dichloromethane (three times in 65 mL increments). The combined organic phase was washed with water (25 mL), 10% by weight sulfuric acid (25 mL), 1 M sodium carbonate, and then water (25 mL). The organic phase was dried on magnesium sulfate, filtered, and concentrated by rotary evaporation to obtain a crude pink oily substance with precipitate. To remove excess pyridine, the oily substance was dissolved in dichloromethane and washed with 10% by weight sulfuric acid (25 mL), followed by water (25 mL). The organic phase was dried on magnesium sulfate, filtered, and concentrated by rotary evaporation to obtain a crude pink oily substance with precipitate. The oily substance was dried under high vacuum to obtain 8.89 g (65.9%) of the product as pink oil with precipitate. 1 H NMR (500MHz, chloroform-d)δ 7.75(dt, J=8.4, 2.0Hz, 4H), 7.35(d, J=7.9Hz, 4H), 4.08~3.94(m, 2H), 3.87~3.74(m, 2H), 2.44( s, 6H), 1.92(h, J=6.5Hz, 1H), 1.79~1.69(m, 1H), 1.51~1.42(m, 1H), 0.85(dd, J=6.8, 1.6Hz, 3H).

[0178] 13 ¹³C NMR (126 MHz, chloroform-d) δ 144.81, 144.79, 132.62, 132.56, 129.77, 127.64, 73.88, 67.75, 31.57, 29.27, 21.46, 15.70.

[0179] [ka]

[0180] Synthesis of 2,2'-((2-methylbutane-1,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene): A three-necked round-bottom flask equipped with a stirring bar, septum, condenser, and nitrogen inlet was filled with 2-methylbutane-1,4-diylbis(4-methylbenzenesulfonate) (3.00 g, 7.27 mmol), 4-fluoro-2-iodo-6-methylphenol (3.67 g, 14.56 mmol, prepared by the method published in U.S. Patent Application Publication No. 2015 / 0291713A1), anhydrous potassium carbonate (4.02 g, 29.08 mmol), and N,N-dimethylformamide (58 mL). The resulting mixture was stirred at 100°C for 5 hours and then cooled to room temperature. The mixture was concentrated to a dry state by rotary evaporation. The residue was dissolved in 50:50 dichloromethane:water (30 mL). The phases were separated. The aqueous phase was extracted with dichloromethane (3 times in 30 mL increments). The combined organic phase was washed with 2N sodium hydroxide aqueous solution (115 mL), water (115 mL), and then brine (115 mL). The organic phase was dried on magnesium sulfate, filtered, and concentrated by rotary evaporation to obtain a crude reddish-brown oil (4.12 g). The oil was dissolved in a minimum amount of hexane and purified by flash column chromatography (ISCO, 220 g silica gel, 5-10% dichloromethane in hexane). The fractions containing the product were combined and concentrated by rotary evaporation to obtain a dark yellow oil. To remove trace amounts of hexane, the oil was dissolved in dichloromethane and concentrated by rotary evaporation to obtain a dark yellow oil (repeated twice). The oily substance was dried under high vacuum to obtain 2.55 g (61.3%) of the product as a dark yellow oil. 1H NMR (400MHz, chloroform-d)δ 7.30(ddd, J=7.5, 3.1, 0.7Hz, 2H), 6.86(ddt, J=8.7, 3.1, 0.7Hz, 2H), 3.96(t, J=6.6Hz, 2H), 3.79~3.71(m, 2H), 2.44~2.34(m, 1 H), 2.32 (dt, J=1.5, 0.7Hz, 6H), 2.25 (dtd, J=13.9, 6.9, 5.6Hz, 1H), 1.86 (ddt, J=14.0, 7.7, 6.3Hz, 1H), 1.24 (d, J=6.8Hz, 3H). 13 ¹³C NMR (101 MHz, chloroform-d) δ 159.57, 159.55, 157.12, 157.09, 153.58, 153.55, 153.23, 153.20, 133.15, 133.12, 133.07, 133.04, 123.50, 123.41, 123.25, 123.17, 118.01, 117.94, 117.79, 117.72, 91.45, 91.35, 91.30, 91.21, 77.46, 77.45, 71.25, 71.23, 33.98, 31.22, 17.36. Multiplicity due to carbon-fluorine bonding was not specified.

