Biphenol polymerization catalyst

Abstract

Embodiments relate to the use of a supported biphenol polymerization catalyst prepared from a biphenol polymerization pre-catalyst of Formula I to prepare a polymer by a slurry phase polymerization process.

Description

Technical Field

[0001] The embodiments disclosed herein relate to biphenol polymerization catalysts, and more specifically, biphenol polymerization catalysts that can be used to prepare polymers via slurry-phase polymerization processes. Background Technology

[0002] Polymers can be used in a variety of products, including, for example, films, fibers, nonwoven and / or woven fabrics, extruded and / or molded products. Polymers can be prepared by reacting one or more types of monomers in a polymerization reaction in the presence of a polymerization catalyst. Summary of the Invention

[0003] This disclosure provides various implementation schemes, including:

[0004] Use of a supported biphenol polymerization catalyst for preparing polymers via a slurry-phase polymerization process, wherein the supported biphenol polymerization catalyst is prepared from a biphenol polymerization precatalyst of Formula I:

[0005]

[0006] Where R 5 R 7 R 8 and R 10 Each of them is independently (C1 to C) 20 )alkyl, aryl, aralkyl, halogen or hydrogen; wherein R 4 and R 11 Each of them is independently either halogen or hydrogen; where R 2 and R 13 Each of them is independently (C1 to C) 20 )alkyl, aryl or aralkyl or hydrogen; wherein R 15 and R 16 Each of them is independently 2,7-disubstituted carbazole-9-yl or 3,6-disubstituted carbazole-9-yl; wherein L is a C3-alkylene or C4-alkylene, which forms a bridge between the two oxygen atoms covalently bonded to L; wherein R 1 R 3 R 12 and R 14 Each of them is independently (C1-C8) alkyl, halogen, or hydrogen; wherein R 6 and R 9 Each of them is hydrogen, (C1-C8) alkyl, or halogen, optionally, R 6 Able to work with R 7 Connect and R 8 Able to work with R 9 Connected to form a ring structure; wherein each X is independently a halogen, hydrogen, (C1-C)20 )alkyl, (C7-C 20 Aryl, (C1-C6)alkyl substituted (C6-C 12 aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R) C ) 3， Where R C It is C1-C 12 Hydrocarbon; and M is zirconium (Zr) or hafnium (Hf). Detailed Implementation

[0007] Supported biphenol polymerization catalysts that can be used to prepare polymers via slurry polymerization processes are prepared from the biphenol polymerization precatalyst of Formula I:

[0008]

[0009] Where R 5 R 7 R 8 and R 10 Each of them is independently (C1 to C) 20 )alkyl, aryl, aralkyl, halogen or hydrogen; wherein R 4 and R 11 Each of them is independently either halogen or hydrogen; where R 2 and R 13 Each of them is independently (C1 to C) 20 )alkyl, aryl or aralkyl or hydrogen; wherein R 15 and R 16 Each of them is independently 2,7-disubstituted carbazole-9-yl or 3,6-disubstituted carbazole-9-yl; wherein L is a C3-alkylene or C4-alkylene, which forms a bridge between the two oxygen atoms covalently bonded to L; wherein R 1 R 3 R 12 and R 14 Each of them is independently (C1-C8) alkyl, halogen, or hydrogen; wherein R 6 and R 9 Each of them is hydrogen, (C1-C8) alkyl, or halogen, optionally, R 6 Able to work with R 7 Connect and R 8 Able to work with R 9 Connected to form a ring structure; wherein each X is independently a halogen, hydrogen, (C1-C) 20 )alkyl, (C7-C 20 Aryl, (C1-C6)alkyl substituted (C6-C) 12aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R) C )3, where R C It is C1-C 12 Hydrocarbon; and where M is Zr or Hf.

[0010] The biphenol polymerization precatalyst represented by Formula I as described herein (i.e., the biphenol polymerization precatalyst) can be used to prepare a biphenol polymerization catalyst. For example, the biphenol polymerization precatalyst represented by Formula I can be contacted with an activator under activating conditions to activate the biphenol polymerization precatalyst represented by Formula I, thereby preparing a biphenol polymerization catalyst.

[0011] As mentioned, R as shown in Equation I 5 R 7 R 8 and R 10 Each of them can be independently defined as (C1 to C). 20 Alkyl, aryl, aralkyl, halogen, or hydrogen. One or more embodiments specify R. 5 R 7 R 8 and R 10 At least one of them is a halogen, such as fluorine. One or more embodiments specify R 5 R 7 R 8 and R 10 Each of these is a halogen, such as fluorine. One or more embodiments specify R. 5 and R 10 Each of these is a halogen, such as fluorine. One or more embodiments specify R. 5 and R 10 Each of these is chlorine. One or more implementation schemes specify R 5 and R 10 Each of them is a methyl group. One or more embodiments specify R 5 and R 10 At least one of them is an alkyl- or aryl-substituted silyl group. One or more embodiments specify R 5 and R 10 Each of them is a dialkyl or trialkyl-substituted silyl group. One or more embodiments specify R 5 and R 10 Each of them is octyl dimethylsilyl.

[0012] One or more implementation schemes specify R 7 and R 8 Each of them is independently hydrogen or methyl. One or more embodiments specify R 7 and R 8At least one of them is hydrogen. One or more implementation schemes specify R 7 and R 8 Each of them is hydrogen. One or more implementation schemes specify R 7 and R 8 At least one of them is a C1 alkyl group, such as methyl. One or more embodiments specify R 7 and R 8 Each of them is a methyl group.

[0013] One or more implementation schemes specify R 1 R 3 R 12 and R 14 Each of these is independently (C1-C8) alkyl, halogen, or hydrogen. One or more embodiments specify R 1 R 3 R 12 and R 14 At least one of them is hydrogen. One or more implementation schemes specify R 1 R 3 R 12 and R 14 Each of them is hydrogen.

[0014] One or more implementation schemes specify R 6 and R 9 Each of them is hydrogen, (C1-C8) alkyl, or halogen, such as fluorine, optionally, R 6 Able to work with R 7 Connect and R 8 Can be used with R 9 Connect to form a ring structure. One or more implementations specify R 6 and R 9 Each of these is hydrogen or a halogen, such as fluorine. One or more embodiments specify R. 6 and R 9 Each of them is hydrogen. One or more implementation schemes specify R 6 and R 9 Each of these is a halogen, such as fluorine. One or more embodiments specify R. 6 Able to work with R 7 Connect and R 8 Able to work with R 9 Connect them to form a ring structure.

[0015] As used herein, "alkyl" includes straight-chain, branched, and cyclic alkane groups lacking one hydrogen atom. Thus, for example, the CH3 group ("methyl") and the CH3CH2 group ("ethyl") are examples of alkyl groups.

[0016] As used herein, "aryl" includes phenyl, naphthyl, pyridyl, and other groups whose molecules have the characteristic ring structures of benzene, naphthalene, phenanthrene, anthracene, etc. It should be understood that "aryl" can be C6 to C6. 20 Aryl. For example, the C6H5-aromatic structure is "phenyl", and the -C6H4-aromatic structure is "phenylene". As used herein, "aralkyl" is an alkyl group having a side aryl group, and may also be referred to as "arylalkyl". It should be understood that "aralkyl" can be C7 to C6. 20 Aryl group. “Alkyl group” is an aryl group having one or more side-attached alkyl groups. As used herein, “hydrocarbon group” includes aliphatic, cyclic, alkene, alkyne and aromatic groups (i.e., hydrocarbon groups) that include hydrogen and a carbon atom lacking one hydrogen atom.

[0017] As described above, R as shown in Equation I 4 and R 11 Each of these can be independently hydrogen or a halogen, such as fluorine. For example, one or more embodiments specify R 4 and R 11 Each of them is hydrogen. One or more implementation schemes specify R 4 and R 11 Each of them is fluorine.

[0018] As described above, R as shown in Equation I 2 and R 13 Each of them can be independently defined as (C1 to C). 20 )alkyl, aryl, or aralkyl or hydrogen. One or more embodiments specify R 2 and R 13 Each of them is a (C3-C4) alkyl group, such as n-butyl, tert-butyl, or 2-methylpentyl. One or more embodiments specify R. 2 and R 13 Each of them is 1,1,3,3-tetramethylbutyl. One or more embodiments specify R 2 and R 13 Each of them is a (C1) alkyl group, i.e., methyl.

[0019] As described above, R as shown in Equation I 15 and R 16 Each of them may be 2,7-disubstituted carbazole-9-yl or 3,6-disubstituted carbazole-9-yl. For example, one or more embodiments specify 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-tert-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 specify R 15and R 16 Each of them is a 3,6-disubstituted carbazole-9-yl selected from the group consisting of 3,6-di-tert-butylcarbazole-9-yl, 3,6-diethylcarbazole-9-yl, 3,6-dimethylcarbazole-9-yl and 3,6-bis(diisopropyl(n-octyl)silyl)carbazole-9-yl.

[0020] As mentioned, L as shown in Formula I can be a C3-alkylene or C4-alkylene, which forms a bridge between the two oxygen atoms covalently bonded to L. For example, in one or more embodiments, L can be a saturated (C3-C4) alkyl, which forms a 3-carbon bridge or a 4-carbon bridge between the two oxygen atoms bonded to L. For example, one or more embodiments specify L as a saturated (C3) alkyl, which forms a bridge between the two oxygen atoms bonded to L. The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double or triple bonds. One or more embodiments specify L as a saturated (C4) alkyl, which forms a bridge between the two oxygen atoms bonded to L.

[0021] As mentioned, each X shown in Equation I can independently be a halogen, hydrogen, (C1-C2) 20 )alkyl, (C7-C 20 Aryl, (C1-C6)alkyl substituted (C6-C) 12 )aryl or (C1-C6)alkyl substituted benzyl, -CH2Si(R C )3 (where R C For C1-C 12 Hydrocarbons). For example, one or more embodiments specify that each X is a (C1) alkyl group.

[0022] As mentioned, M in Formula I is a heteroatom, such as a metal atom. In some embodiments, M may be selected from Zr and Hf. One or more embodiments specify M as zirconium. One or more embodiments specify M as hafnium.

[0023] As described herein, the R group (R) of Formula I 1 -R 16 Each of (C1-C6) and X can be independently substituted or unsubstituted. For example, in some embodiments, each of X in Formula I can be independently (C1-C6) alkyl-substituted (C6-C6) alkyl-substituted ... 12)aryl or (C1-C6)alkyl-substituted benzyl. As used herein, "substituted" indicates that the group following the term has at least one moiety replacing one or more hydrogens at any position, and these moiety are selected from groups such as: halogen groups, hydroxyl groups, carbonyl groups, carboxyl groups, amino groups, phosphinyl groups, alkoxy groups, phenyl groups, naphthyl groups, (C1 to C6)alkyl-substituted benzyl groups. 20 )alkyl groups, (C2 to C 10 Alkenyl groups and combinations thereof. "Disubstituted" means that two or more substituent groups are present at any position, and these moieties are selected from groups such as: halogen groups, hydroxyl groups, carbonyl groups, carboxyl groups, amino groups, phosphinyl groups, alkoxy groups, phenyl groups, naphthyl groups, (C1 to C2) alkenyl ... 20 )alkyl groups, (C2 to C 10 Alkenyl groups and their combinations.

[0024] The metallocene olefin polymerization catalyst and the biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst described herein can be prepared using the reactants mentioned herein. The metallocene olefin polymerization catalyst and the biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst described herein can be prepared by a variety of methods, such as using conventional solvents, reaction conditions, reaction times, and separation procedures used to prepare known catalysts such as known metallocene olefin polymerization catalysts.

[0025] One or more embodiments provide a polymerization catalyst, namely a biphenol polymerization catalyst prepared from a biphenol polymerization precatalyst of Formula I. The biphenol polymerization catalyst can be prepared by contacting a biphenol polymerization precatalyst with an activator under activating conditions to provide a biphenol polymerization catalyst, such as an activated biphenol polymerization precatalyst. Activation conditions are well known in the art.

[0026] As used herein, "activator" means any supported or unsupported compound or combination of compounds that can, for example, activate a complex or catalyst component by generating a cationic species of the catalyst component. For example, this can include abstracting at least one leaving group (e.g., the "X" group described herein) from the metal center of the complex / catalyst component (e.g., a metal complex of formula I). ​​As used herein, "leaving group" means one or more chemical moieties that are bonded to a metal atom and can be abstracted by an activator to produce a substance active for olefin polymerization.

[0027] Activators may include Lewis acids or noncoordinated ionic activators or ionized activators, or any other compound including Lewis bases, alkylaluminum and / or conventional cocatalysts. In addition to the methylaluminoxane (“MAO”) and modified methylaluminoxane (“MMAO”) mentioned above, illustrative activators may include, but are not limited to, aluminoxanes or modified aluminoxanes and / or ionized neutral or ionic compounds, such as dimethylphenylammonium tetra(pentafluorophenyl)borate, triphenylcarbazide tetra(pentafluorophenyl)borate, dimethylphenylammonium tetra(3,5-(CF3)2phenyl)borate, and triphenylcarbazide tetra(3,5-(CF3)2phenyl)borate. 3) 2-phenyl)borate, dimethylphenylammonium tetra(perfluoronaphthyl)borate, triphenylcarbamonium tetra(perfluoronaphthyl)borate, dimethylphenylammonium tetra(pentafluorophenyl)aluminate, triphenylcarbamonium tetra(pentafluorophenyl)aluminate, dimethylphenylammonium tetra(perfluoronaphthyl)aluminate, triphenylcarbamonium tetra(perfluoronaphthyl)aluminate, tri(perfluorophenyl)boron, tri(perfluoronaphthyl)boron, tri(perfluorophenyl)aluminum, tri(perfluoronaphthyl)aluminum or any combination thereof.

[0028] Aluminoxanes can be described as oligoaluminate compounds having an -Al(R)-O- subunit, where R is an alkyl group. Examples of aluminoxanes include, but are not limited to, methylaluminoxane (“MAO”), modified methylaluminoxane (“MMAO”), ethylaluminoxane, isobutylaluminoxane, or combinations thereof. Aluminoxanes can be produced by hydrolyzing the corresponding trialkylaluminum compound. MMAO can be produced by hydrolyzing trimethylaluminum and higher trialkylaluminum (such as triisobutylaluminum). Various known methods exist for the preparation of aluminoxanes and modified aluminoxanes. Aluminoxanes can include type 3A modified methylaluminoxane (“MMAO”) (commercially available under the trade name Modified Methylaluminoxane type 3A from Akzo Chemicals, Inc., as discussed in U.S. Patent No. 5,041,584). The source of MAO can be a solution having, for example, about 1% by weight to about 50% by weight of MAO. Commercially available MAO solutions may include 10% by weight and 30% by weight MAO solutions, which are available from Albemarle Corporation of Baton Rouge, Louisiana.

[0029] One or more organoaluminum compounds, such as one or more alkylaluminum compounds, can be used in combination with aluminum oxanes. Examples of alkylaluminum compounds include, but are not limited to, ethoxydiethylaluminum, diethylaluminum chloride, diisobutylaluminum hydrogenation, and combinations thereof. Examples of other alkylaluminum compounds (e.g., trialkylaluminum compounds) include, but are not limited to, trimethylaluminum, triethylaluminum (“TEAL”), triisobutylaluminum (“TiBAl”), tri-n-hexylaluminum, tri-n-octylaluminum, tripropylaluminum, tributylaluminum, and combinations thereof.

[0030] The metallocene olefin polymerization catalyst can be any metallocene olefin polymerization catalyst. In one or more embodiments, the metallocene olefin polymerization catalyst is selected from the group consisting of: (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, Me2Si(indenyl)2MX2, Me2Si(tetrahydroindenyl)2MX2, (n-propylcyclopentadienyl)2MX2, (n-butylcyclopentadienyl)2MX2, (1-methyl,3-butylcyclopentadienyl)2 MX2, 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 to C5) alkyl or alkenyl. In one or more embodiments, the metallocene olefin polymerization catalyst is selected from the group consisting of bis(indenyl)zirconia dichloride, (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconia dichloride or (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconia dichloride.

[0031] The following polymerization catalyst systems can be used to prepare polymers: metallocene olefin polymerization catalysts; and biphenol polymerization catalysts prepared from biphenol polymerization precatalysts. For example, polymers, such as polyolefin polymers, can be prepared by contacting the polymerization catalyst system with olefins under polymerization conditions in a slurry polymerization reactor.

[0032] As used herein, a "polymer" refers to two or more identical or different polymeric units derived from one or more different monomers, such as homopolymers, copolymers, terpolymers, etc. A "homogeneous polymer" is a polymer having identical polymeric units. A "copolymer" is a polymer having two or more polymeric units that are different from each other. A "terpolymer" is a polymer having three polymeric units that are different from each other. "Different" in relation to polymeric units indicates that the polymeric units differ from each other by at least one atom or areomer. Therefore, as used herein, the definition of a copolymer includes terpolymers, etc. As used herein, a "polymerization process" is a process used to prepare a polymer.

[0033] The implementation scheme specifies that the polymer can be a polyolefin polymer. As used herein, "olefin," which may be referred to as "alkene," means a straight-chain, branched, or cyclic compound comprising carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer is referred to as containing an olefin (e.g., prepared from an olefin), the olefin present in such polymer or copolymer is an olefin in a polymeric form. For example, when a copolymer is claimed to have an ethylene content of 1 wt% to 99 wt%, it should be understood that the polymeric units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present in amounts of 1 wt% to 99 wt% based on the total weight of the polymer. Higher α-olefins refer to α-olefins having three or more carbon atoms.

[0034] Polyolefins include polymers prepared from olefin monomers such as ethylene, i.e., polyethylene, and straight-chain or branched high-carbon α-olefin monomers containing 3 to 20 carbon atoms. Examples of high-carbon 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 ethylene-based polymers having at least 50 wt% ethylene, including copolymers of ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene. Other monomers that may be used include, for example, olefinically unsaturated monomers, dienes having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cycloolefins. Examples of monomers may include, but are not limited to, norbornene, norbornadiene, isobutene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentane. In many embodiments, copolymers of ethylene can be produced, wherein a comonomer having at least one α-olefin having 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably 4 to 8 carbon atoms, is polymerized with ethylene, for example, in a slurry-phase polymerization process. In another embodiment, ethylene and / or propylene can be polymerized with at least two different comonomers to prepare a terpolymer, optionally, one of these comonomers may be a diene.

[0035] One or more embodiments specify that, based on the total weight of the polymer, the polymer may include 1 wt% to 100 wt% of ethylene-derived units. This includes all individual values ​​and sub-ranges from 1 wt% to 100 wt%; for example, based on the total weight of the polymer, the polymer may contain ethylene-derived units ranging from a lower limit of 1 wt%, 5 wt%, 10 wt%, or 50 wt% to an upper limit of 100 wt%, 95 wt%, 90 wt%, 85 wt%, or 75 wt% of ethylene-derived units.

[0036] Polymerization catalyst systems, including biphenol polymerization catalysts prepared from biphenol polymerization precatalysts of Formula I, can facilitate the provision of polymers via a polymerization process in a single slurry 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 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 formed together in a single slurry reactor via a polymerization process employing the polymerization catalyst system. In some applications, having both a high molecular weight polyethylene component and a low molecular weight polyethylene component is desirable.

[0037] Surprisingly, polymerization catalyst systems including biphenol polymerization catalysts prepared from biphenol polymerization precatalysts of Formula I of this disclosure can produce polymers containing high molecular weight polyethylene components that have lower molecular weights than high molecular weight components in polymers formed under similar polymerization conditions using other (non-inventive) polymerization catalysts, as detailed herein. High molecular weight polyethylene components with lower molecular weights than other high molecular weight polyethylene components are desirable in some applications.

[0038] The implementation specifies that the polymer can have a number-average molecular weight (Mn) of 8,000 to 400,000. This includes all individual values ​​and sub-ranges of 8,000 to 400,000; for example, the polymer can have an Mn range 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 implementations, Mn can be in the range of 40,300 to 207,200.

[0039] The embodiments specify that the polymer can have a molecular weight (Mw) of about 150,000 to about 800,000 under B-conditions and / or less than about 500,000 Daltons under K-conditions. This includes all individual values ​​and sub-ranges from 150,000 to 800,000; for example, the polymer can have a Mw from a lower limit of about 50,000, about 100,000, about 150,000, or about 200,000 to an upper limit of about 800,000, about 700,000, or about 600,000 under K-conditions. Some embodiments specify that the polymer can have a molecular weight (Mw) of 150,000 to 800,000 under B-conditions and / or less than 500,000 Daltons under K-conditions. This includes all individual values ​​and sub-ranges from 150,000 to 800,000; for example, a polymer can have a Mw of 150,000 or 200,000 to 800,000, 700,000, or 600,000 under K-conditions. In some examples, a polymer can have a Mw of 50,000 to 500,000 or 100,000 to 500,000 under K-conditions. As used herein, B-conditions are as follows: temperature = 100°C; ethylene = 100 psi; H2 / C2 = 0.0017; C6 / C2 = 0.4. As used herein, K-conditions are as follows: temperature = 100°C; ethylene = 100 psi; H2 / C2 = 0.0068; C6 / C2 = 0.4.

[0040] The implementation scheme specifies that the polymer can have an Mz (z-average molecular weight) of 200,000 to 10,000,000. This includes all individual values ​​and sub-ranges from 200,000 to 10,000,000; for example, the polymer can have an Mz of 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.

[0041] The implementation scheme specifies that the Mz to Mw ratio of the polymer can be in the range of 2.00 to 20.00. This includes all individual values ​​and sub-ranges from 2.00 to 20.00; for example, the polymer can have an Mz to Mw ratio with a lower limit of 2.00, 3.00, or 4.00 to an upper limit of 20.00, 15.00, or 10.00.

[0042] In some embodiments, the Mw to Mn ratio of the polymer can be greater than 2.00, greater than 3.00, greater than 4.00, or greater than 5.00. Some embodiments specify that the Mw to Mn ratio of the polymer can be in the range of 5.00 to 75.00. This includes all individual values ​​and sub-ranges from 5.00 to 75.00; for example, the polymer can have an Mw to Mn ratio with 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.

[0043] The implementation plan stipulates that the ratio of Mz to Mw in the polymer can be less than the ratio of Mw to Mn in the polymer.

[0044] The implementation plan specifies that the polymer may have a melt index (I) in the range of 0.001 dg / 1min to 1000 dg / 1min. 21 ), as measured by ASTM D1238 (at 190°C and a 21 kg load). Includes all individual values ​​and sub-ranges from 0.001 dg / 1 min to 1000 dg / 1 min.

[0045] The implementation scheme specifies that polymers prepared using a gas-phase polymerization reactor can have a melting temperature (Tm) ranging from 110°C to 135°C. This includes all individual values ​​and sub-ranges from 118°C to 135°C; for example, the Tm of the polymer can be 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 D 3418-08. For example, a scan rate of 10°C / min is used for a 10 mg sample, and a second heating cycle is employed.

[0046] The implementation plan specifies that the polymer can have a density of 0.890 g / cm³. 3 Up to 0.970 g / cm 3 The density ranges from 0.890 to 0.970 g / cm³. 3 All individual values ​​and sub-ranges; for example, the density of the polymer can be 0.890, 0.900, 0.910, 0.920 or 0.940 g / cm³. 3 The lower limit is 0.970, 0.960 or 0.950 g / cm³. 3The upper limit. Density can be determined according to ASTM D-792-13, "Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B" (for testing solid plastics in liquids other than water, such as in liquid 2-propanol). It is expressed in grams per cubic centimeter (g / cm³). 3 The results should be reported by unit.

[0047] Gel permeation chromatography (GPC) test method: Weight-average molecular weight test method: Mw and number-average molecular weight (Mw) are determined using chromatograms obtained on a high-temperature gel permeation chromatography system (HTGPC, Polymer Laboratories). n ) and M w / M n The HTGPC is equipped with a transfer line, a differential refractive index detector (DRI), and three polymer laboratory PLgel 10 μm Mixed-B columns, all contained in an oven maintained at 160 °C. The method uses a solvent consisting of BHT-treated TCB at a nominal flow rate of 1.0 mL / min and a nominal injection volume of 300 μL. The solvent is prepared by dissolving 6 g of butylated hydroxytoluene (BHT, an antioxidant) in 4 L of reagent-grade 1,2,4-trichlorobenzene (TCB) and filtering the resulting solution through a 0.1 μm Teflon filter. The solvent is degassed using an online degasser before entering the HTGPC instrument. The column is calibrated using a series of monodisperse polystyrene (PS) standards. Individually, a known concentration of the test polymer dissolved in the solvent is prepared by heating a known amount of the test polymer in a known volume of solvent at 160 °C with continuous shaking for 2 hours to obtain a solution. (All quantities were measured by gravimetric analysis.) The target solution concentration c for the tested polymer ranged from 0.5 mg polymer / mL solution (mg / mL) to 2.0 mg polymer / mL solution, with lower concentrations c used for higher molecular weight polymers. The DRI detector was purged before each sample run. The flow rate in the device was then increased to 1.0 mL / min, and the DRI detector was allowed to stabilize for 8 hours before injecting the first sample. M was calculated using the universal calibration relationship with column calibration. w and M n Calculate the MW per elution volume using the following equation: Where the subscript "X" represents the test sample, the subscript "PS" represents the PS standard, and aPS =0.67, a Ps =0.67K Ps =0.000175 and a X and K X Obtained from published literature. For polyethylene, a x / K x = 0.695 / 0.000579. For polypropylene, a x / K x =0.705 / 0.0002288. At each point in the resulting chromatogram, the DRI signal I minus the baseline is calculated using the following equation. DRI Calculate concentration c: c = K DRI I DRI / (dn / dc), where K DRI For DRI calibration, dn / dc is a constant determined by DRI, / denotes division, and dn / dc is the refractive index increment of the polymer. For polyethylene, dn / dc = 0.109. The polymer mass recovery is calculated from the ratio of the integrated area at the elution volume of the concentration chromatogram to the injected mass, which is equal to the predetermined concentration multiplied by the injected loop volume. Unless otherwise stated, all molecular weights are reported in grams per mole (g / mol). Further details of the methods for determining Mw, Mn, and MWD are described in US 2006 / 0173123, pages 24-25, paragraphs

[0334] to

[0341] . A graph of dW / dLog(MW) on the y-axis against Log(MW) on the x-axis gives the GPC chromatogram, where Log(MW) and dW / dLog(MW) are as defined above.