[0181] [ka]

[0182] Synthesis of 2',2'''-((2-methylbutan-1,4-diyl)bis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol): In a three-necked round-bottom flask equipped with a stirring bar, septum, condenser and nitrogen inlet, 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) A solution of 2,2'-((2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole-9-yl (5.86 g, 8.45 mmol, prepared by the method published in U.S. Patent Application Publication No. 2015 / 0291713A1), 2,2'-((2-methylbutane-1,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene) (2.30 g, 4.02 mmol), 1,2-dimethoxyethane (105 mL), tetrahydrofuran (36 mL), and sodium hydroxide (1.12 g, 27.98 mmol) in water (31 mL) was packed into the container. The mixture was purged with nitrogen for 15 minutes, and then tetrakis(triphenylphosphine)palladium(0) (0) (0.36 g, 0.31 mmol) was added. The mixture was heated at 85°C for 20 hours. A precipitate formed. The reaction mixture was cooled to room temperature and filtered. The solid was dissolved in dichloromethane, and the solution was concentrated by rotary evaporation to obtain a yellowish-brown crystalline solid. The solid was dissolved in a mixture of tetrahydrofuran (43 mL), methanol (43 mL), and chloroform (60 mL). The solution was heated to 60°C, and p-toluenesulfonic acid monohydrate (0.16 g, 0.82 mmol) was added. The reaction mixture was heated at 60°C overnight and cooled to room temperature. The reaction mixture was concentrated by rotary evaporation to obtain a crude brown crystalline solid. The solid was recrystallized from acetonitrile, filtered, and washed with cold acetonitrile (twice in 10 m increments). The ligand was dissolved in dichloromethane and concentrated by rotary evaporation to obtain a light brown crystalline solid. The solid was dried under high vacuum to obtain 4.50 g (87.1%) of the product as a light brown crystalline solid. 1H NMR (400MHz, chloroform-d)δ 8.00(dt, J=8.3, 2.4Hz, 4H), 7.46~7.39(m, 4H), 7.34~7.25(m, 4H), 7.09(dt, J=3.7, 1.8Hz, 4H), 7.00(dt, J=8.9, 3.3Hz, 2H), 6.86(dd, J=8.8, 3.1Hz, 2H), 6.30(s, 2H), 3.54(td, J=9.3, 4.2Hz, 2 H), 3.27(d, J=5.9Hz, 2H), 2.05(s, 3H), 2.01(s, 3H), 1.74(s, 4H), 1.67(m, 1H), 1.39(d, J=2.8Hz , 12H), 1.34~1.24(m, 36H), 1.24~1.09(m, 2H), 0.81(s, 9H), 0.80(s, 9H), 0.56(d, J=6.6Hz, 3H). 13 C NMR (101MHz, cdcl3)δ 160.07, 160.04, 157.65, 157.62, 150.02, 149.99, 149.96, 148.93, 148.90, 148.88, 148.86, 147.74, 147.70, 142.81, 141. 62, 141.60, 133.60, 133.51, 133.03, 132.95, 129.01, 127.44, 127.39, 126.51, 126.49, 126.38, 126.36, 125.23, 125.19, 12 1.05, 121.01, 119.47, 117.68, 117.66, 117.63, 117.35, 117.22, 117.13, 116.99, 116.18, 116.12, 115.95, 115.89, 106.32, 79.01, 71.64, 57.18, 57.13, 38.25, 35.06, 33.34, 32.54, 32.51, 31.96, 31.91, 31.87, 31.79, 31.64, 30.40, 16.45, 16.40. The degree of multiplicity due to carbon-fluorine bonding was not specified.

[0183] The reaction setup was carried out in a glove box under a nitrogen atmosphere. Zirconium tetrachloride (0.054 g, 0.23 mmol) and toluene (15 mL) were packed into a jar. The slurry mixture was cooled to -25°C in the glove box freezer. 3.0 M methylmagnesium bromide (0.35 mL, 1.05 mmol) in diethyl ether was added to the cooled slurry mixture while stirring. The mixture was stirred vigorously for about 4 minutes. The solid dissolved and turned pale yellow. Ligand (0.30 g, 0.23 mmol) was added to the mixture as a solid. The resulting mixture was stirred at room temperature for 2 hours. Then, hexane (15 mL) was added to the mixture and it was filtered. The solution was concentrated under vacuum to obtain 0.36 g of product as a nearly black solid. Hexane (15 mL) was added to the solid and the mixture was stirred at room temperature for 4 hours. A black solid was observed. The mixture was stirred at room temperature for 2 days. To the mixture, toluene was added in 2 mL increments to dissolve most of the solid. A total of 16 mL of toluene was added. The mixture was filtered through a syringe filter and concentrated under vacuum to obtain 0.29 g of product as a brown solid. Hexane (10 mL) was added to the brown solid, and the mixture was stirred overnight at room temperature. The mixture was filtered, the solid was placed in a glass vial, and dried under high vacuum to obtain 0.19 g (56.6%) of product as an off-white solid. 1 The 1H-NMR of the product indicated that it was a mixture of isomers.

[0184] 1H NMR (500MHz, benzene-d6)δ 8.19(m, 5H), 8.12(d, J=8.0Hz, 5H), 7.95~7.82(m, 11H), 7.79(s, 4H), 7.53~7.45(m, 6H), 7.43~7.32(m, 10H), 6.99~6.86( m, 6H), 6.09(s, 5H), 4.03~3.91(m, 3H), 3.49(t, J=9.9Hz, 1H), 3.36~3.20(m, 7H), 1.89~1.61(m, 6H), 1.57(s, 13H), 1.53(d , J=4.7Hz, 41H), 1.27(d, J=2.6Hz, 34H), 1.25~1.15(m, 32H), 1.05(d, J=6.8Hz, 6H), 1.00(d, J=10.7Hz, 9H), 0.90(s, 22H), 0.84(d, J=3.5Hz, 32H), 0.44(d, J=7.1Hz, 6H), 0.17(d, J=7.1Hz, 3H), -0.36(d, J=3.7Hz, 8H), -0.46(s, 5H), -0.54(s, 3H). No isomers were identified, and the integrals were not normalized for each proton ratio.

[0185] [ka]

[0186] The biphenylphenol polymerization precatalyst of structure (xiv) was prepared as follows: The reaction was set up in a glove box under a nitrogen atmosphere. ZrCl4 (0.0561 g, 0.241 mmol) and toluene (15 mL) were packed into a jar. The slurry mixture was cooled to -25°C in a glove box freezer. 3.0 M methylmagnesium bromide (0.36 mL, 1.080 mmol) in diethyl ether was added to the cooled slurry mixture while stirring. The mixture was stirred vigorously for about 4 minutes. The solid dissolved and turned yellow. Ligand (0.3002 g, 0.239 mmol) was added to the mixture as a solid. The resulting mixture was stirred at room temperature for 2 hours. Then, hexane (15 mL) was added to the mixture and it was filtered. The solution was concentrated under vacuum to obtain 0.3793 g of the product as a yellow solid. Hexane (10 mL) was added to the solid, and toluene was added in 2 mL increments to dissolve most of the solid. A total of 8 mL of toluene was added. The cloudy brown solution was stirred overnight. Next, the solution was filtered through a syringe filter and concentrated under vacuum to obtain 0.3345 g of product as a brown solid. To remove excess toluene, hexane (10 mL) was added to the solid, the mixture was vigorously stirred for 1 hour, and then placed under vacuum to obtain 0.2985 g (90.81%) of product as a brown solid.