[0048] Polymers can be used in a variety of products, such as films, fibers, nonwoven and / or woven fabrics, extruded products and / or molded products.

[0049] A polymerization catalyst system is provided for preparing polymers via a slurry-phase polymerization process. The polymerization catalyst system comprises: a metallocene olefin polymerization catalyst; and a supported biphenol polymerization catalyst prepared from a biphenol polymerization precatalyst of Formula I as detailed herein.

[0050] Metallocene olefin polymerization catalysts and / or biphenol polymerization catalysts made from biphenol polymerization precatalysts of Formula I, as well as other components described herein such as activators, may be used with a support. "Support" may also be referred to as "carrier" and refers to any support material, including porous support materials (such as talc), inorganic oxides, and inorganic chlorides.

[0051] Metallocene olefin polymerization catalysts and / or biphenol polymerization catalysts made from biphenol polymerization precatalysts of Formula I, as well as other components described herein, may be supported on the same or different supports, or one or more components may be used in unsupported form. Utilization of the support can be achieved by any technique used in the art. One or more embodiments specify the use of a spray drying process. Spray drying processes are well known in the art. The support may be functionalized.

[0052] The carrier can be a porous carrier material (e.g., talc), an inorganic oxide, or an inorganic chloride. Other carrier materials include resin carrier materials (e.g., polystyrene), functionalized or cross-linked organic carriers (such as polystyrene-divinylbenzene polyolefins or polymeric compounds), zeolites, clay, or any other organic or inorganic carrier material, or mixtures thereof.

[0053] The support material includes inorganic oxides, including metal oxides from Groups 2, 3, 4, 5, 13, or 14. Some preferred supports include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Some other supports include magnesium oxide, titanium dioxide, zirconium oxide, magnesium chloride, montmorillonite, shale silicates, zeolites, talc, clay, etc. Moreover, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium dioxide, etc. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads.

[0054] An example of a carrier could be the trade name Cabosil. TM TS-610 is a fumed silica produced by fusion processing, or other TS- or TG-series carriers available from Cabot Corporation. Fumed silica is typically silica with a particle size of 7 to 30 nanometers, which has been treated with dimethylsilyl dichloride to end most of the surface hydroxyl groups.

[0055] The carrier material can have a range of approximately 10m 2 / g to approximately 700m 2 The surface area is approximately 0.1 g / cm³. 3 Approximately 4.0 g / cm³ 3 The pore volume and average particle size range from about 5 μm to about 500 μm. More preferably, the surface area of ​​the carrier material ranges from about 50 m². 2 / g to approximately 500m 2 / g, pore volume is approximately 0.5g / cm³ 3 Approximately 3.5 g / cm³ 3The average particle size is from about 10 μm to about 200 μm. Most preferably, the surface area of ​​the carrier material is in the range of about 100 m². 2 / g to approximately 400m 2 / g, pore volume is approximately 0.8g / cm³ 3 Approximately 3.0 g / cm³ 3 The average particle size is from about 5 μm to about 100 μm. The average pore size of the delivery medium typically has a pore size in the range of 10 Å to 1000 Å, preferably from 50 Å to about 500 Å, and most preferably from 75 Å to about 350 Å.

[0056] Metallocene olefin polymerization catalysts and / or biphenol polymerization catalysts made from biphenol polymerization precatalysts of Formula I, along with other components described herein such as activators, may be slurries. Slurries are well known in the art. Slurries may include, for example, metallocene olefin polymerization catalysts and / or biphenol polymerization precatalysts made from biphenol polymerization precatalysts of Formula I, activators, and supports.

[0057] In the slurry, the molar ratio of the metal in the activator to the metal in the metallocene olefin polymerization catalyst or the biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst of Formula I can 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. One or more diluents, such as fluids, can be used to promote the combination of any two or more components in the slurry. For example, the metallocene olefin polymerization catalyst or the biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst of Formula I and the activator can be combined together in the presence of toluene or another non-reactive hydrocarbon or mixture of hydrocarbons. Other suitable diluents besides toluene may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. A dry or toluene-mixed support can then be added to the mixture, or a metal-ligand complex / activator can be added to the support. The slurry can be fed into the reactor for polymerization, and / or the slurry can be dried, for example, by spray drying, before being fed into the reactor for polymerization.

[0058] As mentioned, the polymerization process can be a slurry polymerization process via a slurry polymerization reactor. The polymerization process can utilize known equipment and reaction conditions, such as known polymerization conditions. For example, the polymerization temperature can range from about 0°C to about 300°C at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure. Embodiments provide a method for preparing a polyolefin polymer, the method comprising: contacting an olefin with a polymerization catalyst system as described herein under polymerization conditions to polymerize the olefin, thereby preparing the polyolefin polymer.

[0059] One or more embodiments specify that the polymer can be formed via a slurry polymerization system at pressures above atmospheric pressure in the range of 0.07 bar to 68.9 bar, 3.45 bar to 27.6 bar, or 6.89 bar 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 polymerization system can be used.

[0060] Conventional slurry-phase fluidized bed polymerization processes can typically be carried out by continuously passing a feed stream containing one or more olefin monomers through a fluidized bed reactor at a rate sufficient to keep the solid particle bed in suspension, under reaction conditions and in the presence of a catalyst composition (e.g., a composition comprising a polymerization catalyst system (metallocene olefin polymerization catalyst or a biphenol polymerization catalyst prepared from a biphenol polymerization precatalyst of formula I) and an activator). The feed stream, including unreacted monomers, can be continuously recovered from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled back to the reactor. The product (i.e., the polymer) can be removed from the reactor, and substitute monomers can be added to the circulating stream. An inert gas to the catalytic composition and reactants can also be present in the gas stream. The polymerization system can include, for example, a single reactor or two or more reactors in series.

[0061] The feed stream used in the polymerization process may include olefin monomers, non-olefin gases (such as nitrogen and / or hydrogen), and may also include one or more non-reactive alkanes that can be condensed during polymerization and used to remove heat of reaction. Illustrative non-reactive alkanes include, but are not limited to, propane, butane, isobutane, pentane, isopentane, hexane, their isomers, and their derivatives. The feed may enter the reactor at one or more different locations.

[0062] For the polymerization process, the polymerization catalyst (metallocene olefin polymerization catalyst and / or biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst of Formula I) can be continuously fed into the reactor.

[0063] For the polymerization process, the amount of hydrogen used in the reactor can be such that the gaseous molar ratio of hydrogen to ethylene is in the range of about 0.0 to 3.5, 0.0 to 1.0, 0.01 to 0.7, 0.03 to 0.5, 0.005 to 0.3, or 0.0017 to 0.0068. Many embodiments utilize hydrogen.

[0064] Several aspects of this disclosure are provided below.

[0065] Aspect 1 provides the use of a supported biphenol polymerization catalyst to prepare polymers via a slurry polymerization process, wherein the supported biphenol polymerization catalyst is prepared from a biphenol polymerization precatalyst of Formula I:

[0066]

[0067] Where R 5 R 7- R 8 and R 10 Each of them is independently (C1 to C) 20 )alkyl, aryl, aralkyl, halogen or hydrogen; wherein R 4 and R 11 Each of them is independently either halogen or hydrogen; where R 2 and R 13 Each of them is independently (C1 to C) 20 )alkyl, aryl or aralkyl or hydrogen; wherein R 15 and R 16 Each of them is independently 2,7-disubstituted carbazole-9-yl or 3,6-disubstituted carbazole-9-yl; wherein L is a C3-alkylene or C4-alkylene, which forms a bridge between the two oxygen atoms covalently bonded to L; wherein R 1 R 3 R 12 and R 14 Each of them is independently (C1-C8) alkyl, halogen, or hydrogen; wherein R 6 and R 9 Each of them is hydrogen, (C1-C8) alkyl, or halogen, optionally, R 6 Able to work with R 7 Connect and R 8 Able to work with R 9 Connected to form a ring structure; wherein each X is independently a halogen, hydrogen, (C1-C) 20 )alkyl, (C7-C 20 Aryl, (C1-C6)alkyl substituted (C6-C) 12 aryl, or (C1-C6)alkyl-substituted benzyl, -CH2Si(R) C ) 3， Where R C It is C1-C 12 Hydrocarbon; and M is zirconium (Zr) or hafnium (Hf).

[0068] Aspect 2 specifies the use according to aspect 1, wherein the biphenol polymerization precatalyst of formula I is selected from the group consisting of structures of (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv) and (xv), as described herein.

[0069] Aspect 3 specifies that, according to the intended use described in the aspect, the polymer formed under B-conditions (H2 / C2 = 0.0017 and C6 / C2 = 0.4 at 100°C and 100 psi ethylene) has a molecular weight (Mw) in the range of about 150,000 Daltons to about 800,000 Daltons.

[0070] Aspect 4 specifies the use according to Aspect 1, wherein the polymer formed under K-conditions (H2 / C2 = 0.0068 and C6 / C2 = 0.4 at 100°C and 100 psi) 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 of about 150,000 to about 800,000 Daltons under B-conditions or less than about 500,000 Daltons under K-conditions.

[0071] Aspect 5 provides a polymerization catalyst system for preparing polymers via a slurry polymerization process, the polymerization catalyst system comprising: a metallocene olefin polymerization catalyst; and the supported biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst according to aspect 1.

[0072] Aspect 6 provides a slurry-phase polymerization method for preparing a polymer, the method comprising: polymerizing olefin monomers in a slurry-phase polymerization reactor in the presence of a polymerization catalyst system according to aspect 5 to prepare the polymer. In various embodiments, part or all of the polymerization catalyst system (e.g., metallocene and / or biphenol polymerization pre-catalyst / catalyst) is provided as a trimming solution. For example, a portion of the metallocene catalyst may be provided as a trimming solution. Alternatively, a portion of the biphenol polymerization pre-catalyst / catalyst may be provided as a trimming solution.

[0073] Aspect 7 specifies the polymerization catalyst system according to aspect 5 or the slurry polymerization method according to aspect 6, wherein R 15 and R 16 Each of them is 3,6-di-tert-butylcarbazole-9-yl.

[0074] Aspect 8 specifies the polymerization catalyst system according to aspect 5 or the slurry polymerization method according to aspect 6, wherein R 15 and R16 Each of them is 2,7-di-tert-butylcarbazole-9-yl.

[0075] Aspect 9 specifies the polymerization catalyst system according to aspect 5 or the slurry polymerization method according to aspect 6, wherein the metallocene olefin polymerization catalyst is selected from the group consisting of:

[0076] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2,

[0077] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2,

[0078] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2,

[0079] (methylcyclopentadienyl)(1,3-dimethyl-tetrahydroindenyl)MX2,

[0080] (cyclopentadienyl)(1,3-dimethyl-tetrahydroindenyl)MX2,

[0081] (cyclopentadienyl)(4,7-dimethylindenyl)MX2,

[0082] (cyclopentadienyl)(1,5-dimethylindenyl)MX2,

[0083] (cyclopentadienyl)(1,4-dimethylindenyl)MX2,

[0084] Me2Si(indene)2MX2,

[0085] Me2Si(tetrahydroindenyl)2MX2,

[0086] (n-propylcyclopentadienyl)2MX2,

[0087] (n-Butylcyclopentadienyl)2MX2,

[0088] (1-Methyl, 3-butylcyclopentadienyl)2MX2,

[0089] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2、

[0090] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2、

[0091] (Butylcyclopentadienyl)2MX2,

[0092] (propylcyclopentadienyl)2MX2 and mixtures thereof

[0093] Where M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3 and (C1 to C5) alkyl or alkenyl.

[0094] Aspect 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 prepared together in a single slurry reactor by a polymerization process employing a polymerization catalyst system according to aspect 5.

[0095] Example

[0096] The following describes the preparation of a biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst of formula (I), a polymerization catalyst system including the biphenol polymerization catalyst, and a comparative polymerization catalyst (other than the comparative polymerization catalyst prepared from the polymerization precatalyst of formula (I)).

[0097] The following describes the preparation of a biphenol polymerization catalyst and a polymerization catalyst system s comprising the biphenol polymerization catalyst, which are prepared from the biphenol polymerization precatalyst of formula (I).

[0098] The precatalyst for biphenol polymerization with structure (i) was prepared as follows.