[0187] 1H NMR (400MHz, benzene-d6)δ 8.56(d, J=1.9Hz, 2H), 8.38(d, J=1.9Hz, 2H), 7.95(d, J=8.6Hz, 2H), 7.90(d, J=2.5Hz, 2H), 7.79(d, J=8.8 Hz, 2H), 7.76(dd, J=8.6, 1.9Hz, 2H), 7.46(dd, J=8.8, 1.9Hz, 2H), 7.29(d, J=2.5Hz, 2H), 6.83(dd, J=8.9, 3 .2Hz, 2H), 6.15(dd, J=8.2, 3.2Hz, 2H), 3.47(dt, J=9.8, 4.7Hz, 2H), 3.24(dt, J=10.5, 5.4Hz, 2H), 2.11(s, 3H), 1.58(m with s, 24H), 1.33(s, 18H), 1.26(s, 7H), 1.23(s, 7H), 1.19(s, 6H), 0.84(s, 18H), -0.50(s, 6H).

[0188] [ka]

[0189] A biphenylphenol polymerization precatalyst of structure (xv) was prepared as follows.

[0190] The reaction setup was carried out in a glove box under a nitrogen atmosphere. ZrCl4 (0.0563 g, 0.242 mmol) and toluene (15 mL) were packed into a jar. The slurry mixture was cooled to -25°C in the glove box freezer. 3.0 M methylmagnesium bromide in diethyl ether (0.36 mL, 1.080 mmol) was added to the cooled slurry mixture while stirring. The mixture was stirred vigorously for about 5 minutes. The solid dissolved and turned brown. Ligand (0.3008 g, 0.242 mmol) was added to the mixture as a solid. The resulting mixture was stirred at room temperature for 2 hours. Then, hexane (15 mL) was added to the mixture and it was filtered. The light brown solution was concentrated under vacuum to obtain 0.3548 g of the product as a brown solid. Hexane (10 mL) and toluene (2.5 mL) were added to the solid. The turbid gray solution was filtered and concentrated under high vacuum to obtain 0.1860 g (56.53%) of the product as a white solid.

[0191] 1 H NMR (400MHz, benzene-d6)δ 8.53(dd, J=1.9, 0.7Hz, 2H), 8.35(dd, J=1.9, 0.7Hz, 2H), 7.66~7.56(m, 8H), 7.41(d, J=1.9Hz, 1H), 7.39(d, J=1.9Hz, 1H), 7.22(d, J=2.5Hz, 2H), 6.89(dd, J=9.0, 3.1Hz, 2H), 6.57(ddd, J=9.0, 7.3, 3. 2Hz, 2H), 4.93(dd, J=9.0, 4.8Hz, 2H), 4.05(t, J=9.9Hz, 2H), 3.44(d, J=12.3Hz, 2H), 1.56(s, 4H), 1 .42(s, 18H), 1.24(s, 18H), 1.20(s, 6H), 1.15(s, 6H), 0.81~091(m, 4H), 0.77(s, 18H), -0.83(s, 6H).

[0192] [ka]

[0193] A comparative polymerization catalyst (other than one produced from the polymerization pre-catalyst of formula (I)) was prepared as follows.

[0194] A comparative polymerization precatalyst of structure (xxi) can be prepared as described in U.S. Patent Application Publication 2018 / 0298128A1, the entire contents of which are incorporated herein by reference.

[0195] [ka]

[0196] In various embodiments, biphenylphenol polymerization catalysts prepared from pre-catalysts of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv), and / or (xv) can be used to produce polymers.

[0197] Example 1 (EX1), an activated, supported biphenylphenol polymerization catalyst of formula I, was prepared as follows.