[0099]

[0100] Preparation of 4-dodecyl-2-iodo-6-methylphenol: 4-Dodecyl-2-methylphenol (2.12 g, 7.688 mmol) and p-toluenesulfonic acid monohydrate (1.48 g, 7.78 mmol) were added to acetonitrile (25 mL) and stirred at 0 °C to 10 °C (ice-water bath) for about 15 min. At this point, N-iodosuccinimide (1.73 g, 7.668 mmol) was added. The reaction mixture became a thick slurry, so another acetonitrile (25 mL) was added and the mixture was stirred again. The reaction mixture was heated to room temperature and stirred for 24 h, after which approximately 16% of the starting material remained. Therefore, an additional 0.3 equivalent of N-iodosuccinimide (0.52 g, 2.30 mmol) was added to the reaction and stirred at room temperature for 5 h. The reaction mixture was concentrated to dryness, dissolved in dichloromethane (50 mL), washed with 10 wt.% sodium thiosulfate aqueous solution (3 x 50 mL), washed with water and then brine (50 mL each), dried over anhydrous MgSO4, filtered through a silica gel pad, and then concentrated to give 2.80 g of a crude compound as a grayish-white solid with a purity of approximately 95% as determined by GC-MS. The product was recrystallized from hexane (8 mL) to give 1.79 g (58.0%) of pure product.

[0101] 1H NMR (400MHz, CDCl3) δ7.29(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).

[0102]

[0103] 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 min, then cooled and concentrated to dryness by rotary evaporation. The residue was dissolved in a 1:1 mixture of dichloromethane and water (100 mL) and extracted into dichloromethane (3 x 50 mL). The combined organic phases were washed with 200 mL each of 2NNaOH, water, and then brine, dried over anhydrous MgSO₄, filtered through a small silica gel pad, and concentrated to give 1.6 g of the compound as a brown oil. The crude product was recrystallized from hexane (10 mL) to give 1.32 g (77.1%) of the product as a white, fluffy powder.

[0104]

[0105] Add to 40 mL of dimethyl ether 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (prepared as described in WO 2017 / 004462A1), 1.274 g (1.508 mmol) of 1,3-bis(4-dodecyl-2-iodo-6-methylphenoxy)propane, 0.447 g of NaOH (11.2 mmol) of water, and 15 mL of THF. The reaction mixture was bubbled with N2 for about 15 minutes, then 112 mg (0.097 mmol) of Pd(PPh3)4 was added and the mixture was heated to 85 °C for 48 hours, followed by cooling. Once cooled, a precipitate formed, which was separated by vacuum filtration and dried under high vacuum for about 2 hours. The crude protected product was used as is for the next step. 150 mL of 1:1 methanol / THF and about 100 mg of PTSA were added to the crude protected ligand. The solution was heated to 60 °C for 6 hours, cooled, and concentrated. The crude ligand was dissolved in dichloromethane, washed with brine, dried over anhydrous magnesium sulfate, filtered through a silica gel pad, and then concentrated to obtain the crude ligand. This crude product was dissolved in hexane and purified by rapid chromatography using an ISCO purification system (2% ethyl acetate / hexane; isocratic) to give 2.30 g (97.5%) of pure ligand. Add 150 mL of 1:1 methanol / THF and approximately 100 mg of PTSA to the crude protected ligand. Heat the solution to 60 °C for 6 hours, cool, and concentrate. Dissolve the crude ligand in dichloromethane, wash with brine, dry over anhydrous magnesium sulfate, filter through a silica gel pad, and concentrate to obtain the crude ligand. Dissolve this crude product in hexane and purify it by rapid chromatography using an ISCO purification system (2% ethyl acetate / hexane; isocratic) to obtain 2.30 g (97.5%) of pure ligand.

[0106] 1 H NMR(400MHz, CDCl3)δ8.05(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(brs,6H),1.68(quint,4H),1.32(br m,86H),0.93(t,6H),0.85(s,18H).

[0107]

[0108] HfCl4 (0.0516 g, 0.161 mmol) and toluene (10 mL) were added to a glass jar equipped with a stir bar in a nitrogen-purged glove box. The resulting slurry was cooled at -30 °C in a glove box freezer. Diethyl ether containing methyl magnesium bromide (3.0 M, 0.22 mL, 0.66 mmol) was added to the stirred, cooled slurry. The mixture was stirred vigorously for about 4 minutes. The solid dissolved in the solution, and the mixture turned pale yellow. Then, the ligand (0.2500 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 next day. The colorless solid was concentrated under vacuum to give 0.2145 g of the product of structure i as a white solid (yield = 75.8%).

[0109] 1 H NMR(400MHz,C6D6)δ8.24(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,2H),3.64(quint,2H),3.40(quint,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).

[0110]

[0111] As used in this article, "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.

[0112] The pre-catalyst for biphenol polymerization with structure (ii) was prepared as follows.

[0113] The ligands were prepared as described above in the synthesis of structure i.

[0114]

[0115] ZrCl4 (0.0376 g, 0.161 mmol) and toluene (10 mL) were added to a glass jar equipped with a stir bar in a nitrogen-purged glove box. The resulting slurry was cooled at -30 °C in a glove box freezer. Diethyl ether containing methyl magnesium bromide (3.0 M, 0.23 mL, 0.69 mmol) was added to the stirred, cooled slurry. The mixture was stirred vigorously for about 4 minutes. The solid was dissolved in the solution, and the mixture turned pale yellow. Then, the ligand (0.2505 g, 0.161 mmol) in solid form was added to this mixture. 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 next day. The colorless solid was concentrated under vacuum to give 0.2640 g of the structure ii product as a white solid (yield = 97.9%).

[0116] 1 H NMR(400MHz,C6D6)δ8.24(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(quint,2H),3.40(quint,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.

[0117]

[0118] The precatalyst for biphenol polymerization with structure (iii) was prepared as follows.

[0119]

[0120] Preparation of 4,4'-diethyl-2-nitro-1,1'-biphenyl: A three-necked round-bottom flask was equipped with a magnetic stir bar, thermocouple sheath, feeding funnel, and septum. 4,4'-diethylbiphenyl (15.0089 g, 71.366 mmol) and acetic anhydride (382 mL, 4041 mmol) were added to the flask. The solution was cooled using an ice-water 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 continuously 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 highest temperature reached was 10.0 °C. After 10 minutes, the mixture was sampled by GC / MS, indicating the reaction was complete. At 20 minutes, the reaction mixture was poured into a beaker containing approximately 2 L of ice-water (mainly ice) and stirred for 1.5 hours. A yellow oily substance was separated from the aqueous phase. The mixture was transferred to a separatory funnel, and dichloromethane (285 mL) was added. The mixture was thoroughly mixed and allowed to separate. The organic phase was separated and washed with water (230 mL) and 1 M NaOH aqueous solution (230 mL). The yellow solution was dried over anhydrous magnesium sulfate and filtered. The solution was concentrated by rotary evaporation, with the bath temperature starting at 35 °C and finally reaching 50 °C, to give a yellow oily substance (22.46 g) as the crude product. The oily substance was subjected to chromatographic analysis on a 330 g silica gel Grace column on an Isco CombiFlash system using a gradient of 10%–20% dichloromethane / hexane until the product was eluted. The fractions were analyzed by GC / MS and TLC (5% ethyl acetate / hexane). The pure fractions were combined, concentrated by rotary evaporation, and dried under high vacuum to give 15.75 g (86.5%) of the product as a yellow oily substance.

[0121] 1 H NMR(400MHz, CDCl3) δ7.64(d,J=1.7Hz,1H),7.40(dd,J=7.9,1.8Hz,1H),7.32(d,J=7.9Hz,1H),7.25–7 .20(m,4H),2.73(q,J=7.6Hz,2H),2.68(q,J=7.6Hz,2H),1.28(t,J=7.6Hz,3H),1.26(t,J=7.6Hz,3H). 13 CNMR(101MHz, CDCl3)δ149.22,144.50,143.95,134.54,133.42,131.68,131.64,128.04,127.73,123.02,28.43,28.04,15.21,14.96.

[0122]

[0123] Preparation of 2,7-Diethyl-9H-carbazole: Under a nitrogen atmosphere, a three-necked round-bottom flask equipped with a magnetic stir bar was placed in a glove box. 4,4'-Diethyl-2-nitro-1,1'-biphenyl (20.580 g, 80.608 mmol) and triethyl phosphite (81 mL) were added to the flask. The flask was sealed with a septum and taken to a fume hood equipped with a condenser and a nitrogen inlet. The yellow solution was heated to reflux (175 °C heating mantle temperature) and samples were taken for GC / MS analysis after reflux for 2 and 4 hours (0.1 mL sample diluted in dichloromethane). After 4 hours, only trace amounts of the starting material were observed. A main 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 frozen overnight. The white crystalline solid (Crop 1) was collected by vacuum filtration upon cooling and washed with five 20 mL aliquots of cold ethanol. The solid was dried. The filtrate was returned to the freezer overnight. Upon cooling, the crystalline solid precipitated in the mother liquor (Crop 2) was collected by vacuum filtration and washed with five 10 mL aliquots of cold ethanol. Both solids were transferred to vials and placed under high vacuum to give 8.2640 g of crystalline solid from Crop 1 and 2.3351 g of crystalline solid from Crop 2. The total yield was 10.5991 g (58.9%) of product.

[0124] 1 H NMR(400MHz,DMSO-d6)δ7.93(d,J=7.9Hz,2H),7.78(s,1H),7.19(dd,J=1.5,0.7Hz, 2H), 7.08 (ddd, J=8.0, 1.3, 0.6Hz, 2H), 2.82 (q, J=7.7Hz, 4H), 1.33 (t, J=7.6Hz, 6H). 13 C NMR (101MHz, DMSO-d6) δ140.94,140.27,120.51,119.54,118.75,109.55,28.80,16.15.

[0125]

[0126] 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 equipped with a stir bar was placed in a glove box under a nitrogen atmosphere. 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) were added to the flask. In the glove box, copper iodide (0.2860 g, 1.502 mmol) was added to a 20 mL vial and diluted with toluene (1 mL). Remove the flask and vial containing the copper iodide solution from the glove box to a fume hood. The flask was equipped with a nitrogen inlet and a condenser. Add N,N-dimethylethylenediamine (0.602 mL, 5.593 mmol) to the copper iodide solution, and then add the now-slurryed solution to the reaction mixture. Heat the mixture at 125 °C (heating mantle temperature). After 24 hours, GC analysis showed approximately 84.74% conversion, with 15.26% carbazole remaining. Therefore, add dried toluene (1 mL) containing an additional slurry of anhydrous copper iodide (0.2827 g, 1.484 mmol) and N,N-dimethylethylenediamine (0.602 mL, 5.593 mmol). Continue stirring the reaction at 125 °C for another 24 hours. After 48 hours, GC analysis showed approximately 97.60% conversion, with 2.40% carbazole remaining. The reaction was cooled to room temperature, filtered through a small silica gel stopper, washed with three 75 mL aliquots of tetrahydrofuran, and concentrated by rotary evaporation to give a crude product (35.15 g) as a dark brown oil that eventually solidified. The solid did not recrystallize from hexane (75 mL), so the solution was concentrated by rotary evaporation to give a dark brown oil that eventually solidified. The material was dissolved in hot hexane (25 mL), filtered through a glass funnel using cotton heat, and recrystallized. The resulting slurry was too concentrated. The slurry was heated to dissolve the solid, and the resulting solution was concentrated by rotary evaporation to give a dark brown oil that eventually solidified. The solid was recrystallized from hexane (50 mL) to give light brown crystals. The crystals were collected by vacuum filtration, washed with two 10 mL aliquots of cold hexane, and dried under high vacuum to give 14.2792 g (64.9%) of a product as light brown crystals.

[0127] 1H NMR (400MHz, CDCl3+TMS) δ7.95(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(t d, J = 11.1, 2.9 Hz, 1H), 3.46 (dt, J = 11.2, 3.7 Hz, 1H), 2.73 (q, J = 7.6 Hz, 4H), 1.74 (s, 2H), 1.45–1.34 (m, 2H, overlapping with two singlets at 1.38 ppm 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)δ151.07,144.12,142.07,142.03,141.55,141.53,127.76,126.69,126.30,121.29,121.16,119.61,119.57,119 .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.

[0128]

[0129] Preparation of 2,7-diethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole: A three-necked round-bottom flask was equipped with a magnetic stir bar, a septum, and a nitrogen inlet. 10.0012 g (19.544 mmol) of 2,7-diethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole and 130 mL of dry tetrahydrofuran were added to the flask. Cool the solution to 0-10°C using an ice-water bath for approximately 15 minutes, and slowly add 2.5 M n-butyllithium / hexane (20.500 mL, 51.250 mmol). The color of the solution changes from clear pale yellow to clear deep yellow. After stirring for 4 hours, slowly add 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxane (10.200 mL, 49.9967 mmol). The solution changes from clear deep yellow to cloudy pale yellow. Stir the mixture at 0-10°C for 1 hour before allowing the reaction to reach room temperature and stir overnight. Add cold saturated sodium bicarbonate solution (110 mL) to the reaction mixture. Extract the aqueous phase with four 75 mL aliquots of dichloromethane. Combine the organic phases, wash with cold saturated sodium bicarbonate solution (290 mL), wash with brine (290 mL), dry over anhydrous magnesium sulfate, and filter under vacuum. The filtrate was concentrated by rotary evaporation and placed under high vacuum to obtain a crude product (13.76 g) as a pale yellow foam. Before separating the white solid by vacuum filtration, the foam was slurried in acetonitrile (50 mL) and then allowed to stir at room temperature for 30 minutes. The solid was washed with two 20 mL portions of cold acetonitrile and dried under high vacuum to give a product of 7.8165 g (62.7%) as a grayish-white solid.

[0130] 1H NMR(400MHz,CDCl3)δ7.93(d,J=7.9Hz,2H),7.93(d,J=7.9Hz,2H),7.84(dd,J=2.6,0.8Hz,1H),7.45(dd,J=2.5,0.8Hz,1H),7.06(d,J=8.0Hz,2H),7.05(d,J=8.0Hz,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=11.2,3.9Hz,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 C NMR(101MHz,CDCl3)δ156.44,145.68,142.11,142.01,141.71,141.68,133.85,130.95,129.45,121.25,121.01,119.57,119.54,119.23,119.21,109.70,109.51,101.27,83.61,61.20,56.95,38.30,32.37,31.88,31.41,31.36,30.02,29.48,29.45,25.02,25.00,24.75,18.19,16.22,16.16。

[0131]

[0132] Preparation of 2',2”'-(propane-1,3-diylbis(oxy))bis(3-(2,7-diethyl-9H-carbazol-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 equipped with a magnetic stir bar, a septum, a condenser, and a nitrogen inlet. 2,7-diethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3- (4,4,5,5-Tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-5-(2,4,4-trimethylpentane-2-yl)phenyl)-9H-carbazole (3.6936 g, 5.792 mmol), 1,2-dimethoxyethane (72 mL), NaOH (0.7647 g, 19.118 mmol) in water (21 mL), tetrahydrofuran (24 mL), and 1,3-bis(4-fluoro-2-iodo-6-methylbenzene) (1.5002 g, 2.757 mmol) propane. The mixture was purged with nitrogen for about 15 minutes, and then tetrakis(triphenylphosphine)palladium(0) (0.2368 g, 0.2049 mmol) was added. The mixture was heated to reflux at 85 °C for 48 hours, and then allowed to cool to room temperature. Once cooled, the ligand remained in solution. The mixture was transferred to a separatory funnel for phase separation. The phases were not completely separated. Water (30 mL) was added to the mixture, and the phases were still not completely separated. Dichloromethane (30 mL) was added to the mixture, and four phases were separated. The organic phases were combined. The aqueous phases were combined and extracted with dichloromethane (30 mL). All organic phases were combined, dried over magnesium sulfate, and filtered under vacuum. The flask was washed with two 15 mL portions of dichloromethane and filtered into a filter flask containing the organic phases. The organic solution was concentrated by rotary evaporation to give a reddish-brown oil (5.66 g) as the crude protected ligand. 1 The ligand 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. p-Toluenesulfonic acid (0.0556 g, 0.2922 mmol) was added to the solution, and the reaction was stirred at 60 °C for 8 hours, then allowed to cool to room temperature. 1¹H NMR analysis of the mixture confirmed completion. The ligands were considered deprotected. The ligands were concentrated to a brown viscous material (4.86 g) by rotary evaporation. The ligands did not recrystallize in acetonitrile (10 mL) at room temperature. The ligands were concentrated to a brown viscous solid, dissolved in a small amount of dichloromethane, and run on an Isco CombiFlash system on a 220 Grace column using a gradient of 35%–40% dichloromethane / hexane until the ligands were eluted. The fractions were analyzed by TLC (40% dichloromethane / hexane), and the pure fraction was concentrated by rotary evaporation to give 1.59 g of a pale yellow solid. The fraction with minor impurities was also concentrated by rotary evaporation to give 1.16 g of a pale yellow solid. 1 ¹H NMR analysis of the two solids revealed that they were 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 it became acidic (pH = 1–3). After 8 hours, the ligand was analyzed by… 1 The material was analyzed by 1H NMR to ensure deprotection was complete, and then cooled to room temperature. The material was concentrated to a yellow, viscous solid, dissolved in a small amount of dichloromethane, and run on a 120 Grace column on an Isco CombiFlash system using a gradient of 35%–40% dichloromethane / hexane until the ligands were eluted. The pure fraction was concentrated by rotary evaporation to give 0.7084 g of a pale yellow crystalline solid. 1 The solid was analyzed by ¹H NMR. The fraction with minor impurities was concentrated by rotary evaporation, with a small amount of dichloromethane dissolved, and run on an Isco CombiFlash system on a 220 Grace column using a gradient run of 35%–40% dichloromethane / hexane. The pure fraction was concentrated by rotary evaporation to give 1.3092 g of a pale yellow crystalline solid. 1 ¹H NMR analysis of the solid. The total yield was 2.0176 g (64.0%) of the product as a white crystalline solid.

[0133] 1H NMR (400MHz, CDCl3) δ7.98(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,2H),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 C NMR (101MHz, CDCl3) δ160.20,157.78,149.70,149.68,147.86,143.01,141. 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. [No multiplicity due to carbon-fluorine coupling was identified]. 19 F NMR (376MHz, CDCl3) δ-118.04 (t, J=8.8Hz). HRMS(ESI,M+NH4 + For C 77 H 92 The calculated value (m / z) of F2N3O4 is 1160.705, and the experimental value is 1160.704.

[0134]

[0135] Preparation of structure (iii): HfCl4 (0.1410 g, 0.4372 mmol) and toluene (27 mL) were added to a glass jar. The slurry was cooled to -25 °C in a glove box freezer for 30 minutes. Diethyl ether containing 3.0 M methyl magnesium bromide (0.60 mL, 1.8 mmol) was added to the stirred, cold slurry. The mixture was stirred vigorously for 2 minutes. The solid was dissolved in the solution, but the reaction solution was cloudy. The ligand (0.5000 g, 0.4372 mmol) was added to the 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 pale brown reaction mixture was filtered under vacuum using a porous funnel. The filter cake was washed with two 5 mL portions 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 give 0.5933 g (100.5%) of a pale yellow solid. The excess yield was due to the presence of toluene, which was difficult to remove.

[0136] 1 H NMR (400MHz, C6D6) δ8.17(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=9.9,4.8H z,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,8H with s),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)δ161.59,159.14,153.64,149.53,149.50,142.81,142.46,141.56 ,141.32,140.70,135.72,135.63,135.00,134.92,130.50,127.03,123.94,121.63,12 0.90, 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. [No multiplicity due to carbon-fluorine coupling was identified]. 19 F NMR (376MHz, C6D6) δ-115.12 (d, J = 8.7Hz).

[0137]

[0138] The precatalyst for biphenol polymerization with structure (iv) was prepared as follows.

[0139]

[0140] Preparation of 4,4'-dimethyl-2-nitro-1,1'-biphenyl: A three-necked round-bottom flask was equipped with a magnetic stir bar, thermocouple sheath, feeding 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 by an ice-water bath (internal temperature 3.8 °C). A mixture of nitric acid (3.3 mL, 69.8 mmol) and acetic acid (5.3 mL, 92.5 mmol) was added dropwise continuously while monitoring the internal temperature, ensuring it did not exceed 10 °C. After 10 minutes, the reaction mixture was sampled by GC / MS at 0 °C to 10 °C. GC / MS showed the initial biphenyl converted to the product, confirming the completion of the reaction. At 25 minutes, the reaction mixture was poured into a beaker (850 mL) containing ice water (mainly ice) and stirred for 1.5 hours. A yellow oily substance was separated from the aqueous phase. The mixture was transferred to a separatory funnel, dichloromethane (127 mL) was added, and the phases were separated. The organic phase was washed with water (100 mL) and then with 1 M sodium hydroxide aqueous solution (100 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered under vacuum, and concentrated by rotary evaporation to give a product (10.8926 g) as a crude orange oily substance. The oily substance was loaded onto an Isco CombiFlash system and run using a 330 g Grace column and a gradient of 15%–20% dichloromethane / hexane until the product was eluted. The fractions were analyzed by TLC. The pure fractions were combined, concentrated by rotary evaporation, and dried under high vacuum to give a product of 5.07 g (70.1%) as a yellow solid.

[0141] 1 H NMR (400MHz, CDCl3+TMS) δ7.62–7.58(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). 13 C NMR (101MHz, CDCl3+TMS) δ149.10,138.30,137.76,134.33,133.25,132.84,131.59,129.28,127.68,124.19,21.11,20.70.

[0142]

[0143] Preparation of 2,7-dimethyl-9H-carbazole: In a glove box, 4,4'-dimethyl-2-nitro-1,1'-biphenyl (4.9855 g, 21.937 mmol) and triethyl phosphite (22 mL, 128 mmol) were added to a three-necked round-bottom flask equipped with a magnetic stirrer and a septum. The flask was placed in a fume hood with a condenser and a nitrogen inlet. The yellow slurry was placed under a nitrogen atmosphere and heated to reflux (175 °C heating mantle temperature), and a sample was taken for GC / MS analysis. The yellow slurry eventually turned into a brown solution. After 2 hours, GC / MS showed product formation with the remaining starting material. After 5 hours, only trace amounts of starting material were observed, and the reaction was determined to be complete. The reaction was allowed to cool to room temperature. A white crystalline precipitate was observed. The reaction mixture was stored overnight in a freezer. White crystalline solids (crop 1) were collected by vacuum filtration, washed with cold ethanol (5 x 5.5 mL aliquots), and dried under high vacuum to give 1.62 g of product as a white crystalline solid. The filtrate was placed in a freezer over the weekend. White crystalline precipitate was observed. White crystalline solids (crop 2) were collected by vacuum filtration, washed with cold ethanol (5 x 5.5 mL aliquots), and dried under high vacuum to give 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.

[0144] 1 H NMR (400MHz, DMSO-d6) δ10.96 (s, 1H), 7.87 (d, J = 7.9 Hz, 2H), 7.25 (s, 2H), 6.93 (d, J = 7.9 Hz, 2H), 2.45 (s, 6H). 13 C NMR (101MHz, DMSO-d6) δ140.23,134.33,120.32,119.87,119.47,110.82,21.67.

[0145]

[0146] 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 equipped with a magnetic stir bar and a septum. In a glove box, 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) were added to the flask. In a glove box, anhydrous copper iodide (0.0676 g, 0.3549 mmol) and N,N-dimethylethylenediamine (0.1456 mL, 1.353 mmol), slurried in dry toluene (1 mL), were added to the reaction mixture. The flask was equipped with a condenser and a nitrogen inlet in a fume hood. The reaction was placed under a nitrogen atmosphere and heated at 125 °C (heating mantle temperature). After 24 hours, HPLC analysis showed product formation with residual starting carbazole. Therefore, additional anhydrous copper iodide (0.0667 g, 0.3502 mmol) and N,N-dimethylethylenediamine (0.1456 mL, 1.353 mmol), slurried in dry toluene (1 mL), were added. The reaction was continued to be stirred at 125 °C for another 24 hours. After 48 hours, HPLC analysis showed almost no change in the consumption of the starting carbazole, at which point the reaction was stopped. The reaction was allowed to cool to room temperature. The reaction mixture was then filtered through a small silica stopper under vacuum. The stopper was washed with tetrahydrofuran (3 x 50 mL portions), and the filtrate was concentrated by rotary evaporation to obtain a 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 onto an Isco CombiFlash system and run using a gradient of 15%–20% dichloromethane / hexane until the product was 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 dried under high vacuum to remove the solvent. 1 ¹H NMR analysis of the solid revealed the presence of some 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran starting material. Recrystallization from hexane yielded a white solid. The solid was collected by vacuum filtration and washed with cold hexane (2 x 10 mL portions). To remove trace amounts of hexane, the solid was dissolved in dichloromethane and concentrated by rotary evaporation to give a white crystalline solid (repeated twice). Drying the solid under high vacuum gave 2.96 g (58.8%) of a white crystalline solid product.