[0198] General procedure for catalyst preparation: Pre-catalyst loading reaction onto SMAO (all operations are performed in the nitrogen purge box of the Core Module 3 (CM3) high-throughput unit). Before starting the experiment, the stock pre-catalyst was prepared in toluene to the desired concentration. For each reaction vial, the desired amount of SMAO was manually weighed to reach 45 μmol of catalyst per 1 g of SMAO (approximately 1:108 equivalent ratio) and added together with a tumble stirring disk. Toluene was dispensed by CM3, followed by the desired amount of stock pre-catalyst. Certain stock pre-catalysts were delivered manually due to limited available solution volume. After adding all reaction components, the vials were capped, stirred at 300 rpm, and heated to 50°C. After 30 minutes, the vials were cooled to room temperature, the caps were removed, and the reaction plates were placed in the CM3 vortex deck. The reaction vials were mixed while vortexing at 800 rpm for 3 minutes to form a homogeneous slurry. Next, the desired amount of each supported catalyst slurry was daughtered into an 8 mL vial and diluted with Isopar E (trademark) (an isoparaffinic solvent containing a mixture of C8 saturated hydrocarbons). If multiple daughter samples were required, a new PDT tip was used for each subsequent daughtering step. The reactants were daughtered to the desired concentration of PPR.

[0199] Example 2 (EX2) was prepared in the same manner as Example 1, except that the activated and supported biphenylphenol polymerization catalyst of Example 2 was used, as shown in Table 1.

[0200] Example 3 (EX3) was prepared in the same manner as Example 1, except that the activated and supported biphenylphenol polymerization catalyst of Example 3 was used, as shown in Table 1.

[0201] Example 4 (EX4) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 4 was used, as shown in Table 1.

[0202] Example 5 (EX5) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 5 was used, as shown in Table 1.

[0203] Example 6 (EX6) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 6 was used, as shown in Table 1.

[0204] Example 7 (EX7) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 7 was used, as shown in Table 1.

[0205] Example 8 (EX8) was prepared in the same manner as Example 1, except that the activated and supported biphenylphenol polymerization catalyst of Example 8 was used, as shown in Table 1.

[0206] Example 9 (EX9) was prepared in the same manner as Example 1, except that the activated and supported biphenylphenol polymerization catalyst of Example 9 was used, as shown in Table 1.

[0207] Example 10 (EX10) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 10 was used, as shown in Table 1.

[0208] Example 11 (EX11) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 11 was used, as shown in Table 1.

[0209] Example 12 (EX12) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 12 was used, as shown in Table 1.

[0210] Example 13 (EX13) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 13 was used, as shown in Table 1.

[0211] Example 14 (EX14) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst from Example 14 was used, as shown in Table 1.

[0212] Example 15 (EX15) was prepared in the same manner as Example 20, except that an activated and supported biphenylphenol polymerization catalyst from Example 15 was used, as shown in Table 1.

[0213] Example 16 (EX16) was prepared in the same manner as Example 1, except that an activated and supported biphenylphenol polymerization catalyst of Example 16 was used, as shown in Table 1.

[0214] Comparative Example 1 (CE1) was prepared in the same manner as Example 1, except that the catalyst used was the same as in Comparative Example 1, as shown in Table 1.

[0215] The ethylene / 1-hexene copolymerization of each of the catalysts EX1-16 and CE1 was carried out in a slurry phase as follows.

[0216] General parallel pressure reactor (PPR) procedure for slurry phase polymerization: All solutions and PPR solutions were prepared in an inert atmosphere glove box under nitrogen. Isopar E (trademark), ethylene, and hydrogen were purified by passing them through two columns, the first column containing A2 alumina and the second column containing Q5 reactants. Forty-eight PPR-A reactor cells were prepared on weekdays prior to the actual PPR operation as follows: A library of tar-coated glass tubes was manually inserted into the reactor wells, a stirrer paddle was attached to the module head, and the module head was 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, completely evacuated, and the lines were purged. The reactor was then heated to 50°C and the stirrer was operated at 400 rpm. The reactor was filled with Isopar E (trademark) to the appropriate solvent level. A robotic needle was used to obtain a final reaction volume of 5 mL. Solvent injection into modules 1-3 was performed using the left robotic arm, and 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 stirring was increased to the setpoint programmed in the Library Studio design. When the reactor reached the temperature setpoint (requiring 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 (observed by gas uptake). If 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 operation. Next, the robotic synthesis protocol was initiated, by which the comonomer solution (1-hexene) was injected first, followed by the scavenger solution (SMAO), and finally the biphenylphenol polymerization catalyst solution in Isopar-E® was injected. Injections into modules 1-3 were all performed using the left robotic arm, while injections into modules 4-6 were performed using the right robotic arm, with both arms operating simultaneously.The robot completed all three injections into the predetermined cells before initiating the injection of the next cell in the sequence. After each reagent addition, 500 μL of Isopar-E® solvent was used to dislodge the excess and ensure complete reagent injection. After each reagent was added, the inside and outside of the needle were washed with Isopar-E®. The reaction timer was started the moment the biphenylphenol polymerization catalyst was injected into each individual cell. The polymerization reaction proceeded for 60–180 minutes, or until ethylene uptake reached a set pressure of 60–180 psi, whichever came first, and was then quenched by applying a 40 psi overpressure of 10% (v / v) CO2 in argon. Data acquisition continued for 5 minutes after quenching each cell. The reactor was cooled to 50°C, evacuated, and the PPR tubes were removed from the module block. The PPR library was removed from the dry box, and volatile substances were removed using a Genevac rotary evaporator. After reweighing the library vials to obtain the yield, the library was subjected to analysis.