[0147] 1 H NMR(400MHz,CDCl3)δ8.01(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=1.6,0.8Hz,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,1H),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)δ150.91,144.07,141.90,141.88,134.94,134.84,127.68,126.71,126.05,121.00,120.85,120.63,120.60,119.39,119.30,116.06,110.82,110.18,96.67,61.43,57.00,38.18,32.39,31.85,31.60,31.52,29.95,25.10,22.05,21.96,17.57。

[0148]

[0149] Preparation of 2,7-dimethyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (16) (201303282-23): A three-necked round-bottom flask was equipped with a magnetic stir bar, a septum, and a nitrogen 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°C to 10°C (ice-water bath) for approximately 15 minutes, and 2.5 M n-butyllithium / hexane (6.2 mL, 15.500 mmol) was slowly added. After stirring at 0°C to 10°C for 4 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentane (3.1 mL, 15.195 mmol) was slowly added. The mixture was stirred at 0°C to 10°C for 1 hour before allowing the reaction to rise to room temperature and be stirred overnight. Cold saturated sodium bicarbonate solution (40 mL) was added to the reaction mixture. The aqueous phase was extracted with dichloromethane (4 x 20 mL). The organic phases were combined and washed with cold saturated sodium bicarbonate solution (90 mL), and then with brine (90 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered under vacuum, concentrated by rotary evaporation and then placed under high vacuum to give a product as a crude white crystalline solid (3.8902 g). pass 1 The crude product was analyzed by ¹H NMR. Before separating the white solid by vacuum filtration, the crude product was slurried in acetonitrile (30 mL) and stirred at room temperature for 30 min. The solid was washed with cold acetonitrile (2 x 10 mL portions). To remove trace amounts of acetonitrile, the solid was dissolved in dichloromethane and concentrated by rotary evaporation to give a grayish-white crystalline solid (repeated twice). The solid was dried under high vacuum to give 2.24 g (62.2%) of the product as a grayish-white crystalline solid.

[0150] 1H NMR(400MHz, CDCl3)δ7.96,(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), ~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) δ156.66,145.86,142.08,141.96,135.05,134.09,131.09,129.45,120.95,120.68,120.61,119.15,119.10,110. 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.

[0151]

[0152] 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 equipped with a magnetic stir bar, a septum, a condenser, and a nitrogen inlet. The flask was placed under a nitrogen atmosphere and filled with 2,7-dimethyl-9-(2-((tetrahydro-2H))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). -pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-5-(2,4,4-trimethylpentane-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 water (13 mL), tetrahydrofuran (15 mL) The solution and 1,3-bis(4-fluoro-2-iodo-6-methylphenoxy)propane (0.9055 g, 1.664 mmol) were added. The mixture was purged with nitrogen for about 15 minutes, and then tetrakis(triphenylphosphine)palladium(0) (0.1373 g, 0.1188 mmol) were added. The mixture was heated to reflux at 85 °C for 20 hours, and the reaction was completed by HPLC analysis. After 2 hours, HPLC showed the formation of the protected product and the consumption of the bridge. After 20 hours, no changes were observed in the HPLC analysis, and the reaction was determined to be complete. The reaction was allowed to cool to room temperature. Once cooled, the protected product remained in solution. The mixture was transferred to a separatory funnel for phase separation. The phases were separated. The organic phase was dried over magnesium sulfate and filtered under vacuum. The solid was washed with dichloromethane, and the filtrate was concentrated by rotary evaporation to give the protected product (3.3180 g) as a crude, viscous, golden-orange solid. 1 The protected product 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 was stirred overnight at 60 °C, and the results were analyzed by ¹H NMR. 19F NMR analysis was completed. The reaction was cooled to room temperature. The solution was concentrated by rotary evaporation to obtain a deprotected product (2.8889 g) as a crude, golden-orange viscous solid. The solid was dissolved in chloroform, and silica gel was added. The slurry was concentrated by rotary evaporation to obtain a dry, powdery mixture. The powdery mixture was loaded onto an Isco CombiFlash system and run using a 330 Grace column and a gradient of 40%–50% dichloromethane / hexane until the product was eluted. The fractions were analyzed by TLC. The pure fractions were combined and concentrated by rotary evaporation to obtain an orange crystalline solid. To remove trace amounts of hexane, the solid was dissolved in dichloromethane and concentrated by rotary evaporation to obtain an orange crystalline solid (repeated twice). The solid was dried under high vacuum to give 1.35 g (74.9%) of the product as an orange crystalline solid.

[0153] 1 H NMR (400MHz, CDCl3) δ8.04(d,J=7.9Hz,4H),7.52(d,J=2.4Hz,2H),7.50(d,J=2 .4Hz,2H),7.12(dd,J=8.0,1.4Hz,4H),7.06(dd,J=8.9,3.1Hz,2H),6.94(s,4H ),6.91(dd,J=8.8,2.9Hz,2H),6.73(s,2H),3.75(t,J=6.4Hz,4H),2.44(s,12H ), 2.05 (s, 6H), 1.87 (p, J = 6.3Hz, 2H), 1.82 (s, 4H), 1.47 (s, 12H), 0.88 (s, 18H). 13 C NMR (101MHz, CDCl3) δ160.25,157.82,149.58,149.55,147.82,143.12,141.81,135.32,133.52,133.43,133.01,132.92,128.94,127.97,126. 49,125.52,121.14,121.09,119.70,117.44,117.21,116.21,115.98,1 09.87,70.77,57.12,38.21,32.42,31.80,31.55,30.56,22.07,16.28. [No multiplicity due to carbon-fluorine coupling was identified]. 19 F NMR (376MHz, CDCl3) δ-118.04 (t, J=8.8Hz).

[0154]

[0155] Preparation of structure (iv): The reaction was set up in a glove box under a nitrogen atmosphere. HfCl4 (0.0335 g, 1.046 mmol) and toluene (6 mL) were added to a glass jar. The slurry was cooled to -25°C in a glove box freezer for 30 minutes. Diethyl ether containing 3.0 M methyl magnesium bromide (0.14 mL, 0.42 mmol) was added to the stirred, cold slurry. The mixture was vigorously stirred for 2 minutes. The solid was dissolved in the solution, but the reaction solution was cloudy. A solution of the ligand (0.1076 g, 0.0990 mmol) in toluene (2 mL) was added to the solution. 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 pale brown reaction mixture was filtered under vacuum using a porous funnel. The filter cake was washed with two 4 mL aliquots of toluene. Hexane (10 mL) was added to the filtrate (a clear, pale yellow solution). The resulting turbid solution was filtered (using a syringe filter) and concentrated under high vacuum to give 0.1097 g (85.7%) of product.

[0156] 1 H NMR (400MHz, C6D6) δ8.15(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(width s,8H),1.22(s,6H),1.19(t,J=0.7Hz,6H),0.85(s,18H),-0.69(s,6H). 13C NMR (101MHz, C6D6) δ161.49,159.04,153.43,149.47,149.44,142.21,141.32,140. 70,136.21,135.59,135.50,134.90,134.81,134.47,130.43,126.91,123.66,121.9 9,121.37,120.55,119.66,118.07,117.84,117.52,117.29,114.42,111.20,76.10,57.48,49.01,38.19,32.57,31.94,31.66,31.29,30.19,22.50,22.13,16.17,1.38. [No multiplicity due to carbon-fluorine coupling was identified].

[0157]

[0158] The precatalyst for biphenol polymerization with structure (v) was prepared as follows.

[0159]

[0160] Preparation of meso-pentane-2,4-dimethyldiphenylsulfonate: A 250 mL three-necked round-bottom flask equipped with two septa, a stir bar, and placed under nitrogen. 2,4-Pentanediol (7.5 mL, 69.1 mmol) and pyridine (110 mL, placed on molecular sieve 3A before use) were added to the flask. The colorless solution was cooled to approximately 0 °C (ice-water bath). p-Toluenesulfonyl chloride (39.5903 g, 0.2077 mol) was added in portions over 10-minute intervals. The solution turned yellow. The ice bath was removed, and the mixture was allowed to stir overnight. After stirring overnight, the reaction mixture was poured into 550 mL of ice-water and stirred for 3 hours. A white precipitate was collected by vacuum filtration. The solid was washed with two 50 mL portions of water. The solid was air-dried. The crude product... 1 ¹H-NMR showed integration of a sextet at 4.57 ppm and 4.70 ppm, with a meso:racemate ratio of approximately 1:1. A crude bis-toluenesulfonate (23.8423 g) was obtained as a white solid. The solid was transferred to a glass jar and ether (50 mL) was added. The mixture was stirred vigorously for 10 minutes. The solid was separated by vacuum filtration. The filter cake was washed with two 10 mL portions of ether. This extraction procedure was repeated three times. The collected white solid was air-dried. 1 ¹H-NMR showed that it was not rich in the meso isomer. Therefore, the solid was suspended in diethyl ether (240 mL) and stirred vigorously overnight. The solid was filtered and... 1H-NMR analysis of the small sample revealed a meso to racemic ratio of approximately 2:1. Therefore, the solid was suspended in diethyl ether (240 mL) and stirred vigorously overnight. This procedure was repeated twice. Then, after another 66 hours of vigorous stirring, the solid was filtered and subjected to... 1 H-NMR analysis of a small sample. The spectrum showed a meso:racemate ratio of approximately 6:1. The solid was placed under high vacuum to remove diethyl ether, yielding 10.08 g (35.3%) of a white solid rich in meso-toluenesulfonate.

[0161]

[0162] Preparation of 2,2'-(((meta-pentane-2,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene): A 250 mL round-bottom flask was equipped with a condenser, two septa, a magnetic stir bar, and a gas inlet on top of the condenser. The flask was charged with meta-pentane-2,4-diyl diphenylsulfonate (3.0041 g, 7.2823 mmol), 4-fluoro-2-iodo-6-methylphenol (3.6751 g, 14.582 mmol) [prepared as described in US20150291713A1], potassium carbonate (4.0220 g, 29.101 mmol), and N,N-dimethylformamide (55 mL). The reaction was placed under nitrogen and heated to 100 °C. After heating for 2 hours, the brown mixture, which was the sample for GC / MS analysis, showed peaks corresponding to the molecular weight fragments of the product, and the initiating phenol appeared to be consumed. The reaction mixture was cooled to room temperature and concentrated in a rotary evaporator (bath temperature 25°C to 70°C) to give 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 with three 30 mL aliquots of dichloromethane. The combined organic phases were 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 over anhydrous magnesium sulfate, filtered, and concentrated under vacuum to give 4.02 g of brown oil. The oil was chromatographically analyzed using a 120 g Grace column and an automated ISCO instrument. The column was eluted with a 0%–2% ethyl acetate / hexane gradient. Fractions containing the product were identified by a combination of TLC and GC / MS. The fractions were combined and concentrated under high vacuum to obtain a product that was a yellow oil (2.2653 g, 54.4%).

[0163] 1H NMR (400MHz, CDCl3) δ7.32(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).

[0164]

[0165] Preparation of 2',2”'-(((meta-pentane-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-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)-5-(2,4,4-trimethylpentan-2-yl) Phenyl)-9H-carbazole (5.20 g, mmol) (described in the synthesis of structure (iv)) (temperature may be increased to room temperature), 2,2'-((((racemic)-pentane-2,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene) (2.037 g, mmol), NaOH (0.8994 g, mmol) in a solution of water (30 mL) and THF (70 mL). All substances were dissolved in solution before adding NaOH. The reaction mixture was bubbled with N2 for about 15 minutes, then Pd(PPh3)4 was added and heated to 85 °C overnight, followed by cooling. 19 F NMR spectroscopy was used to determine whether the reaction was complete. The reaction was concentrated by dissolving the residue in dichloromethane (200 mL), washing with brine (200 mL), drying over anhydrous magnesium sulfate, filtering through a silica gel pad, and concentrating to obtain the crude protected ligand. THF (50 mL), methanol (50 mL), and approximately 100 mg of PTSA were added to the crude protected ligand. PTSA was added until the solution was acidic (pH paper). The solution was heated to 60 °C overnight, then cooled and concentrated. The crude ligand was dissolved in dichloromethane (100 mL), washed with brine (100 mL), dried over anhydrous magnesium sulfate, filtered through a silica gel pad, and then concentrated to obtain the ligand as a brown crystalline powder. This ligand showed trace impurities, so a dichloromethane:hexane gradient was used to pass it through a 330 g ISCO column, producing 1.92 g of white crystals. There was a small overlap between the impurities and the desired product, so the impure fraction was passed through an ISCO column under the same conditions at a 330 g column.

[0166] 1H NMR (400MHz, CDCl3) δ8.01(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 F NMR(376MHz, CDCl3)δ-118.66(s)

[0167]

[0168] ZrCl4 (0.0399 g, 0.171 mmol) and toluene (10 mL) were added to a glass jar equipped with a stir bar in a nitrogen-purged glove box. The resulting slurry was cooled at -25 °C in a glove box freezer. Diethyl ether containing methyl magnesium bromide (3.0 M, 0.25 mL, 0.75 mmol) was added to the stirred, cooled slurry. The mixture was stirred vigorously for about 4 minutes. The solid was dissolved in the solution, and the mixture turned light brown. Then, the ligand (0.2007 g, 0.1561 mmol) in solid form was added to this mixture. 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 give 0.2248 g of structure v product as a white solid. Some residual solvent remained in the final product.

[0169]

[0170] The precatalyst for biphenol polymerization of structure (vi) was prepared as described in WO 2017 / 004462 A1, the entire contents of which are incorporated herein by reference.

[0171]

[0172] The precatalyst for biphenol polymerization with structure (vii) was prepared as follows. The ligand was prepared as described in WO 2017 / 004462 A1.

[0173]

[0174] The reaction was set up in a glove box under a nitrogen atmosphere. ZrCl4 (0.0333 g, 0.1429 mmol) and toluene (10 mL) were added to a glass jar. The slurry mixture was cooled to -25 °C in a glove box freezer. Diethyl ether containing 3.0 M methyl magnesium bromide (0.22 mL, 0.66 mmol) was added to the stirred, cold slurry mixture. The mixture was stirred vigorously for about 4 minutes. The solid dissolved in the solution and turned brown. The ligand (0.2002 g, 0.1353 mmol) in solid form was added to the mixture. The resulting mixture was stirred at room temperature for 4 hours. Hexane was then added to the mixture and the mixture was filtered. The solution was concentrated under vacuum to give 0.1942 g (theoretical yield: 0.2164; 90%) of a grayish-white solid. The product was further purified. Hexane was added to the solid, followed by toluene, until most of the solid dissolved. The mixture was filtered (using a Whatman syringe filter, 0.45 μL) and the solution was concentrated to obtain the product.

[0175] 1 H NMR(400MHz,C6D6)δ8.10(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).

[0176]

[0177] The precatalyst for biphenol polymerization of structure (viii) was prepared as described in WO2017 / 004456A1, the entire contents of which are incorporated herein by reference.

[0178]

[0179] The pre-catalyst for biphenol polymerization with structure (ix) was prepared as follows.

[0180]

[0181] 2-Iodo-4-fluorophenol, 1,4-dibromobutane, K₂CO₃, and 100 mL of acetone were placed in a 250 mL flask equipped with a stir bar and a condenser. The reaction mixture was stirred and refluxed overnight (60 °C) and examined by GC and GCMS. Both analyses showed that the reaction was complete, so the mixture was cooled, filtered through a silica gel pad, and concentrated by rotary evaporation. Recrystallization of the residue from the hot acetone gave 7.137 g of white crystals. Recrystallization of the filtrate yielded 0.6 g of total mass, which, although it did have an orange hue, was 98% pure with minor impurities.

[0182] 1 H NMR (400MHz, CDCl3) δ7.49(dd,2H),7.00(m,2H),6.75(dd,2H),4.07(m,4H),2.09(m,4H).

[0183]

[0184] 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'-diphenyl]-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-dioxacyclopentaborane-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (prepared as described in US20150291713A1), 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 T HF. The system was bubbled with N2, and then 130 mg of Pd(Ph3)4 was added and heated to 85 °C for 48 hours, followed by cooling and concentration. Upon cooling, the protected ligand precipitated from the solution, which was then separated by vacuum filtration and further dried under high vacuum for about 1 hour to obtain a crude ligand as a gray powder. This ligand was used as is in the next step. 100 mL of 1:1 methanol / THF and about 100 mg of PTSA were added to the crude protected ligand. The solution was heated to 60 °C for 8 hours, followed by cooling and concentration. The residue was dissolved in dichloromethane (200 mL), washed with brine (200 mL), dried over anhydrous magnesium sulfate, filtered through a silica gel pad, and then concentrated to obtain a yellow powder. The compound was purified by rapid chromatography using an ISCO purification system (eluting with 2% ethyl acetate / hexane) to give 1.70 g (54.4%) of the pure compound as a white powder.

[0185]

[0186] HfCl4 (0.0795 g, 0.248 mmol) and toluene (15 mL) were added to a glass jar equipped with a stir bar in a nitrogen-purged glove box. The resulting slurry was cooled at -25 °C in a glove box freezer. Diethyl ether containing methyl magnesium bromide (3.0 M, 0.34 mL, 1.02 mmol) was added to the stirred, cooled slurry. The mixture was stirred vigorously for about 4 minutes. The solid was dissolved in the solution, and the mixture turned pale yellow. Then, the ligand (0.3007 g, 0.237 mmol) in solid form was added to this mixture. 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 give 0.3866 g of 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 collected by filtration. The solid was dried under vacuum to obtain 0.3280 g of the structure ix product as a grayish-white solid (yield = 93.8%).

[0187]

[0188] The biphenol polymerization precatalyst of structure (x) is prepared as described in WO2017 / 058858, and the entire contents of WO2017 / 058858 are incorporated herein by reference.

[0189]

[0190] The precatalyst for biphenol polymerization with structure (xi) was prepared as described in WO2017 / 058858, and the entire contents of WO2017 / 058858 are incorporated herein by reference.

[0191]

[0192] The preparation of the biphenol polymerization precatalyst of structure (xii) is as described in U.S. Patent No. 8,609,794, the entire contents of which are incorporated herein by reference.

[0193]

[0194] The precatalyst for biphenol polymerization with structure (xiii) was prepared as follows.

[0195]

[0196] Synthesis of 2-methylbutane-1,4-diol: In a nitrogen-filled glove box, tetrahydrofuran (109 mL, 217.72 mmol) and tetrahydrofuran (240 mL) containing 2.0 M lithium aluminum hydride were added to a three-necked round-bottom flask equipped with a stir bar and septum. The flask was sealed and removed from the glove box to a hood. The flask was equipped with a nitrogen inlet. The solution was cooled to 0 °C (ice-water bath). A solution of dimethyl 2-methylsuccinate (9.00 g, 56.19 mmol) in tetrahydrofuran (70 mL) was slowly added to the cooled solution using a syringe. The resulting mixture was stirred at room temperature for 17 hours. The mixture was cooled to 0 °C (ice-water bath), and excess lithium aluminum hydride was quenched by the continuous addition of water (4.1 mL), 10% sodium hydroxide aqueous solution (8.4 mL), and water (12.6 mL). The mixture was then 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 oily substance with precipitate. The oily substance was dried under high vacuum to obtain 3.41 g (58.3%) of a yellow oily product with precipitate.

[0197] 1 ¹H NMR (400MHz, chloroform-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 (heptd, 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, chloroform-d) δ 67.62, 60.34, 37.00, 33.53, 16.98.

[0198]

[0199] Synthesis of 2-methylbutane-1,4-dimethylbis(4-methylbenzenesulfonate): p-Toluenesulfonyl chloride (15.06 g, 78.99 mmol) and anhydrous pyridine (26 mL) were charged into a three-necked round-bottom flask equipped with a stir bar, septum, and nitrogen inlet. The solution was cooled to 0 °C (ice-water bath). 2-Methylbutane-1,4-diol (3.41 g, 32.70 mmol) was added dropwise to a solution of anhydrous pyridine (6.5 mL) using a syringe. The resulting mixture was stirred at 0 °C (ice-water bath) for 5 hours. The reaction mixture was poured into a beaker containing ice water (65 mL) with a stirrer, resulting in a thick, pinkish oil phase at the bottom. The phases were separated. The aqueous phase was extracted with dichloromethane (3 x 65 mL portions). The combined organic phases were washed with water (25 mL), 10 wt.% sulfuric acid (25 mL), and 1 M sodium carbonate, followed by washing with water (25 mL). The organic phase was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to obtain a crude pink oily substance with a precipitate. To remove excess pyridine, the oily substance was dissolved in dichloromethane, washed with 10 wt.% sulfuric acid (25 mL), and then washed with water (25 mL). The organic phase was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to obtain a crude pink oily substance with a precipitate. The oily substance was dried under high vacuum to give 8.89 g (65.9%) of a pink oily product with a precipitate. 1 H NMR(500MHz, chloroform-d)δ7.75(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,2 H), 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).

[0200] 13 C NMR (126MHz, 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.

[0201]

[0202] Synthesis of 2,2'-((2-methylbutane-1,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene): 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, formulation disclosed in US2015 / 0291713A1), anhydrous potassium carbonate (4.02 g, 29.08 mmol), and N,N-dimethylformamide (58 mL) were charged into a three-necked round-bottom flask equipped with a stir bar, septum, condenser, and nitrogen inlet. The mixture was stirred at 100 °C for 5 hours and then cooled to room temperature. The mixture was concentrated to dryness by rotary evaporation. The residue was dissolved in a 50:50 dichloromethane:water solution (30 mL). The phases were separated. The aqueous phase was extracted with dichloromethane (3 x 30 mL portions). The combined organic phases were washed with 2N sodium hydroxide aqueous solution (115 mL), water (115 mL), and then with brine (115 mL). The organic phase was dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to provide a crude reddish-brown oil (4.12 g). The oil was dissolved in a minimal amount of hexane and purified by rapid column chromatography (ISCO, 220 g silica gel, 5%–10% dichloromethane / hexane). The fractions containing the product were combined and concentrated by rotary evaporation to give a thick yellow oil. To remove trace amounts of hexane, the oil was dissolved in dichloromethane and concentrated by rotary evaporation to give a thick yellow oil (repeated twice). The oil was dried under high vacuum to give 2.55 g (61.3%) of a thick yellow oil. 1 H NMR (400MHz, chloroform-d) δ7.30 (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,1H),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). 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 coupling was not specified.

[0203]

[0204] Synthesis of 2',2”'-((2-methylbutane-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'-diphenyl]-2-ol): 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)) was charged into a three-necked round-bottom flask equipped with a stir bar, septum, condenser, and nitrogen inlet. 2,2'-((2-methylbutane-1,3,2-dioxane-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole-9-yl (5.86 g, 8.45 mmol, formulation disclosed in US2015 / 0291713A1), 2,2'-((2-methylbutane-1,4-diyl)bis(oxy))bis(5-fluoro-1-iodo-3-methylbenzene) (2.30 g, 4.02 mmol) A solution of 1,2-dimethoxyethane (105 mL), tetrahydrofuran (36 mL), and sodium hydroxide (1.12 g, 27.98 mmol) in water (31 mL) was prepared. The mixture was purged with nitrogen for 15 minutes, and then tetra(triphenylphosphine)palladium (0) (0.36 g, 0.31 mmol) was added. The mixture was heated at 85 °C for 20 hours; a precipitate formed. The reaction was cooled to room temperature and filtered. The solid was dissolved in dichloromethane, and the solution was concentrated by rotary evaporation to give a brownish-yellow 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 was heated at 60 °C overnight and then cooled to room temperature. The reaction was concentrated by rotary evaporation to give a crude brown crystalline solid. The solid was recrystallized from acetonitrile, filtered, and treated with cold acetonitrile (2x) Wash (10 mL). Dissolve the ligand in dichloromethane and concentrate by rotary evaporation to give a light brown crystalline solid. Dry the solid under high vacuum to give 4.50 g (87.1%) of the product as a light brown crystalline solid. 1H NMR (400MHz, chloroform-d) δ8.00(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,2H),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)δ160.07,160.04,157.65,157.62,150.02,149.99,149.96,148.93,148.90,148.88,148.86,147.74,147.7 0,142.81,141.62,141.60,133.60,133.51,133.03,132.95,129.01,127.44,127.39,126.51,126.49,126.38,126.36,125.23, 125.19,121.05,121.01,119.47,117.68,117.66,117.63,117.35,117.22,117.13,116.99,116.18,116.12,115.95,115.89,106.32,79.01,71.64,57.18,57.13,38.25,35.06,33.34,32.54,32.51,31.96,31.91,31.87,31.79,31.64,30.40,16.45,16.40. Multiplicity due to fluorocarbon coupling is not specified.

[0205] The reaction was set up in a glove box under a nitrogen atmosphere. Zirconium tetrachloride (0.054 g, 0.23 mmol) and toluene (15 mL) were added to a glass jar. The slurry mixture was cooled to -25 °C in a glove box freezer. Diethyl ether containing 3.0 M methyl magnesium bromide (0.35 mL, 1.05 mmol) was added to the stirred, cold slurry mixture. The mixture was stirred vigorously for about 4 minutes. The solid dissolved in the solution and turned pale yellow. The 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. Hexane (15 mL) was then added to the mixture and filtered. The solution was concentrated under vacuum to give 0.36 g of the product as an almost 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 another 2 days. Toluene was added to the mixture in 2 mL increments to dissolve most of the solid, for a total of 16 mL of toluene. The mixture was filtered through a syringe filter and concentrated under vacuum to give 0.29 g of 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 give 0.19 g (56.6%) of a grayish-white solid. The product... 1 H-NMR showed that it was a mixture of isomers.

[0206] 1 H NMR (500MHz, benzene-d6) δ8.19(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 to the proton ratio.

[0207]

[0208] The pre-catalyst for biphenol polymerization with 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 added to a glass jar. The slurry mixture was cooled to -25 °C in a glove box freezer. Diethyl ether containing 3.0 M methyl magnesium bromide (0.36 mL, 1.080 mmol) was added to the stirred, cold slurry mixture. The mixture was vigorously stirred for about 4 minutes. The solid dissolved in the solution and turned yellow. The ligand (0.3002 g, 0.239 mmol) in solid form was added to the mixture. The resulting mixture was stirred at room temperature for 2 hours. Hexane (15 mL) was then added to the mixture and filtered. The solution was concentrated under vacuum to give 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, for a total of 8 mL of toluene. The brown turbid solution was stirred overnight. The product was filtered through a syringe filter and concentrated under vacuum to give 0.3345 g of a brown solid. To remove excess toluene, hexane (10 mL) was added to the solid, the mixture was stirred vigorously for 1 hour and placed under vacuum to give 0.2985 g (90.81%) of a brown solid.