[0217] The operation was carried out under conditions B or K, as detailed in Table 1 below. The results for EX1-16 and CE1 are shown in Tables 1 and 2.

[0218] In various embodiments, biphenylphenol polymerization catalysts produced from pre-catalysts of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv), and (xv) can be used in the polymerization catalyst systems herein to produce high molecular weight polyethylene components in multimodal (e.g., bimodal) polyethylene compositions.

[0219] 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.

[0220] The comonomer content (i.e., 1-hexene) (weight %) incorporated into the polymer was determined by GPC measurement using fast FT-IR spectroscopy on the dissolved polymer.

[0221] Productivity (kilograms of polymer / kilograms of catalyst) was determined as the ratio of the polymer produced to the amount of catalyst and activator added to the reactor.

[0222] The melting temperature (i.e., Tm) can be determined by differential scanning calorimetry according to ASTM D3418-08. For example, a scan rate of 10°C / min is used for a 10 mg sample, and a second heating cycle is employed.

[0223] Condition B is as follows: temperature is 100°C, ethylene is 100 pounds / square inch (psi), H2 / C2 is 0.0017, and C6 / C2 is 0.4.

[0224] The K conditions are as follows: temperature is 100°C, ethylene is 100 psi, H2 / C2 is 0.0068, and C6 / C2 is 0.4.

[0225] [Table 1]

[0226] [Table 2]

[0227] As detailed in Tables 1 and 2, Examples 1 to 16 provide the use of supported biphenylphenol polymerization catalysts for producing polymers via a slurry phase polymerization process, the supported biphenylphenol polymerization catalysts being prepared from a biphenylphenol polymerization pre-catalyst of formula I. In particular, each of Examples 1 to 16 provides polymers having molecular weights that may be desirable for specific applications (e.g., molecular weights in the range of about 150,000 to about 800,000 daltons under condition B, and / or molecular weights less than about 500,000 under condition K). For example, each of Examples 1 to 16 provides polymers that are also suitable for use with metallocene olefin polymerization catalysts. That is, each of the supported biphenylphenol polymerization catalysts of Examples 1 to 16 can be used together with a metallocene olefin polymerization catalyst to prepare polymerization catalyst systems that can be used in a single slurry phase polymerization reactor to produce multimodal (e.g., bimodal) polymers.

[0228] The supported biphenylphenol polymerization catalyst of formula I can be used via a slurry-phase polymerization process to produce polymers having improved comonomer integration compared to polymers produced via a solution-phase polymerization process using the biphenylphenol polymerization catalyst of formula I (e.g., the same supported biphenylphenol polymerization catalyst of formula I). ​​The supported biphenylphenol polymerization catalyst of formula I can be used via a slurry-phase polymerization process to produce polymers having improved comonomer integration compared to polymers produced from a comparative catalyst under similar slurry-phase conditions. The present specification includes the following embodiments. Section 1: The use of a supported biphenylphenol polymerization catalyst for producing a polymer via a slurry phase polymerization process, wherein the supported biphenylphenol polymerization catalyst is of formula I: [ka] (In the formula, R 5 , R 7 , R 8 , and R10 Each of them operates independently, (C1~C 20 ) Alkyl, aryl, aralkyl, halogen, or hydrogen, R 4 and R 11 Each of them is independently a halogen or hydrogen. R 2 and R 13 Each of them operates independently, (C1~C 20 ) Alkyl, aryl, or aralkyl, or hydrogen, R 15 and R 16 Each of these is independently 2,7-disubstituted carbazole-9-yl or 3,6-disubstituted carbazole-9-yl, L is a C3 alkylene or C4 alkylene that forms a bridge between the two oxygen atoms to which L is covalently bonded. R 1 , R 3 , R 12 , and R 14 Each of these is independently a (C1-C8) alkyl, halogen, or hydrogen. R 6 and R 9 Each of these is hydrogen, (C1-C8) alkyl, or halogen, and R is optionally selected. 6 R 7 It can be connected to R 8 However, R 9 It can be connected to form a ring structure, Each X independently contains halogen, hydrogen, (C1~C 20 ) Alkyl, (C7~C 20 ) Aralkyl, (C1~C6) alkyl substitution (C6~C 12 )aryl, or (C1~C6) alkyl-substituted benzyl, -CH2Si(R C )3(However, R C However, (C1~C 12 )It is a hydrocarbon) It is produced from a biphenylphenol polymerization pre-catalyst (where M is Zr or Hf) and used. Section 2: The biphenylphenol polymerization precatalyst of formula I has structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv), and (xv): [ka] [ka] [ka] [ka] [ka] The use described in item 1, selected from the group consisting of the following. Section 3: The use described in item 1, wherein the polymer formed under condition B (100°C and 100 pounds / square inch (psi) of ethylene, with an H2 / C2 ratio of 0.0017 and a C6 / C2 ratio of 0.4) has a molecular weight (Mw) in the range of about 150,000 daltons to about 800,000 daltons. Section 4: The use according to item 1, wherein the polymer formed under K conditions (100°C and 100 psi, with an H2 / C2 ratio of 0.0068 and a C6 / C2 ratio of 0.4) has a molecular weight (Mw) of less than about 500,000 daltons. Section 5: A polymerization catalyst system for producing polymers via a slurry phase polymerization process, Metalloceneolefin polymerization catalyst and A polymerization catalyst system comprising a supported biphenylphenol polymerization catalyst produced from the biphenylphenol polymerization precatalyst described in item 1. Item 6: A slurry phase polymerization method for producing polymers, A method comprising polymerizing an olefin monomer in a slurry phase polymerization reactor in the presence of the polymerization catalyst described in item 5 to produce the polymer. Section 7: R 15 and R 16 The polymerization catalyst system according to item 5 or the slurry phase polymerization method according to item 6, wherein each of the is 3,6-di-t-butylcarbazole-9-yl. Section 8: R 15 and R 16 The polymerization catalyst system according to item 5 or the slurry phase polymerization method according to item 6, wherein each of the is 2,7-di-t-butylcarbazole-9-yl. Section 9: The metalloceneolefin polymerization catalyst is (Pentamethylcyclopentadienyl)(Propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(Propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, (methylcyclopentadienyl)(1,3-dimethyltetrahydroindenyl)MX2, (cyclopentadienyl)(1,3-dimethyltetrahydroindenyl)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 A polymerization catalyst system according to claim 5 or a slurry phase polymerization method according to claim 6, 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 alkyl or alkenyl (C1-C5)). Section 10: A polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, wherein the high molecular weight polyethylene component and the low molecular weight polyethylene component are produced together in a single slurry phase reactor via a polymerization process using the polymerization catalyst system described in item 5.