[0209] 1 H NMR (400MHz, benzene-d6) δ8.56(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=8.8Hz,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 as,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).

[0210]

[0211] The precatalyst for biphenol polymerization with structure (xv) was prepared as follows.

[0212] The reaction was set up in a glove box under a nitrogen atmosphere. ZrCl4 (0.0563 g, 0.242 mmol) and toluene (15 mL) were added to a glass jar. The slurry mixture was cooled to -25°C in a glove box freezer. Diethyl ether containing 3.0 M methyl magnesium bromide (0.36 mL, 1.080 mmol) was added to the stirred, cold slurry mixture. The mixture was vigorously stirred for about 5 minutes. The solid dissolved in the solution and turned brown. The 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. Hexane (15 mL) was then added to the mixture and filtered. The pale brown solution was concentrated under vacuum to give 0.3548 g of a brown solid product. Hexane (10 mL) and toluene (2.5 mL) were added to the solid. The gray turbid solution was filtered and concentrated under high vacuum to give 0.1860 g (56.53%) of a white solid product.

[0213] 1 H NMR (400MHz, benzene-d6) δ8.53(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,4 H),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).

[0214]

[0215] The comparative polymerization catalysts (except for the comparative polymerization catalysts prepared from the polymerization precatalyst of formula (I)) are prepared as follows.

[0216] The comparative polymerization precatalyst with structure (xxi) can be prepared as described in U.S. Patent Application No. 2018 / 0298128(A1), the entire contents of which are incorporated herein by reference.

[0217]

[0218] In various embodiments, biphenol polymerization catalysts prepared from precatalysts of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv) and / or (xv) can be used to prepare polymers.

[0219] Example 1 (EX1): The activated and supported biphenol polymerization catalyst of Formula I was prepared as follows.

[0220] General Procedure for Catalyst Preparation – Supporting the Reaction on SMAO: All work was performed in a nitrogen-purge chamber on the Core Module 3 (CM3) high-throughput unit. Before starting the experiment, a pre-catalyst stock solution was prepared in toluene to the desired concentration. The required amount of SMAO was manually weighed into each reaction vial to achieve 45 μmol catalyst / 1 g SMAO (approximately 1:108 equivalence ratio) and added along with a tumbling stirrer. Toluene was dispensed via CM3, followed by the required amount of pre-catalyst stock solution. Due to the limited volume of available solution, some pre-catalyst stock solutions were delivered by hand. After adding all reaction components, the vials were capped, stirred to 300 rpm, and heated to 50 °C. After 30 minutes, the vials were cooled to room temperature, the caps removed, and the reaction plate placed in the CM3 vortex platform position. The reaction vials were vortexed at 800 rpm for 3 minutes to form a homogeneous slurry. The required amount of each supported catalyst slurry was then atomized into 8 mL vials and treated with Isopar E TM (Dilution with isoparaffin solvent, including a mixture of C8 saturated hydrocarbons). When multiple subsamples are required, a new PDT tip is used for each subsequent sub-sample conversion step. Sub-sample the reaction to the desired concentration in the PPR.

[0221] Example 2 (EX2) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 2 was used, as indicated in Table 1.

[0222] Example 3 (EX3) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 3 was used, as indicated in Table 1.

[0223] Example 4 (EX4) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 4 was used, as indicated in Table 1.

[0224] Example 5 (EX5) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 5 was used, as indicated in Table 1.

[0225] Example 6 (EX6) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 6 was used, as indicated in Table 1.

[0226] Example 7 (EX7) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 7 was used, as indicated in Table 1.

[0227] Example 8 (EX8) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 8 was used, as indicated in Table 1.

[0228] Example 9 (EX9) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 9 was used, as indicated in Table 1.

[0229] Example 10 (EX10) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 10 was used, as indicated in Table 1.

[0230] Example 11 (EX11) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 11 was used, as indicated in Table 1.

[0231] Example 12 (EX12) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 12 was used, as indicated in Table 1.

[0232] Example 13 (EX13) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 13 was used, as indicated in Table 1.

[0233] Example 14 (EX14) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 14 was used, as indicated in Table 1.

[0234] Example 15 (EX15) was prepared in the same manner as Example 20, except that the activated and supported biphenol polymerization catalyst of Example 15 was prepared under the conditions indicated in Table 1.

[0235] Example 16 (EX16) was prepared in the same manner as Example 1, except that the activated and supported biphenol polymerization catalyst of Example 16 was used, as indicated in Table 1.

[0236] Comparative Example 1 (CE1) was prepared in the same manner as in Example 1, except that the catalyst of Comparative Example 1 was used, as indicated in Table 1.

[0237] The following describes the copolymerization of ethylene / 1-hexene using individual catalysts from EX1 to EX16 and CE1 in the slurry phase.

[0238] General parallel pressure reactor (PPR) procedure for slurry phase polymerization: All PPR solutions are prepared under nitrogen in an inert atmosphere glove box. (Isopar E) TM Ethylene and hydrogen were purified using two columns: the first column contained A2 alumina, and the second column contained Q5 reactants. On the workday prior to the actual PPR operation, 48 PPR-A reactor cells were prepared as follows: tare glass tubing was manually inserted into the reactor orifices; stirrer blades were 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 then cooled to 50°C. On the day of the experiment, the reactor was purged twice with ethylene and completely vented to purge the tubing. The reactor was then heated to 50°C, and the stirrer was started at 400 rpm. A robotic needle was used with an Isopar-E... TM The reactor is filled to the appropriate solvent level to obtain a final reaction volume of 5 mL. Solvent injection for modules 1-3 is performed using the left robotic arm, and solvent injection for modules 4-6 is performed using the right robotic arm, with both arms operating simultaneously. After solvent injection, the reactor is heated to the final desired temperature, and stirring is increased to the setpoint programmed in the Library Studio design. When the reactor reaches the temperature setpoint, which takes approximately 10-30 minutes depending on the desired temperature, the pools are pressurized to the desired setpoint with pure ethylene or a mixture of ethylene and hydrogen from the gas accumulator, and the solvent is saturated (as observed by gas absorption). If an ethylene-hydrogen mixture is used, the gas feed line is switched from the ethylene-hydrogen mixture to pure ethylene for the remainder of the run once the solvent is saturated in all pools. The robotic synthesis program is then initiated, thereby first injecting the comonomer solution (1-hexene), followed by the scavenger solution (SMAO), and finally Isopar-E. TM The biphenol polymerization catalyst solution was used. Injections to modules 1-3 were performed using the left robotic arm, and injections to modules 4-6 were performed using the right robotic arm; both arms operated simultaneously. All three injections to a given cell were completed before the robot began injecting the next cell in the sequence. Each reagent addition was accompanied by 500 μl of Isopar-E. TM Solvents are used to ensure complete injection of the reagent. After each reagent addition, Isopar-E is applied to both the inside and outside of the needle. TMWash needles. Start the reaction timer while injecting the biphenol polymerization catalyst into each individual cell. The polymerization reaction proceeds for 60-180 minutes or until the set ethylene absorption of 60-180 psi, whichever occurs first, and is then quenched by adding 10% (v / v) CO2 in argon at 40 psi overpressure. Data collection continues for 5 minutes after quenching in each cell. Cool the reactor to 50°C, vent, and remove the PPR tubing from the module block. Remove the PPR library from the drying oven and then remove volatiles using a Genevac rotary evaporator. Once the library vial is reweighed to obtain the yield, submit the library for analysis.

[0239] The operation is performed under condition B or K, as detailed in Table 1 below. The results of EX1-16 and CE1 are shown in Tables 1 and 2.

[0240] In various embodiments, biphenol polymerization catalysts prepared from precatalysts 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 system s of this document to prepare high molecular weight polyethylene components in multimodal (e.g., bimodal) polyethylene compositions.

[0241] Mn (number-average molecular weight), Mw (weight-average molecular weight), and z-average molecular weight (Mz) were determined by gel permeation chromatography (GPC), as known in the art.

[0242] The content of comonomers incorporated into the polymer (i.e., 1-hexene) (wt%) was determined by rapid FT-IR spectroscopy of the dissolved polymer in GPC measurements.

[0243] Yield (kg polymer / kg catalyst) is defined as the ratio of the amount of polymer prepared to the amount of catalyst and activator added to the reactor.

[0244] The melting temperature (i.e., Tm) can be determined by differential scanning calorimetry according to ASTM D 3418-08. For example, a 10 mg sample is tested using a scan rate of 10 °C / min and a second heating cycle.

[0245] The following conditions (B-) apply: Temperature = 100°C; Ethylene = 100 psi; H2 / C2 = 0.0017; C6 / C2 = 0.4.

[0246] K-conditions are as follows: temperature = 100℃; ethylene = 100psi; H2 / C2 = 0.0068; C6 / C2 = 0.4.

[0247] Table 1

[0248]

[0249]

[0250] Table 2

[0251] Precatalyst structure Mn(da) Mw(da) Mw / Mn Tm (°C) EX1 (i) 83,500 454,500 5.5 131.5 EX2 (ii) 42,800 149,500 3.5 133.3 EX3 (iii) 40,300 289,500 7.5 126.8 EX4 (iv) 36,700 222,500 6.4 124.8 EX5 (v) 108,800 488,800 5.0 127.3 EX6 (vi) 42,400 263,900 6.3 129.3 EX7 (vii) 92,000 287,300 6.0 131.0 EX8 (viii) 21,200 414,400 20.8 130.0 EX9 (ix) 41,000 199,000 4.8 ** EX10 (x) 102,600 360,100 3.6 113.1 EX11 (xi) 72,500 275,500 3.8 120.0 EX12 (xii) 28,300 184,900 6.5 124.5 EX13 (xiii) 27,500 234,000 14.1 ** EX14 (xiv) 111,300 457,400 4.3 133.0 EX15 (xiv) 58,500 331,400 5.8 134.0 EX16 (xv) 72,300 215,900 3.0 101.8 CE1 (xxi) 107,095 788,704 7.36 131.18

[0252] As detailed in Tables 1 and 2, EX1 to EX16 provide polymers prepared via slurry-phase polymerization using supported biphenol polymerization catalysts, wherein the supported biphenol polymerization catalysts are prepared from biphenol polymerization precatalysts of Formula I. Notably, each of EX1 to EX16 provides polymers having molecular weights (e.g., molecular weights in the range of about 150,000 to about 800,000 Daltons under B-conditions and / or less than about 500,000 Daltons under K-conditions), which may be desirable for certain applications. For example, each of EX1 to EX16 provides polymers prepared under conditions equally suitable for use with metallocene olefin polymerization catalysts. That is, each of the supported biphenol polymerization catalysts of EX1 to EX16 can be used with a metallocene olefin polymerization catalyst to prepare a polymerization catalyst system that can be used in a single slurry-phase polymerization reactor to prepare multi-peak (e.g., bimodal) polymers.

[0253] The supported biphenol polymerization catalyst of Formula I can be used to prepare polymers via a slurry-phase polymerization process, which provides improved comonomer incorporation compared to polymers prepared via a solution-phase polymerization process using a biphenol polymerization catalyst of Formula I (e.g., the same supported biphenol polymerization catalyst of Formula I). ​​The supported biphenol polymerization catalyst of Formula I can also be used to prepare polymers via a slurry-phase polymerization process, which provides improved comonomer incorporation compared to polymers prepared by a comparative catalyst under similar slurry-phase conditions.

Claims

1. Use of a supported biphenol polymerization catalyst for preparing a polymer via a slurry-phase polymerization process, wherein the polymer is a polyolefin polymer, and wherein the supported biphenol polymerization catalyst is prepared from a biphenol polymerization precatalyst selected from the group consisting of structures (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv), and (xv). (i)； (ii); (iii); (iv); (v)； (vi); (vii); (viii); (ix); (x)； (xi); (xii); (xiii); (xiv); and (xv).

2. A polymerization catalyst system for preparing a polymer via a slurry polymerization process, wherein the polymer is a polyolefin polymer, the polymerization catalyst system comprising: Metallocene olefin polymerization catalysts; as well as The supported biphenol polymerization catalyst prepared from the biphenol polymerization precatalyst according to claim 1.

3. A slurry-phase polymerization method for preparing a polymer, wherein the polymer is a polyolefin polymer, the method comprising: The polymer is prepared by polymerizing olefin monomers in a slurry polymerization reactor in the presence of the polymerization catalyst system according to claim 2.

4. The polymerization catalyst system according to claim 2, wherein the metallocene olefin polymerization catalyst is selected from: (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2, (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2, (methylcyclopentadienyl)(1,3-dimethyl-tetrahydroindenyl)MX2, (cyclopentadienyl)(1,3-dimethyl-tetrahydroindenyl)MX2, (cyclopentadienyl)(4,7-dimethylindenyl)MX2, (cyclopentadienyl)(1,5-dimethylindenyl)MX2, (cyclopentadienyl)(1,4-dimethylindenyl)MX2, Me2Si(indene)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 Their mixture, Where M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3 and C1 to C5 alkyl or alkenyl.

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