Claims

1. The use of a supported biphenylphenol polymerization catalyst for producing an olefin polymer via a slurry phase polymerization process, wherein the supported biphenylphenol polymerization catalyst is of formula I: 【Chemistry 1】 (In the formula, R ５ , R ７ , R ８ , and R １０ Each of them independently, (C １ ~C ２０ ) Alkyl, aryl, aralkyl, halogen, or hydrogen, R ４ and R １１ Each of them is independently a halogen or hydrogen. R ２ and R １３ each are independently (C １ to C ２０ ) alkyl, aryl, aralkyl, or hydrogen, R １５ and R １６ Each of these is independently 2,7-disubstituted carbazole-9-yl or 3,6-disubstituted carbazole-9-yl, L may have a methyl substituent that forms a bridge between the two oxygen atoms to which L is covalently bonded, C ３ Alkylene or C ４ It is alkylene, R １ , R ３ , R １２ , and R １４ Each of them independently, (C １ ~C ８ ) Alkyl, halogen, or hydrogen, R ６ and R ９ Each of them is hydrogen, (C １ ~C ８ ) Alkyl or halogen, optionally R ６ R ７ It can be connected to R ８ However, R ９ It can be connected to form a ring structure, Each X independently contains halogen, hydrogen, (C １ ~C ２０ ) alkyl, (C ７ ~C ２０ ) Aralkir, (C １ ~C ６ ) Alkyl substitution (C ６ ~C １２ )aryl, or (C １ ~C ６ ) Alkyl-substituted benzyl, -CH ２ Si(R Ｃ ) ３ (However, R Ｃ However, (C １ ~C １２ ) is a hydrocarbon, It is produced from a biphenylphenol polymerization pre-catalyst (where M is Zr or Hf) and used.

2. The biphenylphenol polymerization precatalyst of formula I has structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viiii), (ix), (x), (xi), (xii), (xiii), (xiv), and (xv): 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 The use according to claim 1, selected from the group consisting of the following.

3. Condition B (ethylene at 100°C and 690 kPa (100 psi), H ２ / C ２ However, it is 0.0017, and C ６ / C ２ The use according to claim 1, wherein the olefin polymer formed with (where 0.4) has a molecular weight (Mw) in the range of about 150,000 daltons to about 800,000 daltons.

4. K conditions (ethylene at 100°C and 690 kPa (100 psi), H ２ / C ２ However, it is 0.0068, and C ６ / C ２ The use according to claim 1, wherein the olefin polymer formed with (but which is 0.4) has a molecular weight (Mw) of less than about 500,000 daltons.

5. A polymerization catalyst system for producing olefin polymers via a slurry phase polymerization process, Metalloceneolefin polymerization catalyst and A polymerization catalyst system comprising a supported biphenylphenol polymerization catalyst produced from a biphenylphenol polymerization pre-catalyst of formula I described in claim 1.

6. A slurry phase polymerization method for producing an olefin polymer, A method comprising polymerizing an olefin monomer in a slurry phase polymerization reactor in the presence of the polymerization catalyst described in claim 5 to produce the olefin polymer.

7. R １５ and R １６ The polymerization catalyst system according to claim 5, wherein each of the is 3,6-di-t-butylcarbazole-9-yl.

8. R １５ and R １６ The polymerization catalyst system according to claim 5, wherein each of the is 2,7-di-t-butylcarbazole-9-yl.

9. The metalloceneolefin polymerization catalyst is (Pentamethylcyclopentadienyl)(Propylcyclopentadienyl)MX ２ , (Tetramethylcyclopentadienyl)(Propylcyclopentadienyl)MX ２ , (Tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX ２ , (Methylcyclopentadienyl)(1,3-dimethyltetrahydroindenyl)MX ２ , (Cyclopentadienyl)(1,3-dimethyltetrahydroindenyl)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 (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 polymerization catalyst system according to claim 5, selected from the group consisting of alkyl or alkenyl (selected from the group consisting of alkyl or alkenyl (the

10. A method for producing a polyethylene composition comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component, the method comprising the step of producing the high molecular weight polyethylene component and the low molecular weight polyethylene component together in a single slurry phase reactor via a polymerization process using the polymerization catalyst system described in claim 5.

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